CN115763883B - Zero-carbon-emission solid oxide fuel cell power generation system integrated with oxygen permeable membrane - Google Patents
Zero-carbon-emission solid oxide fuel cell power generation system integrated with oxygen permeable membrane Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 167
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 167
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000000446 fuel Substances 0.000 title claims abstract description 128
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000007787 solid Substances 0.000 title claims abstract description 42
- 238000010248 power generation Methods 0.000 title claims description 43
- 238000002485 combustion reaction Methods 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 230000002950 deficient Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 90
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000002737 fuel gas Substances 0.000 claims description 15
- 238000002407 reforming Methods 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 230000006835 compression Effects 0.000 claims description 9
- 238000007906 compression Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000037427 ion transport Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 24
- 239000001569 carbon dioxide Substances 0.000 abstract description 20
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 4
- 239000003546 flue gas Substances 0.000 abstract 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
Classifications
-
- 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
The system mainly comprises a solid oxide fuel cell, an oxygen permeable membrane device, an external reformer, a combustion chamber, a compressor and the like. In the system mode, after air is introduced into the oxygen permeable membrane device, oxygen is separated and introduced into the cathode of the solid oxide fuel cell, so that the electrochemical performance of the cell is improved; the cathode circulation of the solid oxide fuel cell improves the total oxygen amount entering the electric pile, and plays a better role in cooling; in mode two, oxygen is directly connected to the combustion chamber; the oxygen-deficient air is introduced into the cathode of the solid oxide fuel cell, so that the solid oxide fuel cell has better cooling effect, the required cooling air quantity is reduced, and the system efficiency is improved; the anode circulation of the battery improves the utilization rate of the total fuel; the flue gas at the outlet of the combustion chamber only contains water and carbon dioxide, so that the energy consumption in the carbon dioxide capturing process is reduced; after passing through the flue gas separation device, part of the flue gas is circularly introduced into the combustion chamber to maintain the temperature of the flue gas at the outlet.
Description
Technical Field
The invention belongs to the field of zero-carbon-emission solid oxide fuel cells, and particularly relates to a zero-carbon-emission solid oxide fuel cell power generation system integrated with an oxygen permeable membrane. In particular to a solid oxide fuel cell power generation system which utilizes an oxygen permeable membrane to prepare oxygen and introduce the oxygen into a solid oxide fuel cell to realize zero carbon emission.
Background
With the rapid development of industry worldwide, the world's demand for energy is increasing. In addition, the energy source is mainly fossil fuel, and a large amount of CO is discharged 2 、N 2 The pollutants such as O, sulfides and the like cause environmental pollution and seriously harm the health of people, so that a clean and efficient energy utilization mode is adopted to actively develop new energy, and the sustainable development of the national and social economy is facilitated; the solid oxide fuel cell is an energy conversion device for directly converting chemical energy into electric energy, and is operated at 650-850 ℃ without noble metal catalyst to improve catalytic activity, and the system has high efficiency, and the power generation is thatThe direct conversion process of chemical energy into electric energy, and therefore the power generation efficiency is not limited by the carnot cycle.
The solid oxide fuel cell is composed of a solid oxide electrolyte made of, for example, yttria stabilized zirconia ceramic, which allows oxygen atoms to be reduced from electrons on the surface of its porous cathode to oxygen ions, which are transferred through the ceramic electrolyte to the porous anode side where the fuel gas is sufficient to react with the fuel and release the electrons to an external circuit; because of the working mechanism that the fuel is not directly mixed with air, N is avoided 2 For CO 2 Provides convenience for reducing emissions. The oxygen permeable membrane can be used for preparing high-purity oxygen, and under the action of pressure difference at two sides, selective permeation of oxygen is realized through LSCF and other materials in the oxygen permeable membrane; the operating temperature is typically 800-1000C.
In patent CN 102518482A published under 2012, 6 and 27, CO integrated with OTM is described 2 The system comprises a solid oxide fuel cell system, an oxygen ion transmission membrane system, a waste heat boiler system and CO 2 A plurality of systems such as a recovery liquefaction system; the oxygen required by the back combustion chamber is produced by separating air through an oxygen ion transmission membrane system, and the main component of the obtained product is CO 2 And H 2 O, the combustion tail gas is separated out from water by a condenser and then is compressed and cooled to obtain CO 2 Liquid, the system can capture CO 2 But with higher efficiency, the performance of the battery is not further optimized.
