CN108232206B - Direct power generation method and system by utilizing ventilation air methane or low-concentration gas - Google Patents
Direct power generation method and system by utilizing ventilation air methane or low-concentration gas Download PDFInfo
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- CN108232206B CN108232206B CN201711261254.9A CN201711261254A CN108232206B CN 108232206 B CN108232206 B CN 108232206B CN 201711261254 A CN201711261254 A CN 201711261254A CN 108232206 B CN108232206 B CN 108232206B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000009423 ventilation Methods 0.000 title claims abstract description 63
- 238000010248 power generation Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 118
- 239000000446 fuel Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims description 24
- 238000006477 desulfuration reaction Methods 0.000 claims description 19
- 230000023556 desulfurization Effects 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- 230000006378 damage Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000004880 explosion Methods 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- 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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
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- 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
- H01M8/0675—Removal of sulfur
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- 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
- H01M8/0687—Reactant purification by the use of membranes or filters
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- 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
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Abstract
A direct power generation method and system using ventilation air methane or low-concentration gas, on one hand, after the ventilation air methane or the extracted low-concentration gas is desulfurized and dedusted, part of oxygen in the gas is removed by a gas separation device, and then the gas enters an anode gas passage of a solid oxide fuel cell to participate in electrochemical reaction; on the other hand, the outside air enters the cathode air passage of the solid oxide fuel cell to participate in the electrochemical reaction, and simultaneously the solid oxide fuel cell outputs direct current to the outside. The invention directly converts the chemical energy of ventilation air methane or low-concentration gas into electric energy, obviously improves the generating efficiency and does not generate noise, nitrogen oxide and other pollution; an external reformer is not required to be added, so that the complexity and the cost of the system are reduced; meanwhile, the explosion risk of the solid oxide fuel cell when low-concentration gas is used as fuel is avoided, the damage of oxidation damage, carbon deposition, poisoning and the like of the anode of the cell can be effectively prevented, and the method is a safe, reliable and efficient ventilation air methane or low-concentration gas power generation technology.
Description
Technical Field
The invention relates to the technical field of gas utilization, in particular to a direct power generation method and system by utilizing ventilation air methane or low-concentration gas.
Background
China coal mine ventilation air methane (also called coal mine air methane discharge, C)CH4<1%) and extracted low-concentration gas (C)CH4<30%) are particularly large, reaching over 250 billions of cubic meters per year, but because of the low methane concentration and the great difficulty in utilization, these gas gases are usually directly discharged into the atmosphere, causing serious energy waste and greenhouse gas pollution. Therefore, the high-efficiency utilization of the ventilation air and the extracted low-concentration gas has important significance for relieving the energy crisis and improving the ecological environment.
At present, the utilization technology of ventilation air methane and extracted low-concentration gas mainly comprises a separation and purification technology, a combustion power generation technology and a countercurrent oxidation technology. The separation and purification technology has complex process and high cost, and the purification efficiency of ventilation air methane and low-concentration gas is low; the combustion power generation technology mainly comprises a power generation technology of an internal combustion engine and a gas turbine, the technology can convert chemical energy in gas into electric energy only by a multi-stage energy conversion process of heat energy, mechanical energy and the like, wherein related mechanical operation parts are complex, the technology has the defects of low power generation efficiency (< 30%), poor reliability, large noise and the like, and in addition, the atmospheric pollutants such as nitrogen oxides and the like are discharged in the power generation process; the countercurrent oxidation technology is mainly applied to mine ventilation air methane, the technology enables the gas with ultralow concentration to be slowly oxidized in a reactor and emit heat, but the energy conversion rate is low, and the technology is mainly applied to mine heat supply at present and has poor economic benefit.
The solid oxide fuel cell is an all-solid-state clean and efficient energy conversion device, can directly convert chemical energy in fuel into electric energy, has high power generation efficiency (more than 50 percent), and does not generate gas pollutants such as nitrogen oxides and the like and noise pollution. The existing solid oxide fuel cell power generation technology mainly uses pure hydrogen or pure methane as fuel, and does not use ventilation air with a large amount of air or extracted low-concentration gas as fuel. However, if the solid oxide fuel cell uses ventilation air or extracted low-concentration gas as fuel, there is a risk of gas explosion, and problems such as oxidation destruction, carbon deposition, and poisoning of the anode may occur. Therefore, a safe, reliable and efficient solid oxide fuel cell direct power generation technology using ventilation air or low-concentration gas is needed.
Disclosure of Invention
The invention aims to provide a direct power generation method and a system by utilizing ventilation air methane or low-concentration gas, the method and the system can directly convert chemical energy in the ventilation air methane or the low-concentration gas into electric energy, can improve the power generation efficiency and the energy utilization rate, reduce the discharge amount of the ventilation air methane and the extracted low-concentration gas and reduce the environmental pollution; meanwhile, the explosion of ventilation air methane or low-concentration gas in the high-temperature environment in the fuel cell stack can be avoided, and the problems of oxidation damage, carbon deposition, poisoning and the like of the anode of the fuel cell can be avoided.
