CN113224359A - Molten carbonate fuel cell system based on hydrogen adsorption circulation and working method thereof - Google Patents
Molten carbonate fuel cell system based on hydrogen adsorption circulation and working method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000001257 hydrogen Substances 0.000 title claims abstract description 114
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 113
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 72
- 239000000446 fuel Substances 0.000 title claims abstract description 71
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 127
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000003034 coal gas Substances 0.000 claims description 16
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 11
- 238000002309 gasification Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 8
- 239000000567 combustion gas Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
-
- 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
- H01M8/0643—Gasification of solid fuel
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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
- H01M8/14—Fuel cells with fused electrolytes
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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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
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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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- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention discloses a molten carbonate fuel cell system based on hydrogen adsorption circulation and a working method thereof, belonging to the technical field of high-temperature fuel cells2And CO2Separating into over 90% hydrogen-rich gas, and separating to obtain CO2Gas in catalytic burner to convert H2Total removal of, catalytically combusted, O2With CO2The mixture ratio can meet the gas component requirement of the cathode of the cell stack, and the CO in the tail gas of the anode2And unreacted H2Is pumped to the inlet of the medium temperature pressure swing adsorption device, separated again and circulated to the cell stack for electrochemical reaction to form H2And CO2The cycle of (2). The invention simplifies meltingThe fuel treatment process flow of the molten carbonate fuel cell is realized, and the anode tail gas is circulated to a medium-temperature pressure swing adsorption device to recover CO2And unreacted hydrogen, further improving the system efficiency and performance of the molten carbonate fuel cell.
Description
Technical Field
The invention belongs to the technical field of high-temperature fuel cells, and relates to a molten carbonate fuel cell system based on hydrogen adsorption circulation and a working method thereof.
Background
The Molten Carbonate Fuel Cell (MCFC) is a high-temperature Fuel Cell working at 650 ℃, has the advantages of no need of noble metal as a catalyst, wide Fuel source, low noise, nearly zero emission of pollutants, high power generation efficiency, realization of combined heat and power supply and the like, is suitable for distributed power stations or fixed power stations of hundreds kilowatt level to megawatt level, and has good development prospect.
The electricity generation process of the molten carbonate fuel cell involves electrochemical reactions, wherein oxygen mainly absorbs electrons at a cathode to convert the electrons into positive ions, the positive ions and the carbon dioxide are subjected to electrochemical reactions to generate carbonate, the carbonate is conveyed to an anode through an electrolyte layer, the carbonate and hydrogen are subjected to electrochemical reactions at the anode to generate water and carbon dioxide, electrons are released, the released electrons are conveyed to the cathode through an external circuit to participate in the electrochemical reactions to generate the carbonate, and the electrons migrate in the external circuit to generate current, so that electric energy is generated.
Molten carbonate fuel cells have good fuel flexibility and can use methanol, natural gas, coal gas, hydrogen-rich gas, etc. as fuel, but the electrochemical reaction at the anode is essentially the reaction of hydrogen and carbonate, so that any fuel needs to be converted into hydrogen before the electrochemical reaction at the anode can generate electric energy and heat. The traditional gas conversion hydrogen production technology adopts a reaction mode of a fixed bed reactor, namely, fuel is preheated in the fixed bed reactor and is converted into hydrogen-containing mixed gas under the action of a catalyst, and hydrogen with higher purity is obtained by a pressure swing adsorption or wet decarburization method. The traditional fuel treatment method has complex process, and in order to avoid the overtemperature of a fixed bed, the fuel is gradually and completely converted into hydrogen by adopting a conversion method with multiple temperature sections and multiple concentration sections, and the problems of complex assembly system and low energy conversion efficiency caused by the temperature rise, purification and cooling of the hydrogen in the hydrogen production process are also caused; in addition, the anode reaction of the molten carbonate fuel cell is not complete reaction, a small part of hydrogen flows out of the anode without participating in the electrochemical reaction, and the traditional method is to mix and catalyze unreacted hydrogen and cathode tail gas for combustion so as to utilize the energy of the hydrogen.
