A near-zero carbon emission direct coal fuel cell stack power generation device and power generation method

Abstract

The present invention provides a near-zero carbon emission direct coal fuel cell stack power generation device and power generation method. The device includes a ceramic shell, a first ceramic plate, a second ceramic plate, and a direct coal fuel cell stack reaction chamber and a carbon dioxide catalytic-mineralization conversion reaction chamber separated by the ceramic shell, the first ceramic plate and the second ceramic plate; and also includes a bifunctional ceramic membrane embedded in the first ceramic plate. The present invention separates the direct coal fuel cell stack reaction chamber and the carbon dioxide catalytic-mineralization conversion reaction chamber, and couples them through a bifunctional ceramic membrane, so that the carbon dioxide gas generated during coal fuel cell power generation permeates through the bifunctional ceramic membrane for in-situ conversion, thereby achieving near-zero carbon emission of coal power generation; the bifunctional ceramic membrane is embedded in the center of the plate, and the tubular fuel cells are distributed around it, which is feasible for construction and has a compact structure, avoiding the gas pressure flow loss caused by CO2 pipeline transportation and the thermodynamic loss caused by cooling.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to a near-zero carbon emission direct coal fuel cell stack power generation device and a power generation method. Background Art

[0002] At present, direct coal fuel cell stacks, as a highly efficient coal power generation device, release a large amount of CO2 in the process of using electrochemical oxidation of coal to generate electricity. However, the existing technology does not effectively treat the generated CO2 gas. As the main greenhouse gas, CO2 directly discharged into the atmosphere will aggravate global warming and cause damage to the environment. Therefore, how to effectively utilize the CO2 generated by electrochemical oxidation of coal for power generation, realize the coupling of CO2 in-situ conversion and direct coal fuel cell stacks, and realize the continuous delivery of coal fuel is still a blank in this field.

[0003] Therefore, the prior art needs to be improved. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a near-zero carbon emission direct coal fuel cell stack power generation device and power generation method, aiming to solve the problem in the prior art that a large amount of CO2 released by the direct coal fuel cell stack during the electrochemical oxidation discharge of coal cannot be effectively treated.

[0005] The technical solution of the present invention is as follows:

[0006] In the first aspect, the present invention provides a near-zero carbon emission direct coal fuel cell stack power generation device, which includes: a hollow ceramic shell; a first ceramic plate and a second ceramic plate arranged in the ceramic shell; a tubular fuel cell group, a coal fuel feed pipe and a coal fuel exhaust pipe passing through the first ceramic plate and the second ceramic plate; a catalytic-mineralization conversion reactant feed pipe and a chemical product collection pipe passing through the second ceramic plate; and a dual-function ceramic membrane embedded in the first ceramic plate.

[0007] The near-zero carbon emission direct coal fuel cell stack power generation device further includes an air inlet pipe and an air outlet pipe arranged on the top of the tubular fuel cell group.

[0008] The near-zero carbon emission direct coal fuel cell stack power generation device, wherein the first ceramic plate and the second ceramic plate separate the ceramic shell to form a direct coal fuel cell stack reaction chamber and a carbon dioxide catalytic-mineralization conversion reaction chamber.

[0009] The near-zero carbon emission direct coal fuel cell stack power generation device, wherein the direct coal fuel cell stack reaction chamber is provided with coal fuel.

[0010] The near-zero carbon emission direct coal fuel cell stack power generation device, wherein the tubular fuel cell group includes at least one tubular fuel cell, and the tubular fuel cell is composed of an anode layer inside the tube and a cathode layer outside the tube, and an electrolyte arranged between the anode layer and the cathode layer.

[0011] The near-zero carbon emission direct coal fuel cell stack power generation device, wherein the first ceramic plate and the second ceramic plate are arranged in parallel, the first ceramic plate includes at least four first holes, and the second ceramic plate includes at least five second holes.