In order to achieve the purpose, the ventilation air methane or the low-concentration gas methane extracted by a gas ventilation air methane or a gas extraction vacuum pump firstly enters a dust removal and desulfurization device for desulfurization and dust removal pretreatment, the ventilation air methane or the low-concentration gas methane after pretreatment is then conveyed to a gas separation device for removing partial oxygen, the ventilation air methane or the low-concentration gas methane after removing partial oxygen enters an anode air passage of a solid oxide fuel cell for participating in electrochemical reaction, meanwhile, outside air is conveyed to a cathode air passage of the solid oxide fuel cell for participating in electrochemical reaction, and the solid oxide fuel cell outputs direct current to the outside to realize that the chemical energy of the ventilation air methane or the low-concentration gas methane is directly converted into electric energy.
Furthermore, the dedusting and desulfurizing device reduces the content of hydrogen sulfide gas in ventilation air methane or low-concentration gas to be less than 10ppm and reduces the content of dust in the ventilation air methane or the low-concentration gas to be 5mg/m3The following.
Furthermore, the gas separation device separates oxygen from the ventilation air methane or the low-concentration gas through membrane separation or pressure swing adsorption, so that the volume ratio of the oxygen to the methane in the separated ventilation air methane or the separated low-concentration gas methane is 0.3-1, and the volume content of the oxygen in the separated ventilation air methane or the separated low-concentration gas methane is not higher than 12%.
Preferably, the operating temperature of the solid oxide fuel cell is 650 ℃ to 800 ℃.
Preferably, the solid oxide fuel cell employs a Ni-based anode.
A direct power generation method and system utilizing ventilation air or low-concentration gas comprise a mine ventilator or a gas extraction vacuum pump, a desulfurization and dust removal device, a gas separation device and a solid oxide fuel cell, wherein the mine ventilator or the gas extraction vacuum pump is connected with the desulfurization and dust removal device, the desulfurization and dust removal device is connected with the gas separation device, and the gas separation device is connected with the solid oxide fuel cell.
On one hand, after low-concentration gas extracted by a ventilation air methane or gas extraction vacuum pump discharged by a mine ventilator is subjected to desulfurization and dust removal treatment, part of oxygen in the gas is removed through a gas separation device, then the gas enters an anode gas passage of a solid oxide fuel cell to participate in electrochemical reaction, and pure oxygen separated by the gas separation device is collected and reserved for later use (such as oxygen supply of a coal mine emergency rescue system); on the other hand, the outside air enters a cathode air passage of the solid oxide fuel cell to participate in electrochemical reaction, and the solid oxide fuel cell outputs direct current to the outside to realize the direct conversion of the chemical energy of ventilation air methane or low-concentration gas into electric energy. Compared with the prior art, the invention has the following advantages:
(1) the solid oxide fuel cell directly converts chemical energy in ventilation air methane or low-concentration gas into electric energy without the limitation of Carnot cycle efficiency, avoids the multi-stage energy conversion process of power generation of an internal combustion engine or a gas turbine, has high power generation efficiency, does not generate noise in the power generation process, and does not generate air pollutants such as nitrogen oxides and the like;
(2) the desulfurization and dust removal device carries out proper dust removal and desulfurization pretreatment on the ventilation air methane or the low-concentration gas, thereby avoiding the damage of dust and hydrogen sulfide gas in the ventilation air methane or the low-concentration gas to the anode of the fuel cell;
(3) the gas separation device separates partial oxygen in the ventilation air methane or the low-concentration gas, so that the ventilation air methane or the low-concentration gas is prevented from exploding in a high-temperature environment in the fuel cell stack, and the oxygen with proper concentration can prevent the anode of the fuel cell from being damaged by high oxygen concentration and can also prevent the anode of the fuel cell from being deposited with carbon;
(4) the gas separation device only needs to separate part of oxygen and does not need to separate nitrogen, so that the requirement on the separation technology is low, and the separation cost is low;
(5) the operation temperature of the solid oxide fuel cell ensures that the solid oxide fuel cell has higher generating power, does not influence the long-term stability of the operation of the cell, and simultaneously reduces the performance requirement on the fuel cell material;
(6) the solid oxide fuel cell adopts the Ni-based anode to support the fuel cell, so that the internal reforming reaction of low-concentration gas in an anode region in the cell can be promoted, and gases such as hydrogen, carbon monoxide and the like which easily participate in the electrochemical reaction are generated, an external reformer is avoided, and the complexity and the cost of a system are reduced.
Drawings
FIG. 1 is a system set-up diagram of the present invention;
in the figure: 1. a desulfurization and dust removal device 2, a gas separation device 3 and a solid oxide fuel cell.
Detailed Description
The present invention will be described in further detail with reference to examples.