Disclosure of Invention
In order to overcome the defects of complex molten carbonate fuel cell system, low energy conversion efficiency and low hydrogen fuel utilization rate in the prior art, the invention aims to provide a molten carbonate fuel cell system based on hydrogen adsorption cycle and a working method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a molten carbonate fuel cell system based on hydrogen adsorption circulation comprises a medium-temperature pressure swing adsorption hydrogen production device, a fuel cell reactor and a catalytic combustor;
the fuel cell reactor comprises a cathode part and an anode part which are positioned at two ends, and an electrolyte layer is arranged between the cathode part and the anode part;
the medium-temperature pressure swing adsorption hydrogen production device is provided with a hydrogen-rich gas outlet, an exhaust gas outlet and a raw material gas inlet, and the hydrogen-rich gas outlet is connected with the inlet of the anode part;
the outlet of the anode part is connected with a first heat exchanger; two channels are arranged in the first heat exchanger, the inlet of one channel is connected with the coal gas outlet of an externally-connected IGCC system gasification furnace, and the outlet of the channel is connected with the raw material gas inlet; the inlet of the other channel is connected with the outlet of the anode part, and the outlet of the channel is connected with the raw material gas inlet;
the exhaust gas outlet is connected to the inlet of the cathode section via a catalytic burner.
Preferably, a second heat exchanger is connected between the inlet of the anode portion and the hydrogen-rich gas outlet.
Preferably, the catalytic combustor is provided with an air inlet and a hydrogen-containing gas inlet, the air inlet is connected to the atmosphere, and the hydrogen-containing gas inlet is connected with the exhaust gas outlet.
Preferably, a third heat exchanger is mounted between the outlet of the catalytic burner and the inlet of the cathode section.
Further preferably, the third heat exchanger is provided with a desalted water inlet and a catalytic combustion gas inlet;
the catalytic combustion gas inlet is connected with the outlet of the catalytic combustor, and the desalted water inlet is connected with external desalted water;
a steam outlet and a heat exchange gas outlet are formed in the third heat exchanger;
the steam outlet is connected to the atmosphere, and the heat exchange gas outlet is connected with the inlet of the cathode part.
Preferably, the second heat exchanger is provided with two outlets and two inlets;
one inlet is connected with the hydrogen-rich gas outlet, and the other inlet is connected with the outlet of the cathode part;
an outlet connected to the inlet of the anode portion; the other is a tail gas outlet which is connected to the atmosphere.
Preferably, the first heat exchanger is provided with a passage connected to the outlet of the anode portion, the outlet of the passage is provided with a supercharger, and the outlet of the supercharger is connected to the feed gas inlet.
A working method of a molten carbonate fuel cell system based on hydrogen adsorption circulation comprises the following specific processes:
the coal gas in the gasification furnace of the IGCC system enters the medium-temperature pressure swing adsorption hydrogen production device after passing through the anode part of the fuel cell reactor, and the water-vapor transformation reaction, the hydrogen and the CO are generated in the medium-temperature pressure swing adsorption hydrogen production device2Separating to obtain pure hydrogen gas and small amount of H2Dehydrogenating gas and pure hydrogen gas by a catalytic combustor, then entering an anode part of a fuel cell reactor, and carrying out electrochemical reaction with carbonate of an electrolyte layer to generate raw material gasThe feed gas enters the medium-temperature pressure swing adsorption hydrogen production device again for H2With CO2Separation of (2) to form H2And CO2(ii) recycling of (d); containing a small amount of H2The exhaust gas enters a cathode part in a fuel cell reactor after being dehydrogenated by a catalytic combustor, reacts with oxygen from air at the cathode to generate carbonate, is transmitted to an anode part through an electrolyte layer, and is communicated with H of the anode part2Reaction to CO2And H2O, form CO2The recycling of (2).