[0012] In a second aspect, the present invention further provides a method for generating electricity using a near-zero carbon emission direct coal fuel cell stack power generation device as described above, comprising the steps of:

[0013] feeding coal fuel into a direct coal fuel cell stack reaction chamber through a coal fuel feed pipe;

[0014] Air is introduced from the air inlet pipe to generate an electrochemical reaction with the coal fuel to generate electricity and produce carbon dioxide gas;

[0015] The generated carbon dioxide gas permeates through the dual-function ceramic membrane and reaches the carbon dioxide catalytic-mineralization conversion reaction chamber;

[0016] The reactants are introduced from the catalytic-mineralization conversion reactant feed pipe to chemically react with the carbon dioxide gas in the carbon dioxide catalytic-mineralization conversion reaction chamber to generate chemical products.

[0017] The power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device, wherein the specific reaction process of the air introduced from the air inlet pipe and the coal fuel undergoing an electrochemical reaction to generate electricity and produce carbon dioxide gas includes:

[0018] The oxygen contained in the air obtains electrons on the cathode layer of the tubular fuel cell to generate oxygen ions; the oxygen ions pass through the electrolyte layer to reach the anode layer in the tubular fuel cell, and undergo an electrochemical reaction with the coal fuel at the anode layer to generate carbon dioxide, and release electrons to the external circuit, forming a complete current loop to generate electricity.

[0019] The power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device, wherein the operating temperature of the direct coal fuel cell stack reaction chamber is 750-800°C; the operating temperature of the direct coal fuel cell stack reaction chamber is 50°C higher than the operating temperature of the carbon dioxide catalytic-mineralization conversion reaction chamber.

[0020] In the power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device, the reactants introduced from the catalytic-mineralization conversion reactant feed pipe include one or more of gas and serpentine.

[0021] Beneficial effects: The present invention provides a near-zero carbon emission direct coal fuel cell stack power generation device and power generation method. The device comprises: a ceramic shell with a hollow interior; a first ceramic plate and a second ceramic plate arranged in sequence in the ceramic shell; a direct coal fuel cell stack reaction chamber and a carbon dioxide catalytic-mineralization conversion reaction chamber separated by the ceramic shell, the first ceramic plate and the second ceramic plate; a tubular fuel cell group, a coal fuel feed pipe and a coal fuel exhaust pipe penetrating the first ceramic plate and the second ceramic plate; a bifunctional ceramic membrane embedded in the first ceramic plate; a catalytic-mineralization conversion reactant feed pipe and a chemical product collection pipe penetrating the second ceramic plate; an air inlet pipe and an outlet pipe arranged at the top of the tubular fuel cell group; and coal fuel arranged in the direct coal fuel cell stack reaction chamber. When the device is working, the coal fuel in the direct coal fuel cell stack reaction chamber reacts electrochemically with the air introduced to generate electricity and generate carbon dioxide gas; thereafter, the generated carbon dioxide gas permeates through the bifunctional ceramic membrane, reaches the carbon dioxide catalytic-mineralization conversion reaction chamber, and reacts chemically with the reactant introduced by the catalytic-mineralization conversion reactant feed pipe to generate high value-added products. The present invention achieves in-situ conversion of carbon dioxide by separately setting up the direct coal fuel cell stack reaction chamber and the carbon dioxide catalytic-mineralization conversion reaction chamber and coupling them through a bifunctional ceramic membrane, which effectively solves the problem that the carbon dioxide gas generated by the direct coal fuel cell stack power generation cannot be effectively treated, and can achieve near-zero carbon emissions from coal power generation; the bifunctional ceramic membrane is embedded in the center of the plate, and the tubular fuel cells are distributed around it, which is feasible for device construction and has a compact structure, avoiding the gas pressure flow loss caused by pipeline transportation of CO2 and the thermodynamic loss caused by cooling. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of a near-zero carbon emission direct coal fuel cell stack power generation device in an embodiment of the present invention.