As shown in figure 1, the direct power generation method by using the ventilation air methane or the low-concentration gas is characterized in that firstly, the ventilation air methane or the low-concentration gas extracted by a gas extraction vacuum pump exhausted by a mine ventilator enters a dust removal and desulfurization device 1 for desulfurization and dust removal pretreatment, the ventilation air methane or the low-concentration gas after pretreatment is then conveyed to a gas separation device 2 to remove partial oxygen, the ventilation air methane or the low-concentration gas after partial oxygen removal enters an anode air passage of a solid oxide fuel cell 3 to participate in electrochemical reaction, meanwhile, outside air is conveyed to a cathode air passage of the solid oxide fuel cell 3 to participate in the electrochemical reaction, and the solid oxide fuel cell 4 outputs direct current to the outside to realize the direct conversion of chemical energy in the ventilation air methane or the low-concentration gas into electric energy.
In order to further avoid the damage of dust and hydrogen sulfide gas in ventilation air methane or low-concentration gas to the anode of the battery, the dedusting and desulfurizing device 1 reduces the content of the hydrogen sulfide gas in the ventilation air methane or the low-concentration gas to be less than 10ppm and reduces the content of the dust in the ventilation air methane or the low-concentration gas to be 5mg/m3The following.
In order to further avoid explosion of the ventilation air methane or the low-concentration gas in the high-temperature environment in the fuel cell stack and further prevent oxidation damage or carbon deposition of the anode of the cell, the gas separation device 2 separates partial oxygen from the ventilation air methane or the low-concentration gas through membrane separation or pressure swing adsorption separation, so that the volume ratio of the oxygen to the methane in the separated ventilation air methane or the separated gas methane is 0.3-1, and the volume content of the oxygen in the separated ventilation air methane or the separated low-concentration gas methane is not higher than 12%.
In order to improve the power generation power of the solid oxide fuel cell 3, not affect the long-term stability of the cell operation, and simultaneously reduce the performance requirement of the fuel cell stack material, the operating temperature of the solid oxide fuel cell 3 is 650-800 ℃.
In order to further promote the internal reforming reaction of low-concentration gas in the anode region inside the cell, generate hydrogen, carbon monoxide and other gases which are easy to participate in the electrochemical reaction, avoid the use of an external reformer, reduce the complexity of the system and reduce the cost, the solid oxide fuel cell 3 adopts a Ni-based anode to support the fuel cell.
As shown in fig. 1, the direct power generation system using ventilation air or low-concentration gas comprises a mine ventilator or a gas extraction vacuum pump, a desulfurization and dust removal device 1, a gas separation device 2 and a solid oxide fuel cell 3, wherein the mine ventilator or the gas extraction vacuum pump is connected with the desulfurization and dust removal device 1, the desulfurization and dust removal device 1 is connected with the gas separation device 2, and the gas separation device 2 is connected with the solid oxide fuel cell 3.
Claims (4)
1. A direct power generation method utilizing ventilation air methane or low-concentration gas is characterized in that firstly, the ventilation air methane discharged by a mine ventilator or the low-concentration gas extracted by a gas extraction vacuum pump enters a dust removal and desulfurization device (1) for desulfurization and dust removal pretreatment, the ventilation air methane or the low-concentration gas after pretreatment is then conveyed to a gas separation device (2) for removing partial oxygen, the ventilation air methane or the low-concentration gas after partial oxygen removal enters an anode air passage of a solid oxide fuel cell (3) for participating in electrochemical reaction, meanwhile, outside air is conveyed to a cathode air passage of the solid oxide fuel cell (3) for participating in the electrochemical reaction, and the solid oxide fuel cell (3) outputs direct current to the outside to realize that the chemical energy of the ventilation air methane or the low-concentration gas is directly converted into electric energy; the dedusting and desulfurizing device (1) reduces the content of hydrogen sulfide gas in ventilation air methane or low-concentration gas to be less than 10ppm and reduces the content of dust in the ventilation air methane or the low-concentration gas to be 5mg/m3The following; the gas separation device (2) separates part of the oxygen by membrane separation or pressure swing adsorptionAnd (3) separating the gas from the ventilation air methane or the low-concentration gas, so that the volume ratio of oxygen to methane in the separated ventilation air methane or the low-concentration gas is 0.3-1, and the volume content of the oxygen in the separated ventilation air methane or the low-concentration gas is not higher than 12%.
2. The direct power generation method using ventilation air methane or low-concentration gas as claimed in claim 1, wherein the operating temperature of the solid oxide fuel cell (3) is 650 ℃ to 800 ℃.
3. A direct power generation method using ventilation air methane or low concentration gas according to claim 1, characterized in that the solid oxide fuel cell (3) employs a Ni-based anode.
4. The direct power generation system utilizing the ventilation air or the low-concentration gas is characterized by comprising a mine ventilator or a gas extraction vacuum pump, a desulfurization and dust removal device (1), a gas separation device (2) and a solid oxide fuel cell (3), wherein the mine ventilator or the gas extraction vacuum pump is connected with the desulfurization and dust removal device (1), the desulfurization and dust removal device (1) is connected with the gas separation device (2), and the gas separation device (2) is connected with the solid oxide fuel cell (3).
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