Patent CN 108604697A published on 2018, 9 and 87 relates to a method for capturing CO from fuel cell 2 The system comprises a solid oxide fuel cell, a purifier, an anode gas oxidizer and other devices; in this system, the cell anode exhaust comprising carbon dioxide, water and unreacted hydrogen is split into two streams, one stream being fed directly to the anode gas oxidizer and the other stream being fed to the purifier and a portion of which is mixed with the fuel stream, the purifier exhaust being passed to the anode gas oxidizer; the purifier can internally reform and purify hydrogen from fuel and generate oxygen, and the oxygen is introduced into the anode gas oxidizer to reactThe oxidizer exhaust gas consists essentially of CO 2 And H 2 O and a small amount of H 2 And O 2 The method comprises the steps of carrying out a first treatment on the surface of the When the anode gas oxidizer exhaust stream is removed, water is first cooled to condense out, ultimately obtaining a high concentration of carbon dioxide.
The invention patent CN 112864438A published in the 5 th year and 28 th year of 2021 relates to a high-temperature fuel cell coupling power generation system and a method capable of realizing carbon dioxide capture, wherein the system comprises a solid oxide fuel cell, a molten hydrochloride fuel cell and other devices; in the system, oxygen is directly put into a burner to react with anode exhaust of a solid oxide fuel cell, combustion tail gas is introduced into a cathode of the molten carbonate fuel cell after heat exchange, and CO is obtained after the exhaust at the outlet of the cathode exchanges heat with fuel introduced into the cell 2 A gas; the system improves the fuel utilization rate in the molten electrolyte fuel cell, the power generation efficiency of the coupling power generation system and the comprehensive utilization rate of heat, but the system has larger investment.
In patent CN 113851671A published at 28, 12, 2021, a clean zero emission solid oxide fuel cell system is disclosed; the LNG cold energy air separator is used in the system, when liquefied natural gas is converted into natural gas, a proper amount of air is introduced, oxygen in the natural gas is separated to prepare pure oxygen, then the pure oxygen is introduced into the anode tail gas burner to enable the outlet components of the pure oxygen to be water and carbon dioxide, and the high-purity carbon dioxide obtained through the steam-water separation device after the tail gas is subjected to heat exchange by the heat exchanger is finally stored and utilized, but the system efficiency of the system is still provided with a space for improving.
Aiming at the defects of the prior art, the invention provides a zero-carbon emission solid oxide fuel cell power generation system integrated with an oxygen permeable membrane, which reasonably couples the solid oxide fuel cell system with the oxygen permeable membrane technology, improves the working environment of the cell and prolongs the service life of the cell; the fuel utilization rate of the system is improved, and the system efficiency is improved; liquefied capture of CO 2 Zero emission of the system is realized.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a zero-carbon emission solid oxide fuel cell power generation system integrated with an oxygen permeable membrane, which has the following technical scheme:
the zero-carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is characterized by comprising an oxygen enrichment module, a fuel gas preparation module, a galvanic pile tail gas treatment module and a combustion chamber tail gas treatment and recycling module; the oxygen enrichment module is connected with the pile module in the power generation system mode to provide pure oxygen for the pile module; the oxygen enrichment module is connected with the pile module and the combustion chamber tail gas treatment and recirculation module in the second power generation system mode to respectively provide oxygen-deficient air and pure oxygen; the fuel gas preparation module is connected with the electric pile module and is used for providing fuel gas for the electric pile module; the electric pile module is respectively connected with the electric pile tail gas treatment module, the combustion chamber tail gas treatment and recirculation module for treating tail gas at an electric pile outlet.
The invention also discloses a zero-carbon emission solid oxide fuel cell power generation control method of the integrated oxygen permeable membrane, which comprises the zero-carbon emission solid oxide fuel cell power generation system of the integrated oxygen permeable membrane, and is characterized in that: according to the control method, the system is used for establishing the tail gas recirculation of the galvanic pile, so that the fuel utilization rate of the system is improved, and the system efficiency is improved; establishing combustion chamber tail gas recirculation, and controlling the temperature of the tail gas at an outlet of the combustion chamber; liquefying and capturing CO in tail gas 2 Zero emission of the system is realized.