[0023] Figure 2 This is a schematic diagram of a first ceramic plate of a near-zero carbon emission direct coal fuel cell stack power generation device in an embodiment of the present invention.

[0024] Figure 3 This is a schematic diagram of a second ceramic plate of a near-zero carbon emission direct coal fuel cell stack power generation device in an embodiment of the present invention.

[0025] Figure 4 The present invention is a flow chart of an optimal power generation method of a near-zero carbon emission direct coal fuel cell stack power generation device in an embodiment of the present invention.

[0026] Among them: 1-ceramic shell; 2-first ceramic plate; 3-second ceramic plate; 4-direct coal fuel cell stack reaction chamber; 5-carbon dioxide catalytic-mineralization conversion reaction chamber; 6-tubular fuel cell; 7-coal fuel feed pipe; 8-coal fuel exhaust pipe; 9-catalytic-mineralization conversion reactant feed pipe; 10-chemical product collection pipe; 11-dual-function ceramic membrane; 12-air inlet pipe; 13-air outlet pipe; 14-high-temperature sealant. Holes 2-1, 2-2, 2-3, and 2-4 are located on the first ceramic plate 2; holes 3-1, 3-2, 3-3, 3-4, and 3-5 are located on the second ceramic plate 3. DETAILED DESCRIPTION

[0027] The present invention provides a near-zero carbon emission direct coal fuel cell stack power generation device and power generation method. In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0028] The embodiment of the present invention discloses a near-zero carbon emission direct coal fuel cell stack power generation device, such as Figure 1-3 As shown, it includes: a hollow ceramic shell 1; a first ceramic plate 2 and a second ceramic plate 3 arranged in the ceramic shell 1 in sequence; the first ceramic plate 2 and the second ceramic plate 3 divide the interior of the ceramic shell 1 into a direct coal fuel cell stack reaction chamber 4 and a carbon dioxide catalytic-mineralization conversion reaction chamber 5. At least one tubular fuel cell 6, a coal fuel feed pipe 7, and a coal fuel exhaust pipe 8 are arranged in the direct coal fuel cell stack reaction chamber 4; at least one catalytic-mineralization conversion reactant feed pipe 9 and a chemical product collection pipe 10 are arranged in the carbon dioxide catalytic-mineralization conversion reaction chamber 5. At least one dual-function ceramic membrane 11 is arranged on the first ceramic plate 2. The first ceramic plate 2 is also provided with at least four holes 2-1, 2-2, 2-3, 2-4; the second ceramic plate 3 is provided with at least five holes 3-1, 3-2, 3-3, 3-4, 3-5; the tubular fuel cell 6, coal fuel feed pipe 7 and coal fuel exhaust pipe 8 respectively penetrate the holes 2-1, 2-2 and 2-3 of the first ceramic plate 2, and the holes 3-1, 3-2 and 3-3 of the second ceramic plate 3; the catalytic-mineralization conversion reactant feed pipe 9 and the chemical product collection pipe 10 respectively penetrate the holes 3-4 and 3-5 of the second ceramic plate 3; the dual-function ceramic membrane 11 is installed in the hole 2-4 of the first ceramic plate 2. The tubular fuel cell stack is also provided with an air inlet pipe 12 and an air outlet pipe 13.

[0029] During operation, the power generation device introduces air through the air inlet pipe 12 and generates electrons in the tube of the tubular fuel cell 6 to generate oxygen. 2- , O2- The electrochemical reaction occurs with the coal fuel outside the tubular fuel cell 6, and carbon dioxide is generated while releasing electrons outward. The generated carbon dioxide gas permeates through the bifunctional ceramic membrane 11 and reaches the carbon dioxide catalytic-mineralization conversion reaction chamber 5; the reactant introduced from the catalytic-mineralization conversion reactant feed pipe 9 and the carbon dioxide gas undergo a chemical reaction in the carbon dioxide catalytic-mineralization conversion reaction chamber 5.