Preferably, the tail gas comprises unreacted H2And CO formed by the reaction2And H2O；
Before entering a fuel cell reactor, firstly, exchanging heat for gas, wherein the gas temperature of a cathode part inlet and the gas temperature of an anode part inlet are both 500 ℃;
the gas temperature at the feed gas inlet of the medium-temperature pressure swing adsorption hydrogen production device is 270 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a molten carbonate fuel cell system based on hydrogen adsorption circulation, which is characterized in that CO and CH in coal gas synthesis gas of an IGCC system gasification furnace4The equal components are directly converted into H in the medium-temperature pressure swing adsorption hydrogen production device2And CO2，H2And CO2The gas is separated into more than 90 percent hydrogen-rich gas in a medium-temperature pressure swing adsorption hydrogen production device, and CO is obtained by separation2The gas contains a small amount of H2In a catalytic burner, H2All are removed, H is removed2Post-catalytic combustion of O2With CO2The proportion can meet the gas component requirement of the cathode of the cell stack. CO in anode tail gas2And unreacted H2Is pumped to the inlet of the medium temperature pressure swing adsorption device, separated again and circulated to the cell stack for electrochemical reaction to form H2And CO2The cycle of (2). The invention simplifies the fuel processing process flow of the molten carbonate fuel cell, and the anode tail gas is circulated to the medium-temperature pressure swing adsorption device to recover CO2And unreacted hydrogen to further improve the system efficiency of molten carbonate fuel cellsRate and performance. The invention aims to convert coal gas fuel into hydrogen-rich gas by improving medium-temperature pressure swing adsorption, and fully utilize the hydrogen by an anode hydrogen circulation method, thereby improving the overall efficiency of the system.
Further, the first heat exchanger reduces the temperature of the anode tail gas to 200-300 ℃ through heat exchange, the anode tail gas can be sent to a compressor for pressurization under the condition of lower temperature, and the coal gas is preheated to 270 ℃; the second heat exchanger can further raise the temperature of hydrogen-rich gas generated by medium-temperature pressure swing adsorption to 500 ℃ and then the hydrogen-rich gas enters the anode of the cell stack to participate in reaction; the third heat exchanger can cool the high-temperature gas with the temperature of 800-1000 ℃ after catalytic combustion to 500 ℃ through water cooling, and generate a certain amount of hot water or steam, so that the comprehensive efficiency of the system can be fully improved.
The invention also discloses a working method of the molten carbonate fuel cell system based on hydrogen adsorption circulation, which is completed based on the system, wherein coal gas in the gasification furnace of the IGCC system enters the medium-temperature pressure swing adsorption hydrogen production device after passing through the anode part of the fuel cell reactor, and water vapor transformation reaction and hydrogen and CO are generated in the medium-temperature pressure swing adsorption hydrogen production device2To obtain pure hydrogen gas and a small amount of H2Gas and pure hydrogen enter the anode of the cell stack after heat exchange and temperature rise, and are subjected to electrochemical reaction with carbonate of an electrolyte layer to generate tail gas, and the tail gas enters the medium-temperature pressure swing adsorption hydrogen production device again after heat exchange and pressurization to carry out H2With CO2Separation of (2) to form H2And CO2(ii) recycling of (d); containing a small amount of H2Dehydrogenating the gas with a catalytic combustor, feeding the gas into the cathode of a fuel cell reactor, reacting the gas with oxygen from the air at the cathode to generate carbonate, transferring the carbonate to the anode through an electrolyte layer, and reacting with H of the anode2Reaction to CO2And H2O, form CO2The recycling of (2). The method has simple process, and the device structure is easy to build, easy to implement and high in practicability.