Advantageous effects
The solid oxide fuel cell power generation system has high efficiency and solves the problem of CO 2 Has the following characteristics:
(1) The oxygen permeable membrane device is adopted to separate air, pure oxygen is obtained in a mode and then is sent to the cathode of the electric pile, so that the concentration overpotential in the operation of the solid oxide fuel cell can be effectively reduced, and the electrochemical performance of the cell is improved; in the second mode, pure oxygen is obtained and then sent into a combustion chamber, and oxygen-deficient air passing through an oxygen permeable membrane device is sent into a cathode of a galvanic pile after being treated, so that the cooling capacity of the galvanic pile is improved, the air quantity required by a system is reduced, and the investment cost is reduced; the total power consumption of components in the system is reduced, and the system efficiency is improved.
(2) In mode, stack cathode and anode outlet gases are controlled to enter the burner by gas circulationFlow, directly controlling the flow of oxygen entering the burner in the second mode, and realizing complete reaction of combustible gas and oxygen in the burner, wherein the combustion product is only CO 2 And H 2 O can directly obtain high-purity CO after cooling and steam-water separation 2 Greatly reduce CO 2 And (5) collecting energy consumption.
(3) In the mode, the oxygen entering the cathode of the electric pile can be effectively increased by circulating the oxygen at the outlet of the cathode of the electric pile, and the cooling capacity of the electric pile is improved; the capacity of the oxygen separation unit can be effectively reduced, and the investment cost is reduced; can be used for controlling the flow of oxygen entering the burner, and realizing the complete reaction of the combustible gas and the oxygen in the burner according to the stoichiometric ratio.
(4) The method has the advantages that by circulating the gas at the anode outlet of the electric pile, part of unreacted fuel is treated and then is fed into the anode of the electric pile again, so that the concentration of reactants in the electric pile can be increased, the local operation environment of the electric pile is improved, and the service life of the electric pile is prolonged under the condition that the total fuel utilization rate of the system is unchanged; the total fuel utilization rate of the system can be properly improved and the overall energy efficiency of the system can be improved on the premise of not causing the deterioration of the local operation environment of the electric pile through the circulation.
(5) After the tail gas after combustion is cooled by a plurality of heat exchangers, part of the tail gas (CO 2 +H 2 O) is recycled back to the burner in order to control the combustion temperature, maintaining the combustion chamber outlet temperature in the range 850-950 ℃.
Drawings
Fig. 1 is a schematic diagram of a zero carbon emission solid oxide fuel cell power generation system mode integrating oxygen permeable membranes.
Fig. 2 is a schematic diagram of a zero carbon emission solid oxide fuel cell power generation system mode two integrating oxygen permeable membranes.
In the figure: 1-feed pump, 2-low temperature feed water heat exchanger, 3-high temperature feed water heat exchanger, 4-fuel compressor, 5-fuel mixer, 6-external reforming heat exchanger, 7-external reformer, 8-high temperature fuel heat exchanger, 9-anode recycle heat exchanger, 10-air compressor, 11-air mixer, 12-medium temperature air heat exchanger, 13-high temperature air heat exchanger, 14-oxygen permeable membrane device, 15-air turbine, 16-oxygen mixer, 17-electric pile, 18-DC/AC inverter, 19-cathode recycle high temperature heat exchanger, 20-cathode recycle low temperature heat exchanger, 21-cathode recycle compressor, 22-anode recycle compressor, 23-combustion chamber, 24-condenser, 25-carbon dioxide compressor, 201-oxygen-lean air cool heat exchanger, 202-oxygen-lean air compressor, 203-oxygen-lean air medium temperature heat exchanger, 204-oxygen-lean air high temperature heat exchanger.
Detailed Description
The invention provides a zero-carbon emission solid oxide fuel cell power generation system integrated with an oxygen permeable membrane, and the power generation system is described below with reference to the accompanying drawings.