[0030] In some embodiments, the direct coal fuel cell stack reaction chamber 4 is provided with coal fuel. The coal fuel may use pyrolysis treated coal coke, which can avoid the poisoning effect of a small amount of sulfur-containing gas contained in the gas after the raw coal is gasified on the anode catalyst. For example, when the anode catalyst is Ni particles, the sulfur-containing gas can cause the catalyst Ni particles to be sulfurized to form NiS, Ni3S x The above situation can be avoided by using pyrolysis treated coal char.

[0031] In some embodiments, the near-zero carbon emission direct coal fuel cell stack power generation device adopts a tubular fuel cell group, which includes at least one tubular fuel cell, and the tubular fuel cell is composed of an anode layer inside the tube and a cathode layer outside the tube, and an electrolyte arranged between the anode layer and the cathode layer. The anode layer is a composite porous anode of Ni and electrolyte powder used in traditional solid oxide fuel cells; the electrolyte is a commonly used cationic electrolyte, such as 8mol% Y2O3-ZrO2, Ce 0.8 Sm 0.2 O 1.9 、Ce 0.8 G 0.2 O 1.9 The cathode layer is mainly composed of the above electrolyte material and the cathode material commonly used in solid oxide batteries, such as (La 0.80 Sr 0.20 ) 0.95 MnO3, (La 0.60 Sr 0.40 ) 0.95 Co 0.20 Fe 0.80 O3 and other components of the composite porous electrode.

[0032] In some embodiments, the first ceramic plate 2 and the second ceramic plate 3 divide the interior of the ceramic shell 1 into a direct coal fuel cell stack reaction chamber 4 and a carbon dioxide catalytic-mineralization conversion reaction chamber 5. The present invention sets the direct coal fuel cell stack reaction chamber and the carbon dioxide catalytic-mineralization conversion reaction chamber in the same shell, the whole device has a compact structure, the pipeline loss of gas transmission is small, and the heat generated by the electrochemical reaction of the battery can maintain the temperature of the battery stack through the shell heat conduction, thermal radiation, etc., without external heating, which can improve the power generation efficiency of the device.

[0033] In some embodiments, the power generation device is further provided with a coal fuel feed pipe 7 connected to the direct coal fuel cell stack reaction chamber 4. The coal fuel feed pipe 7 is used to add coal powder to the direct coal fuel cell stack reaction chamber 4, so as to realize the circulation and continuous supply of coal. In the following specific embodiments, the addition rate and amount of coal powder in the coal fuel feed pipe 7 can be controlled to control the power generation of the stack: when the demand for electricity is small, the stack will operate at a lower current. At this time, the CO generation rate can be controlled by reducing the rate or amount of coal powder addition to reduce the electrochemical reaction rate and reduce the output power; conversely, when the demand for electricity is large, the amount or rate of coal powder addition can be increased.

[0034] In some embodiments, the power generation device is further provided with a coal fuel exhaust pipe 8 connected to the direct coal fuel cell stack reaction chamber 4. The inert coal particles in the direct coal fuel cell stack reaction chamber 4 settle at the bottom thereof, and after a period of accumulation, the coal fuel exhaust pipe 5 can be opened for exhaust operation, thereby ensuring a rapid and continuous supply of active coal fuel.