Drawings
FIG. 1 is a schematic flow diagram of a molten carbonate fuel cell system based on hydrogen adsorption cycling according to the present invention;
wherein, 1-a first heat exchanger; 2-medium temperature pressure swing adsorption hydrogen production device; 3-a second heat exchanger; 4-a fuel cell reactor; 41-an anode portion; 42-an electrolyte layer; 43-a cathode portion; 5-a supercharger; 6-a catalytic burner; 7-third heat exchanger.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
Referring to fig. 1, a molten carbonate fuel cell system based on hydrogen adsorption cycle includes: the device comprises a medium-temperature pressure swing adsorption hydrogen production device 2, a second heat exchanger 3, a fuel cell reactor 4, a supercharger 5 and a catalytic combustor 6, wherein the number of the medium-temperature pressure swing adsorption hydrogen production device 2 is two. The medium temperature pressure swing adsorption hydrogen production device 2 is provided with a hydrogen-rich gas outlet, an exhaust gas outlet and a raw material gas inlet, the hydrogen-rich gas outlet is connected with the inlet of the anode part 41, and the exhaust gas outlet is connected with the inlet of the cathode part 43 through the catalytic combustor 6.
The outlet of the anode part 41 is connected with a first heat exchanger 1, two channels are arranged in the first heat exchanger 1, the inlet of one channel is connected with the coal gas outlet of an externally-connected IGCC system gasification furnace, and the outlet of the channel is connected with the feed gas inlet; the inlet of the other channel is connected to the outlet of the anode portion 41, and the outlet of the channel is connected to the raw material gas inlet.
The fuel cell reactor 4 includes a cathode portion 43 and an anode portion 41 at both ends, and an electrolyte layer 42 is provided between the cathode portion 43 and the anode portion 41; the inlet of the anode part 41 is connected with the outlet of the medium temperature pressure swing adsorption hydrogen production device 2 through the second heat exchanger 3.
Example 2
The contents are the same as those of example 1 except for the following.
The molten carbonate fuel cell system based on hydrogen adsorption cycle also comprises a first heat exchanger 1 and a third heat exchanger 7. A third heat exchanger 7 is installed between the outlet of the catalytic combustor 6 and the inlet of the cathode portion 43. A desalted water inlet and a catalytic combustion gas inlet are formed in the third heat exchanger 7; the catalytic combustion gas inlet is connected with the outlet of the catalytic combustor 6, and the desalted water inlet is connected with the external desalted water; a steam outlet and a heat exchange gas outlet are arranged on the third heat exchanger 7; the steam outlet is connected to the atmosphere and the heat exchange gas outlet is connected to the inlet of the cathode portion 43.
Example 3
The contents are the same as those of example 1 except for the following.
The catalytic combustor 6 is provided with an air inlet and a hydrogen-containing gas inlet, the air inlet is connected to the atmosphere, and the hydrogen-containing gas inlet is connected with an exhaust gas outlet on the medium-temperature pressure swing adsorption hydrogen production device 2. The exhaust gas outlet of the medium temperature pressure swing adsorption hydrogen production device 2 is connected with the inlet of the cathode part 43 after passing through the catalytic combustor 6 and the third heat exchanger 7 in sequence.
The first heat exchanger 1 is provided with two outlets, coal gas of an externally-connected IGCC system gasification furnace enters the medium temperature pressure swing adsorption device 2 after being preheated by the first heat exchanger 1, an outlet of the anode part 41 enters the compressor 5 for pressurization after being cooled by the first heat exchanger 1, and then enters the medium temperature pressure swing adsorption device 2 through a feed gas inlet.
The second heat exchanger 3 is provided with two outlets and two inlets; one inlet is connected to the hydrogen-rich gas outlet, and the other inlet is connected to the outlet of the cathode portion 43; one outlet is connected to the inlet of the anode portion 41; the other is a tail gas outlet which is connected to the atmosphere.