In the mode shown in fig. 1, the zero-carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is characterized in that the feed water is heated by a low-temperature feed water heat exchanger 2 and a high-temperature feed water heat exchanger 3 after passing through a feed water pump 1 and is introduced into a fuel mixer 5; the fuel is compressed by the fuel compressor 4 and then is introduced into the fuel mixer 5; the two are mixed with the fuel for circulation through a fuel mixer 5, and the outlet fuel is heated through an external reforming heat exchanger 6 and then is introduced into an external reformer 7, and is heated through a high-temperature fuel heat exchanger and then is introduced into the anode of a galvanic pile 17; air is compressed by an air compressor 10 and then divided into two paths, one path is introduced into an air mixer 11 after passing through a cathode circulating low-temperature heat exchanger 20, the other path is directly introduced into the air mixer 11, the outlet of the air mixer 11 is heated by a medium-temperature air heat exchanger 12 and a high-temperature air heat exchanger 13 and then introduced into a raw material side inlet of an oxygen permeable membrane device 14, oxygen at a permeation measuring outlet of the oxygen permeable membrane device 14 and circulated oxygen are mixed by an oxygen mixer 16 and then introduced into the cathode of a galvanic pile 17, and oxygen-depleted oxygen at a retention side outlet of the oxygen permeable membrane device 14 is discharged after passing through the medium-temperature air heat exchanger 12 and an air turbine 15; the cathode oxygen exhaust of the stack 17 is divided into two paths: one path of the mixture is fed into a combustion chamber 23 for combustion, the other path of the mixture circulates, the mixture is pressurized by a cathode circulating compressor 21 after being cooled by a cathode circulating high-temperature heat exchanger 19 and a cathode circulating low-temperature heat exchanger 20, and then the mixture is fed into an oxygen mixer 16 for mixing after being heated by the cathode circulating high-temperature heat exchanger 19; the stack 17 anode fuel exhaust is split into two paths: one path is communicated with a combustion chamber 23 for combustion, the other path circulates, the anode circulation heat exchanger 9 and the low-temperature water supply heat exchanger 2 are cooled and then pressurized by an anode circulation compressor 22, and outlet fuel is introduced into a fuel mixer 5 for enteringMixing the rows; the output end of the electric pile 17 is connected with a direct current/alternating current inverter 18 to output electric energy; the gas at the outlet of the combustion chamber is divided into two paths after heat exchange by a high-temperature air heat exchanger 13, a high-temperature fuel heat exchanger 8, an external reformer 7, an external reforming heat exchanger 6 and a high-temperature water supply heat exchanger 3: one is returned to the combustion chamber 23 to ensure proper outlet temperature, and the other is led to the condenser 24 to separate out water, thus obtaining high-purity CO 2 The gas is introduced into a carbon dioxide compressor 25 for compression and liquefaction to obtain CO 2 The liquid was stored.
In the mode two, as shown in fig. 2, the zero-carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is characterized in that the feed water is heated by the low-temperature feed water heat exchanger 2 and the high-temperature feed water heat exchanger 3 after passing through the feed water pump 1, and is introduced into the fuel mixer 5; the fuel is compressed by the fuel compressor 4 and then is introduced into the fuel mixer 5; the two are mixed with the fuel for circulation through a fuel mixer 5, and the outlet fuel is heated through an external reforming heat exchanger 6 and then is led into an external reformer 7, and is heated through a high-temperature fuel heat exchanger 8 and then is led into the anode of a galvanic pile 17; air is compressed by the air compressor 10, heated by the high-temperature air heat exchanger 13 and then introduced into a raw material side inlet of the oxygen permeable membrane device 14, and lean oxygen air at a detention side outlet of the oxygen permeable membrane device 14 is cooled by the lean oxygen air cooling heat exchanger 201 and then reduced in pressure by the lean oxygen air compressor 202, heated by the lean oxygen air cooling heat exchanger 201, the lean oxygen air medium-temperature heat exchanger 203 and the lean oxygen air high-temperature heat exchanger 204 and then introduced into the cathode of the electric pile 17; oxygen at the permeation measuring outlet of the oxygen permeation membrane device 14 is introduced into the combustion chamber 23; the stack 17 anode fuel exhaust is split into two paths: one path is communicated with a combustion chamber 23 for combustion, the other path circulates, the anode circulation heat exchanger 9 and the low-temperature water supply heat exchanger 2 are cooled and then pressurized by an anode circulation compressor 22, and outlet fuel is communicated with a fuel mixer 5 for mixing; the cathode exhaust gas of the electric pile 17 exchanges heat with the oxygen-depleted air medium-temperature heat exchanger 203 and the high-temperature air heat exchanger 13 and is discharged; the output end of the electric pile 17 is connected with a direct current/alternating current inverter 18 to output electric energy; the outlet gas of the combustion chamber is divided into two paths after heat exchange by an oxygen-depleted air high-temperature heat exchanger 204, a high-temperature fuel heat exchanger 8, an external reformer 7, an external reforming heat exchanger 6 and a high-temperature water supply heat exchanger 3: one is returned to the combustion chamber 23 to ensure proper outlet temperature, and the other is led into the condenser 24 to separate out waterObtaining high-purity CO 2 The gas is introduced into a carbon dioxide compressor 25 for compression and liquefaction to obtain CO 2 The liquid was stored.