[0035] In some embodiments, the first ceramic plate 2 and the first ceramic plate 3 are arranged in parallel, and the first ceramic plate 2 is provided with at least four first holes 2-1, 2-2, 2-3, and 2-4; the second ceramic plate 3 is provided with at least five second holes 3-1, 3-2, 3-3, 3-4, and 3-5; the tubular fuel cell 6, the coal fuel feed pipe 7, and the coal fuel exhaust pipe 8 respectively penetrate the first holes 2-1, 2-2, and 2-3 of the first ceramic plate 2, and the second holes 3-1, 3-2, and 3-3 of the second ceramic plate 3; the catalytic-mineralization conversion reactant feed pipe 9 and the chemical product collection pipe 10 respectively penetrate the second holes 3-4 and 3-5 of the second ceramic plate 3; the dual-function ceramic membrane 11 is installed in the first hole 2-4 of the first ceramic plate 2. In some specific embodiments, the hole 2-1 on the first ceramic plate 2 and the hole 3-1 on the second ceramic plate 3 are symmetrically arranged. If the hole 2-1 is arranged at the center of the first ceramic plate 2, the hole 3-1 is also arranged at the center of the second ceramic plate 3. The tubular fuel cell 6 is installed on the symmetrical holes of the first ceramic plate 2 and the second ceramic plate 3, so that the tubular fuel cell 6 is arranged perpendicular to the direct coal fuel cell stack reaction chamber 4, which can reduce internal stress and improve battery life. Similarly, the hole 2-2 on the first ceramic plate 2 and the hole 3-2 on the second ceramic plate 3 are symmetrically arranged, and the coal fuel feed pipe 7 is installed on the symmetrical holes of the first ceramic plate 2 and the second ceramic plate 3; the hole 2-3 on the first ceramic plate 2 and the hole 3-3 on the second ceramic plate 3 are symmetrically arranged, and the coal fuel exhaust pipe 8 is installed on the symmetrical holes of the first ceramic plate 2 and the second ceramic plate 3.

[0036] In some embodiments, the size of the hole 2-1 and the hole 3-1 matches the size of the two ends of the tubular fuel cell 6 and the size of the cross-sectional area of ​​the two ends. If the cross-sections of the two ends of the tubular fuel cell 6 are rectangular, the hole 2-1 and the hole 3-1 are also rectangular. If the cross-sections of the two ends of the tubular battery 6 are circular, the hole 2-1 and the hole 3-1 are also circular. Moreover, the area of ​​the hole 2-1 and the hole 3-1 is set slightly larger than the area of ​​the cross-sections of the two ends of the tubular fuel cell 6, so that the two ends of the tubular fuel cell 6 are just inserted into the hole 2-1 and the hole 3-1. Furthermore, in order to make the CO2 generated in the direct coal fuel cell stack reaction chamber 4 diffuse only through the dual-function ceramic membrane 11 to the carbon dioxide catalytic-mineralization conversion reaction chamber 5, and not flow into other places to cause carbon dioxide emissions, this embodiment is sealed and connected by a high-temperature sealant 14 at the connection between the tubular fuel cell 6 and the hole 2-1 and the hole 3-1. And the working temperature of the high-temperature sealant 14 must be higher than the working temperature of the tubular fuel cell 6. Specifically, the high temperature sealant 14 is a high temperature glass sealant that can withstand 1250°C.

[0037] In some embodiments, the tubular fuel cell group may include a plurality of tubular fuel cells. Accordingly, a corresponding number of first holes and second holes are set on the first ceramic plate and the second ceramic plate, and the first holes and the second holes are symmetrically arranged, and a plurality of tubular fuel cells are passed through the plurality of first holes and second holes. Similarly, the size of the first hole and the second hole matches the size of the two ends of the tubular fuel cell and the size of the cross-sectional area at the two ends, and the area is set slightly larger than the area of ​​the cross-sectional area at the two ends of the tubular fuel cell. The connection between the tubular fuel cell and the corresponding hole is sealed by a high-temperature sealant.

[0038] In some embodiments, at least one catalytic-mineralized conversion reactant feed pipe 9 and a chemical product collection pipe 10 are provided in the carbon dioxide catalytic-mineralized conversion reaction chamber 5. At least one bifunctional ceramic membrane 11 is provided on the first ceramic plate 2. The bifunctional ceramic membrane has carbon dioxide permeation and catalytic effects. The carbon dioxide produced by the direct coal fuel cell stack reaction penetrates into the carbon dioxide catalytic-mineralized conversion reaction chamber through the bifunctional ceramic membrane, and reacts with the reactants introduced by the catalytic-mineralized conversion reactant feed pipe to generate high value-added products. Afterwards, the generated high value-added products can be collected through the chemical product collection pipe. The present invention can achieve in-situ conversion of the generated carbon dioxide by separately arranging the direct coal fuel cell stack reaction chamber and the carbon dioxide catalytic-mineralized conversion reaction chamber, and arranging a bifunctional ceramic membrane with permeation and carbon dioxide catalytic-mineralized conversion effects between the two.