Example 4
A working method of a molten carbonate fuel cell system based on hydrogen adsorption circulation comprises the following specific processes:
the coal gas in the gasification furnace of the IGCC system enters the medium-temperature pressure swing adsorption hydrogen production device 2 after passing through the anode part 41 of the fuel cell reactor 4, and generates water vapor shift reaction and hydrogen and CO in the medium-temperature pressure swing adsorption hydrogen production device 22Separating to obtain pure hydrogen gas and small amount of H2The gas and pure hydrogen gas are dehydrogenated by the catalytic combustor 6 and enter the anode part 41 of the fuel cell reactor 4 to generate electrochemical reaction with carbonate of the electrolyte layer 42 to generate feed gas, and the feed gas enters the medium-temperature pressure swing adsorption hydrogen production device 2 again to carry out H2With CO2Separation of (2) to form H2And CO2(ii) recycling of (d); containing a small amount of H2The exhaust gas enters the cathode portion 43 of the fuel cell reactor 4 after being dehydrogenated by the catalytic combustor 6, reacts with oxygen from the air at the cathode to generate carbonate, and is transmitted to the anode portion 41 through the electrolyte layer 42, and then is mixed with H of the anode portion 41 to generate hydrogen2Reaction to CO2And H2O, form CO2The recycling of (2).
Example 5
The working method of the system specifically comprises the following steps: the coal gas in the gasification furnace of the IGCC system exchanges heat with the tail gas of the anode part 41 in the first heat exchanger 1, is heated and then enters the medium-temperature pressure swing adsorption hydrogen production device 2, and generates a water vapor transformation reaction and hydrogen and CO in the medium-temperature pressure swing adsorption hydrogen production device 22To obtain pure hydrogen gas and a small amount of H2Gas, pureThe hydrogen gas is heated by the second heat exchanger 3 and enters the anode part 41 of the fuel cell reactor 4, and reacts with carbonate of the electrolyte layer 42 to generate tail gas, wherein the tail gas comprises unreacted H2CO formed by the reaction2And H2O, the tail gas sequentially passes through the first heat exchanger 1 for cooling and the compressor 5 for pressurizing, then enters the raw material gas inlet of the adsorption hydrogen production device 2 again, and H in the tail gas of the anode part 41 is recovered2Generating hydrogen-rich gas with small amount of H2The gas enters a third heat exchanger 7 for heat exchange and temperature reduction after being subjected to catalytic combustion by a catalytic combustor 6, demineralized water is heated to generate steam and hot water, the cooled gas enters a cathode part 43 of a fuel cell reactor 4, wherein O is2And CO2React to generate CO3 2-Carbonate radical CO3 2-The electrochemical reaction occurs while moving to the stack anode 41 in the electrolyte layer 42 to generate electric energy and heat. The tail gas after the anode reaction of the fuel cell reactor 4 is cooled to 200 ℃ in the first heat exchanger 1, then sent to the supercharger 5 for boosting pressure, and then sent to the inlet of the medium temperature pressure swing adsorption hydrogen production device 2, and H in the tail gas of the anode part 412And CO2Separating again in the medium-temperature pressure swing adsorption hydrogen production device 2 to form H2And CO2Is recycled.