The working principle of the zero-carbon-emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is as follows: the feed water is heated by a low-temperature feed water heat exchanger and a high-temperature accumulated water heat exchanger after passing through a feed water pump, and is introduced into a fuel mixer; the fuel is compressed by a fuel compressor and then is introduced into a fuel mixer; mixing the two with the fuel to be circulated through a fuel mixer, heating the outlet fuel through an external reforming heat exchanger, introducing the heated outlet fuel into an external reformer, heating the reformed fuel through a high-temperature fuel heat exchanger, and introducing the heated reformed fuel into a galvanic pile anode; in the mode, air is compressed by an air compressor and then divided into two paths, one path is introduced into an air mixer after heat exchange by a cathode circulating low-temperature heat exchanger, the other path is directly introduced into the air mixer, an outlet of the air mixer is heated by the cathode circulating low-temperature heat exchanger, a middle-temperature air heat exchanger and a high-temperature air heat exchanger and then introduced into a raw material side inlet of an oxygen permeable membrane device, oxygen at a permeation measuring outlet of the oxygen permeable membrane device and circulated oxygen are mixed by the oxygen mixer and then introduced into a cathode of a galvanic pile, and lean oxygen at a retention side outlet of the oxygen permeable membrane device is discharged after heat exchange by the middle-temperature air heat exchanger and air turbine work; the cathode oxygen exhaust of the electric pile is divided into two paths: one path of the mixed gas is fed into a combustion chamber for combustion, the other path of the mixed gas circulates, the mixed gas is pressurized by a cathode circulating compressor after being cooled by a cathode circulating high-temperature heat exchanger and a cathode circulating low-temperature heat exchanger, and then is fed into an oxygen mixer for mixing after being heated by the cathode circulating high-temperature heat exchanger, so that the total oxygen quantity fed into a galvanic pile is improved, and a better cooling effect is achieved on the galvanic pile; the stack anode fuel exhaust is divided into two paths: one path is communicated with a combustion chamber for combustion, the other path circulates, the anode circulation heat exchanger and the low-temperature water supply heat exchanger are cooled and then pressurized by an anode circulation compressor, and outlet fuel is introduced into a fuel mixer for mixing, so that the utilization rate of total fuel is improved; the output end of the electric pile is connected with the direct current/alternating current inverter to output electric energy; the outlet gas of the combustion chamber is divided into two paths after heat exchange by a high-temperature air heat exchanger, a high-temperature fuel heat exchanger, an external reformer, an external reforming heat exchanger and a high-temperature water supply heat exchanger: one way returns to the combustion chamber to ensure proper outputThe temperature of the mouth is the same as that of the other way, and the water is separated out by a condenser to obtain high-purity CO 2 Introducing the gas into a carbon dioxide compressor for compression and liquefaction to obtain CO 2 Liquid and store; in the second mode, air is compressed by an air compressor, heated by an air heat exchanger and then introduced into a raw material side inlet of an oxygen permeable membrane device, and oxygen-depleted air at a retention side outlet of the oxygen permeable membrane device is cooled by an oxygen-depleted air cooling heat exchanger and then reduced in pressure by the oxygen-depleted air compressor, and then heated by the oxygen-depleted air cooling heat exchanger, an oxygen-depleted air medium-temperature heat exchanger and an oxygen-depleted air high-temperature heat exchanger and then introduced into a cathode of a galvanic pile; oxygen at the permeation measuring outlet of the oxygen permeation membrane device is introduced into the combustion chamber; the stack anode fuel exhaust is divided into two paths: one path is communicated with a combustion chamber for combustion, the other path circulates, the anode circulation heat exchanger and the low-temperature water supply heat exchanger are cooled and then pressurized by an anode circulation compressor, and outlet fuel is introduced into a fuel mixer for mixing, so that the utilization rate of total fuel is improved; the cathode exhaust gas of the electric pile is discharged after heat exchange with the oxygen-depleted air medium-temperature heat exchanger and the air heat exchanger; the output end of the electric pile is connected with the direct current/alternating current inverter to output electric energy; the outlet gas of the combustion chamber is divided into two paths after heat exchange by an oxygen-depleted air high-temperature heat exchanger, a high-temperature fuel heat exchanger, an external reformer, an external reforming heat exchanger and a high-temperature water supply heat exchanger: one path returns to the combustion chamber to ensure proper outlet temperature, and the other path is led into a condenser to separate out water, thus obtaining high-purity CO 2 Introducing the gas into a carbon dioxide compressor for compression and liquefaction to obtain CO 2 The liquid was stored. An oxygen ion transport membrane is adopted between the raw material side and the permeation side of the oxygen permeable membrane device, and the working temperature of the oxygen permeable membrane device is about 700-900 ℃.