[0039] In some embodiments, the dual-function ceramic membrane includes a permeable membrane and a catalyst. After the carbon dioxide gas passes through the permeable membrane, it reacts with the reactants introduced through the catalytic-mineralization conversion reactant feed pipe under the action of the catalyst.

[0040] In some embodiments, the bifunctional ceramic membrane has a porous oxygen ion conductor electrolyte and a catalyst composite as a matrix, and the matrix is ​​impregnated with an alkali metal carbonate.

[0041] In some embodiments, the catalyst of the bifunctional ceramic membrane is La 0.7 Sr 0.3 Fe 0.8 Ni 0.2 O 3-δ (LSFN), but not limited thereto, and may also be any other suitable perovskite catalyst, such as La 0.7 Sr 0.3 Co 0.8 Fe 0.2 O 3-δ (LSCF), La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3-δ .

[0042] In some embodiments, the power generation device further includes an air inlet pipe 12 and an air outlet pipe 13. The air introduced from the air inlet pipe 12 obtains electrons on the cathode of the tubular fuel cell 6 to generate O 2- , O 2- Driven by the concentration difference and potential difference, the oxygen passes through the electrolyte layer to reach the anode layer in the tubular fuel cell 6, where it undergoes an electrochemical reaction with the coal material, and releases electrons to the external circuit to form a complete current loop, thereby generating electricity. The oxygen-depleted air is directly discharged to the outside through the air outlet pipe 13, thereby increasing the air circulation in the tubular fuel cell 6, which is conducive to accelerating the electrochemical reaction of the tubular fuel cell 6.

[0043] The embodiment of the present invention separates the reaction chamber of the direct coal fuel cell stack and the carbon dioxide catalytic-mineralization conversion reaction chamber, and sets a bifunctional ceramic membrane with carbon dioxide catalytic-mineralization conversion function between the two, so that the carbon dioxide generated by the direct coal fuel cell stack reaction can penetrate into the carbon dioxide catalytic-mineralization conversion reaction chamber and complete the in-situ conversion, and the high value-added products generated in the carbon dioxide catalytic-mineralization conversion reaction chamber can be collected through the chemical product collection pipe. In addition, compared with a single primary cell (such as a direct coal fuel cell) that cannot add fuel, the present invention realizes the coupling of the bifunctional ceramic membrane with the direct coal fuel cell stack and achieves the continuous delivery of coal fuel.

[0044] The present invention also discloses a method for generating electricity using a near-zero carbon emission direct coal fuel cell stack power generation device. Figure 4 As shown, the steps include:

[0045] S100, feeding coal fuel into a direct coal fuel cell stack reaction chamber through a coal fuel feed pipe;

[0046] S200, introducing air from the air inlet pipe to generate an electrochemical reaction with the coal fuel to generate electricity and produce carbon dioxide gas;

[0047] S300, the generated carbon dioxide gas permeates through the dual-function ceramic membrane and reaches the carbon dioxide catalytic-mineralization conversion reaction chamber;

[0048] S400, introducing reactants from the catalytic-mineralization conversion reactant feed pipe to chemically react with the carbon dioxide gas in the carbon dioxide catalytic-mineralization conversion reaction chamber to generate chemical products.

[0049] In some embodiments, the specific reaction process of step S200 includes:

[0050] The oxygen contained in the air obtains electrons on the cathode layer of the tubular fuel cell to generate oxygen ions; the oxygen ions pass through the electrolyte layer to reach the anode layer in the tubular fuel cell, and undergo an electrochemical reaction with the coal fuel at the anode layer to generate carbon dioxide, and release electrons to the external circuit, forming a complete current loop to generate electricity.