Example 6
The CO of the coal gas synthesis gas from the gasification furnace of the IGCC system is 55.85 percent; h225.66%; CH (CH)42900 ppm; 1.76% of carbon dioxide, N216.7 percent, the temperature is 138 ℃ and the pressure is 2.85MPa, the mixture sequentially enters the anode part 41 and the first heat exchanger 1, is heated to 270 ℃ and then is sent to the medium temperature pressure swing adsorption hydrogen production device 2, and CH in the coal gas synthesis gas in the medium temperature pressure swing adsorption hydrogen production device 24Reforming with CO and steam-gas shift reaction to generate H2With CO2，H2With CO2Separating in the medium temperature pressure swing adsorption hydrogen production device 2 to obtain hydrogen-rich gas with the concentration of more than 90%, heating the hydrogen-rich gas to 500 ℃ by the second heat exchanger 3 after passing through the tail gas of the cathode part 43 of the fuel cell reactor 4, and then entering the anode part 41 and the carbonate CO from the electrolyte layer 423 2-Electrochemical reaction to generate CO2And H2O, tail gas of an anode part 41 of the fuel cell reactor 4 is 650 ℃, the temperature of the tail gas is reduced to 200-300 ℃ in the first heat exchanger 1, the tail gas is sent to a supercharger 5 to be boosted to an inlet of the medium-temperature pressure swing adsorption hydrogen production device 2 to be boosted to 2.85MPa, then the tail gas enters the medium-temperature pressure swing adsorption hydrogen production device 2, and H in the tail gas of the anode part 41 is2And CO2Separating again in the medium-temperature pressure swing adsorption hydrogen production device 2 to form H2And CO2Is recycled. CO separated from medium temperature pressure-change adsorption hydrogen production device 22Containing a small amount of H2This gas is mixed with excess air in the catalytic burner 6 and reacted to remove H therefrom2The high-temperature gas after catalytic combustion enters a heat exchanger 7 to heat demineralized water to generate steam and hot water, and the gas after catalytic combustion is cooled to 500 ℃ and then enters a cathode part 43 of a fuel cell reactor 4, wherein O is2And CO2React to generate CO3 2-Carbonate radical CO3 2-Moves to the anode part 41 of the cell stack in the electrolyte layer 42 to generate electrochemical reaction, and N is on the cathode side2And unreacted small amount of O2And CO2And the temperature is reduced to 80 ℃ after heat exchange and then is discharged out of the system.
In conclusion, the coal gas directly generates water vapor conversion in the medium-temperature pressure swing adsorption hydrogen production device, and CO is directly converted into H2And CO2，H2And CO2The hydrogen-rich gas with the concentration of more than 90 percent is generated by separation in the medium-temperature pressure swing adsorption hydrogen production device. Containing a small amount of H2CO of2Gas in catalytic burner to convert H2Total removal of, catalytically combusted, O2With CO2The mixture ratio meets the gas component requirement of the cathode of the cell stack. CO in anode tail gas2And unreacted H2Is pumped to the inlet of the medium temperature pressure swing adsorption device, separated again and circulated to the cell stack for electrochemical reaction to form H2And CO2The efficiency and the performance of the system are improved.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A molten carbonate fuel cell system based on hydrogen adsorption circulation is characterized by comprising a medium-temperature pressure swing adsorption hydrogen production device (2), a fuel cell reactor (4) and a catalytic combustor (6);
the fuel cell reactor (4) comprises a cathode part (43) and an anode part (41) which are positioned at two ends, and an electrolyte layer (42) is arranged between the cathode part (43) and the anode part (41);
the medium-temperature pressure swing adsorption hydrogen production device (2) is provided with a hydrogen-rich gas outlet, an exhaust gas outlet and a raw material gas inlet, and the hydrogen-rich gas outlet is connected with the inlet of the anode part (41);
the outlet of the anode part (41) is connected with a first heat exchanger (1);
two channels are arranged in the first heat exchanger (1), the inlet of one channel is connected with the coal gas outlet of an externally-connected IGCC system gasification furnace, and the outlet of the channel is connected with the feed gas inlet; the inlet of the other channel is connected with the outlet of the anode part (41), and the outlet of the channel is connected with the raw material gas inlet;
the exhaust gas outlet is connected to the inlet of the cathode portion (43) via a catalytic burner (6).
2. The molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 1, characterized in that a second heat exchanger (3) is connected between the inlet of the anode portion (41) and the hydrogen rich gas outlet.
3. The molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 1, wherein the catalytic combustor (6) is provided with an air inlet connected to the atmosphere and a hydrogen-containing gas inlet connected to the exhaust gas outlet.
4. The molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 1, characterized in that a third heat exchanger (7) is installed between the outlet of the catalytic combustor (6) and the inlet of the cathode section (43).