Example 1
In this embodiment, the above solid oxide fuel cell power generation system is used, wherein the fuel is natural gas, and the stack anode tail gas circulation ratio is 0.2.
As shown in fig. 1, the water supply is pressurized and heated and then mixed with natural gas and recycled stack anode tail gas in a fuel mixer, the outlet fuel is heated and then reformed in an external reformer to produce hydrogen, and the reformed fuel gas is heated and then fed into a stack; air is pressurized and heated, oxygen is enriched by utilizing an oxygen permeable membrane device, and the air is mixed with recirculated cathode tail gas of the galvanic pile in an oxygen mixer and then is put into the galvanic pile, and oxygen-depleted air at an outlet of the oxygen permeable membrane device exchanges heat with inlet air and is discharged; the tail gas of the electric pile is divided into two parts, one part is put into a combustion chamber for combustion in a proper proportion, the other part is recycled, and the tail gas is put into the electric pile again after heat exchange and compression; the tail gas of the combustion chamber is divided into two parts after heat exchange, one part is thrown into the combustion chamber again to control the outlet temperature of the tail gas, the other part condenses out water in the tail gas through a condenser, and the rest carbon dioxide gas is pressurized and liquefied through a carbon dioxide compressor to realize storage.
The power generation system parameter settings of this embodiment are shown in table 1:
TABLE 1
The power generation system results of this example are shown in table 2:
TABLE 2
As can be seen from Table 2, the efficiency of the zero carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is 41.69%, and the system efficiency is slightly lower than that of the conventional system, so that the influence of the oxygen permeable membrane device on the system efficiency in the process of enriching oxygen and liquefying and recovering carbon dioxide is shown.
The embodiment and the beneficial effects of the invention are described in detail, and the oxygen permeation membrane device is utilized to enrich oxygen to be put into the galvanic pile, so that the electrochemical performance of the battery is improved; the tail gas recirculation of the electric pile controls the flow rate of the fuel gas introduced into the combustion chamber, so that the complete reaction of the combustible gas and oxygen is realized, the combustion products are only CO2 and H2O, and the energy consumption for capturing CO2 is reduced; the cathode tail gas circulation can improve the cooling capacity of the galvanic pile and reduce the cost of enriching oxygen; the anode tail gas circulation improves the fuel utilization rate of the system and improves the system efficiency; the tail gas circulation of the combustion chamber controls the outlet temperature of the combustion chamber to be kept in a proper range; after water in the tail gas is separated by utilizing the condenser, the carbon dioxide gas is liquefied by pressurization, so that zero emission of the system is realized.
Example 2
In this embodiment, the above solid oxide fuel cell power generation system is used, wherein the fuel is natural gas, and the stack anode tail gas circulation ratio is 0.2.
As shown in fig. 2, the water supply is pressurized and heated and then mixed with natural gas and recycled stack anode tail gas in a fuel mixer, the outlet fuel is heated and then reformed in an external reformer to produce hydrogen, and the reformed fuel gas is heated and then fed into a stack; air is pressurized and heated, oxygen is enriched by an oxygen permeable membrane device and is put into a combustion chamber, and oxygen-depleted air at an outlet of the oxygen permeable membrane device is treated and then is introduced into a cathode of a galvanic pile; the tail gas of the anode of the electric pile is divided into two parts, one part is put into a combustion chamber for combustion in a proper proportion, the other part is recycled, and the two parts are put into the electric pile again after heat exchange and compression; discharging the tail gas of the cathode of the electric pile after heat exchange; the tail gas of the combustion chamber is divided into two parts after heat exchange, one part is thrown into the combustion chamber again to control the outlet temperature of the tail gas, the other part condenses out water in the tail gas through a condenser, and the rest carbon dioxide gas is pressurized and liquefied through a carbon dioxide compressor to realize storage.