[0051] In some embodiments, the specific reaction formula is:

[0052] Anode reaction: C+2O 2- =CO2+4e - ;

[0053] Cathode zone reaction: 2O2+4e - =2O 2- .

[0054] In some embodiments, the operating temperature of the direct coal fuel cell stack reaction chamber is 750-800°C. The operating temperature of the tubular fuel cell is 750-800°C to avoid affecting the long-term stability of the entire device due to excessive temperature, so that the entire device is in a self-sustaining state.

[0055] In some embodiments, the operating temperature of the direct coal fuel cell stack reaction chamber is 50°C higher than the operating temperature of the carbon dioxide catalytic-mineralization conversion reaction chamber, so that the carbon dioxide generation rate of the direct coal fuel cell stack reaction chamber matches the carbon dioxide consumption rate of the carbon dioxide catalytic-mineralization conversion reaction chamber. Moreover, the heat conducted from the direct coal fuel cell stack reaction chamber to the carbon dioxide catalytic-mineralization conversion reaction chamber can maintain the operating temperature of the carbon dioxide catalytic-mineralization conversion reaction chamber at 700-750°C.

[0056] In some embodiments, in step S400, the reactants introduced from the catalytic-mineralization conversion reactant feed pipe include one or more of gas and serpentine, but are not limited thereto. The purpose of introducing the reactants is to allow the reactants to react with the carbon dioxide gas generated when the power generation equipment generates electricity to generate high value-added products. Taking the introduction of gas as an example, its main component is methane (CH4). After methane reaches the bifunctional ceramic membrane, it is directly reformed with the permeated carbon dioxide gas on the bifunctional ceramic membrane, and the carbon dioxide gas is converted in situ into a synthesis gas composed of carbon monoxide and hydrogen. The specific reaction formula is: CO2+CH4=CO+2H2.

[0057] In summary, the present invention provides a near-zero carbon emission direct coal fuel cell stack power generation device and power generation method. The device includes: a ceramic shell with a hollow interior; a first ceramic plate and a second ceramic plate arranged in sequence in the ceramic shell; a direct coal fuel cell stack reaction chamber and a carbon dioxide catalytic-mineralization conversion reaction chamber separated by the ceramic shell, the first ceramic plate and the second ceramic plate; a tubular fuel cell group, a coal fuel feed pipe and a coal fuel exhaust pipe that penetrate the first ceramic plate and the second ceramic plate; a bifunctional ceramic membrane embedded in the first ceramic plate; a catalytic-mineralization conversion reactant feed pipe and a chemical product collection pipe that penetrate the second ceramic plate; an air inlet pipe and an outlet pipe arranged at the top of the tubular fuel cell group; and coal fuel arranged in the direct coal fuel cell stack reaction chamber. When the device is working, the coal fuel in the direct coal fuel cell stack reaction chamber reacts electrochemically with the air introduced to generate electricity and generate carbon dioxide gas; thereafter, the generated carbon dioxide gas permeates through the bifunctional ceramic membrane, reaches the carbon dioxide catalytic-mineralization conversion reaction chamber, and reacts chemically with the reactant introduced by the catalytic-mineralization conversion reactant feed pipe to generate high value-added products. The present invention achieves in-situ conversion of carbon dioxide by separately setting up the direct coal fuel cell stack reaction chamber and the carbon dioxide catalytic-mineralization conversion reaction chamber and coupling them through a bifunctional ceramic membrane, which effectively solves the problem that the carbon dioxide gas generated by the direct coal fuel cell stack power generation cannot be effectively treated, and can achieve near-zero carbon emissions from coal power generation; the bifunctional ceramic membrane is embedded in the center of the plate, and the tubular fuel cells are distributed around it, which is feasible for device construction and has a compact structure, avoiding the gas pressure flow loss caused by pipeline transportation of CO2 and the thermodynamic loss caused by cooling.