The power generation system parameter settings of this embodiment are shown in table 1; the power generation system results of this example are shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, the efficiency of the zero carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is 48.12%, and the system efficiency is still better under the conditions that the system utilizes the oxygen permeable membrane device to enrich oxygen and liquefy and recycle carbon dioxide.
The embodiment and the beneficial effects of the invention are described in detail, the oxygen is enriched by the oxygen permeable membrane device and is put into the combustion chamber, so that the complete reaction of the combustible gas and the oxygen is realized, the combustion products are only CO2 and H2O, and the energy consumption for capturing CO2 is reduced; the treated oxygen-deficient air is introduced into the cathode of the electric pile, so that the cooling capacity of the electric pile can be improved, the air flow of the system can be reduced, and the system efficiency can be improved; the anode tail gas circulation improves the fuel utilization rate of the system and improves the system efficiency; the tail gas circulation of the combustion chamber controls the outlet temperature of the combustion chamber to be kept in a proper range; after water in the tail gas is separated by utilizing the condenser, the carbon dioxide gas is liquefied by pressurization, so that zero emission of the system is realized.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The zero-carbon emission solid oxide fuel cell power generation system integrated with the oxygen permeable membrane is characterized by comprising an oxygen enrichment module, a fuel gas preparation module, a galvanic pile tail gas treatment module and a combustion chamber tail gas treatment and recycling module; the oxygen enrichment module is connected with the pile module in the power generation system mode to provide pure oxygen for the pile module; the oxygen enrichment module is connected with the pile module and the combustion chamber tail gas treatment and recirculation module in the second power generation system mode to respectively provide oxygen-deficient air and pure oxygen; the fuel gas preparation module is connected with the electric pile module and is used for providing fuel gas for the electric pile module; the electric pile module is respectively connected with the electric pile tail gas treatment module, the combustion chamber tail gas treatment and recirculation module and is used for treating tail gas at an electric pile outlet; the oxygen enrichment module in the power generation system mode is used for enriching oxygen by utilizing the oxygen permeable membrane device (14) after compressing and exchanging heat of air introduced into the system, and the air is mixed with the recycled cathode tail gas and then is input into the pile (17) module; the oxygen enrichment module main equipment comprises an air compressor (10), a cathode circulation low-temperature heat exchanger (20), an air mixer (11), a medium-temperature air heat exchanger (12), a high-temperature air heat exchanger (13), an oxygen permeable membrane device (14), an air turbine (15) and an oxygen mixer (16); the system components are connected as follows: an outlet of the air compressor (10) is divided into two paths, one path is connected with the cathode circulating low-temperature heat exchanger (20) and then is introduced into the air mixer (11), the other path is connected with the air mixer (11), is connected with the medium-temperature air heat exchanger (12) and the high-temperature air heat exchanger (13) in series and then is introduced into a raw material side inlet of the oxygen permeable membrane device (14), an infiltration measuring outlet of the oxygen permeable membrane device (14) is connected with the oxygen mixer (16) in series and then is introduced into a cathode of the electric pile (17), and a detention side outlet of the oxygen permeable membrane device (14) is connected with the medium-temperature air heat exchanger (12) and the air turbine (15); the oxygen enrichment module in the second power generation system mode is used for compressing and exchanging heat of air introduced into the system, enriching oxygen by utilizing the oxygen permeable membrane device (14) and inputting the enriched oxygen into the tail gas treatment and recirculation module of the combustion chamber (23); the oxygen enrichment module main equipment comprises an air compressor (10), a high-temperature air heat exchanger (13), an oxygen permeable membrane device (14), an oxygen-depleted air cooling heat exchanger (201), an oxygen-depleted air compressor (202), an oxygen-depleted air medium-temperature heat exchanger (203) and an oxygen-depleted air high-temperature heat exchanger (204); the system components are connected as follows: an air compressor (10) is connected in series with a high-temperature air heat exchanger (13) and then is introduced into a raw material side inlet of an oxygen permeable membrane device (14), a permeation measuring outlet of the oxygen permeable membrane device (14) is connected into a combustion chamber (23), and a detention side outlet of the oxygen permeable membrane device (14) is connected in series with an oxygen-deficient air cooling heat exchanger (201), an oxygen-deficient air compressor (202), an oxygen-deficient air cooling heat exchanger (201), an oxygen-deficient air medium-temperature heat exchanger (203) and an oxygen-deficient air high-temperature heat exchanger (204) and then is connected into a cathode of a galvanic pile (17);