[0058] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A near-zero carbon emission direct coal fuel cell stack power generation device, characterized in that: include: A hollow ceramic shell; a first ceramic plate and a second ceramic plate disposed in the ceramic shell; a tubular fuel cell stack, a coal fuel feed pipe, and a coal fuel exhaust pipe penetrating the first ceramic plate and the second ceramic plate; a catalytic-mineralization conversion reactant feed pipe and a chemical product collection pipe penetrating the second ceramic plate; and a dual-function ceramic membrane embedded in the first ceramic plate; The first ceramic plate and the second ceramic plate separate the ceramic shell to form a direct coal fuel cell stack reaction chamber and a carbon dioxide catalytic-mineralization conversion reaction chamber; The bifunctional ceramic membrane includes a permeable membrane and a catalyst; The bifunctional ceramic membrane has a porous oxygen ion conductor electrolyte and a catalyst complex as a matrix, and the matrix is ​​impregnated with an alkali metal carbonate; The catalyst of the dual-function ceramic membrane is La 0.7 Sr 0.3 Fe 0.8 Ni 0.2 O 3-δ .

2. The near-zero carbon emission direct coal fuel cell stack power generation device according to claim 1, characterized in that: The invention also includes an air inlet pipe and an air outlet pipe which are arranged on the top of the tubular fuel cell stack.

3. The near-zero carbon emission direct coal fuel cell stack power generation device according to claim 2, characterized in that: The direct coal fuel cell stack reaction chamber is provided with coal fuel.

4. The near-zero carbon emission direct coal fuel cell stack power generation device according to claim 1, characterized in that: The tubular fuel cell stack comprises at least one tubular fuel cell, which is composed of an anode layer inside a tube, a cathode layer outside the tube, and an electrolyte arranged between the anode layer and the cathode layer.

5. The near-zero carbon emission direct coal fuel cell stack power generation device according to claim 1, characterized in that: The first ceramic plate and the second ceramic plate are arranged in parallel, the first ceramic plate includes at least four first holes, and the second ceramic plate includes at least five second holes.

6. A method for generating electricity using a near-zero carbon emission direct coal fuel cell stack power generation device as claimed in any one of claims 1 to 5, characterized in that: Includes steps: feeding coal fuel into a direct coal fuel cell stack reaction chamber through a coal fuel feed pipe; Air is introduced from the air inlet pipe to generate an electrochemical reaction with the coal fuel to generate electricity and produce carbon dioxide gas; The generated carbon dioxide gas permeates through the dual-function ceramic membrane and reaches the carbon dioxide catalytic-mineralization conversion reaction chamber; The reactants are introduced from the catalytic-mineralization conversion reactant feed pipe to chemically react with the carbon dioxide gas in the carbon dioxide catalytic-mineralization conversion reaction chamber to generate chemical products.

7. The power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device according to claim 6, characterized in that: The specific reaction process of the air introduced from the air inlet pipe and the coal fuel undergoing electrochemical reaction to generate electricity and produce carbon dioxide gas includes: The oxygen contained in the air obtains electrons on the cathode layer of the tubular fuel cell to generate oxygen ions; the oxygen ions pass through the electrolyte layer to reach the anode layer in the tubular fuel cell, and undergo an electrochemical reaction with the coal fuel in the anode layer to generate carbon dioxide, and release electrons to the external circuit, forming a complete current loop to generate electricity.

8. The power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device according to claim 6, characterized in that: The operating temperature of the direct coal fuel cell stack reaction chamber is 750-800°C; the operating temperature of the direct coal fuel cell stack reaction chamber is 50°C higher than the operating temperature of the carbon dioxide catalytic-mineralization conversion reaction chamber.

9. The power generation method of the near-zero carbon emission direct coal fuel cell stack power generation device according to claim 6, characterized in that: The reactants introduced from the catalytic-mineralization conversion reactant feed pipe include one or more of gas and serpentine.

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