or: the stack (17) tail gas recirculation module in the power generation system mode respectively inputs the tail gases of the anode and cathode parts of the stack (17) of the input module to the fuel mixer (5) of the fuel gas preparation module and the oxygen mixer (16) of the oxygen enrichment module after heat exchange and compression; the main equipment of the tail gas recirculation module of the electric pile (17) comprises an anode circulation heat exchanger (9), a low-temperature water supply heat exchanger (2), an anode circulation compressor (22), a cathode circulation high-temperature heat exchanger (19), a cathode circulation low-temperature heat exchanger (20) and a cathode circulation compressor (21); the system components are connected as follows: the cathode of the electric pile (17) is connected with a cathode circulation high-temperature heat exchanger (19), a cathode circulation low-temperature heat exchanger (20), a cathode circulation compressor (21) in series and then is connected with an oxygen mixer (16) to form a loop; the anode of the electric pile (17) is connected with the anode circulating heat exchanger (9), the low-temperature water supply heat exchanger (2) and the anode circulating compressor (22) in series and then connected with the fuel mixer (5) to form a loop; the tail gas treatment module of the electric pile (17) in the second power generation system mode is used for inputting the tail gas of the anode part of the electric pile (17) of the input module into the fuel mixer (5) of the fuel gas preparation module after heat exchange and compression, and the tail gas of the cathode of the electric pile (17) is introduced into the oxygen-depleted air medium-temperature heat exchanger (203) of the oxygen enrichment module; the main equipment of the tail gas treatment module of the electric pile (17) comprises an anode circulating heat exchanger (9), a low-temperature water supply heat exchanger (2) and an anode circulating compressor (22); the system components are connected as follows: the anode of the electric pile (17) is connected with the anode circulating heat exchanger (9), the low-temperature water supply heat exchanger (2) and the anode circulating compressor (22) in series and then connected with the fuel mixer (5) to form a loop; the cathode of the electric pile (17) is connected with an oxygen-deficient air medium temperature heat exchanger (203).
2. The oxygen permeable membrane integrated zero carbon emission solid oxide fuel cell power generation system of claim 1, characterized by: the fuel gas preparation module of the system is used for mixing fuel and water fed into the system after compression and heat exchange with the recirculated anode tail gas and then reforming, and the reformed fuel gas is input into the pile module; the main equipment of the fuel gas preparation module comprises a water feed pump (1), a low-temperature water feed heat exchanger (2), a high-temperature water feed heat exchanger (3), a fuel compressor (4), a fuel mixer (5), an external reforming heat exchanger (6), an external reformer (7), a high-temperature fuel heat exchanger (8) and an anode circulating heat exchanger (9); the system components are connected as follows: the water feed pump (1) is connected in series with the low-temperature water feed heat exchanger (2), the high-temperature water feed heat exchanger (3) and the fuel mixer (5); the fuel compressor (4) is connected in series with the fuel mixer (5), and the outlet of the fuel mixer (5) is connected in series with the external reforming heat exchanger (6), the external reformer (7), the high-temperature fuel heat exchanger (8) and the anode circulating heat exchanger (9) and then connected to the anode of the electric pile (17).
3. The membrane-integrated zero-carbon-emission solid oxide fuel cell power generation system according to claim 1, wherein,
an oxygen ion transport membrane is adopted between the raw material side and the permeation side of the oxygen permeable membrane device (14), and the working temperature of the oxygen permeable membrane device is 700-900 ℃.
4. A method for controlling the power generation of an integrated oxygen permeable membrane-based solid oxide fuel cell, comprising the integrated oxygen permeable membrane-based solid oxide fuel cell power generation system according to any one of claims 1 to 3, characterized in that: according to the control method, the system is used for establishing the tail gas recirculation of the galvanic pile, so that the fuel utilization rate of the system is improved, and the system efficiency is improved; establishing combustion chamber tail gas recirculation, and controlling the temperature of the tail gas at an outlet of the combustion chamber; liquefying and capturing CO in tail gas 2 Zero emission of the system is realized.
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