5. The molten carbonate fuel cell system based on hydrogen absorption cycle according to claim 4, characterized in that the third heat exchanger (7) is provided with a desalted water inlet and a catalytic combustion gas inlet;
the catalytic combustion gas inlet is connected with the outlet of the catalytic combustor (6), and the desalted water inlet is connected with external desalted water;
a steam outlet and a heat exchange gas outlet are arranged on the third heat exchanger (7);
the steam outlet is connected to the atmosphere, and the heat exchange gas outlet is connected to the inlet of the cathode part (43).
6. The molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 2, characterized in that the second heat exchanger (3) is provided with two outlets and two inlets;
one inlet is connected with the hydrogen-rich gas outlet, and the other inlet is connected with the outlet of the cathode part (43);
one outlet is connected with the inlet of the anode part (41); the other is a tail gas outlet which is connected to the atmosphere.
7. The molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 1, wherein a booster (5) is installed on a channel of the first heat exchanger (1) connected to the outlet of the anode portion (41), and the outlet of the booster (5) is connected to the feed gas inlet.
8. The operation method of the molten carbonate fuel cell system based on hydrogen adsorption cycle according to any one of claims 1 to 7, characterized by comprising the following steps:
the coal gas in the gasification furnace of the IGCC system enters the medium-temperature pressure swing adsorption hydrogen production device (2) after passing through an anode part (41) of a fuel cell reactor (4), and a water-vapor transformation reaction, hydrogen and CO are generated in the medium-temperature pressure swing adsorption hydrogen production device (2)2Separating to obtain pure hydrogen gas and small amount of H2The gas and pure hydrogen enter an anode part (41) of a fuel cell reactor (4) after being dehydrogenated by a catalytic combustor (6) to generate electrochemical reaction with carbonate of an electrolyte layer (42) to generate raw material gas, and the raw material gas enters a medium-temperature pressure swing adsorption hydrogen production device (2) again to carry out H2With CO2Separation of (2) to form H2And CO2(ii) recycling of (d); containing a small amount of H2The exhaust gas enters a cathode part (43) in a fuel cell reactor (4) after being dehydrogenated by a catalytic combustor (6), reacts with oxygen from air at the cathode to generate carbonate, is transmitted to an anode part (41) through an electrolyte layer (42), and is communicated with H of the anode part (41)2Reaction to CO2And H2O, form CO2The recycling of (2).
9. The method of claim 8, wherein the off-gas comprises unreacted H2And CO formed by the reaction2And H2O。
10. The operating method of a molten carbonate fuel cell system based on hydrogen adsorption cycle according to claim 8, wherein the gas is first heat-exchanged before entering the fuel cell reactor (4), and the gas temperature at the inlet of the cathode part (43) and the inlet of the anode part (41) are both 500 ℃;
the gas temperature at the feed gas inlet of the medium-temperature pressure swing adsorption hydrogen production device (2) is 270 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114142583A (en) * | 2021-10-29 | 2022-03-04 | 西安交通大学 | Hybrid power supply system |
| CN115466637A (en) * | 2022-09-15 | 2022-12-13 | 西安交通大学 | Fuel cell power generation system and method for coupling biomass energy and solar energy |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09330731A (en) * | 1996-04-11 | 1997-12-22 | Mitsui Petrochem Ind Ltd | Method for recovering and fixing carbon dioxide gas, nitrogen gas and argon gas in fuel cell power generation |
| CN104377375A (en) * | 2014-11-03 | 2015-02-25 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification molten carbonate fuel cell power generating system |
| CN106025313A (en) * | 2016-07-15 | 2016-10-12 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification fuel cell power generation system capable of realizing CO2 trapping before combustion |
| CN107829826A (en) * | 2017-11-21 | 2018-03-23 | 中国华能集团清洁能源技术研究院有限公司 | One kind three circulates type coal gasification melting carbonate fuel cell generation system and method |
| CN109301283A (en) * | 2018-09-28 | 2019-02-01 | 中国华能集团清洁能源技术研究院有限公司 | A kind of band CO2The integral coal gasification fuel cell system of trapping |
| CN111480254A (en) * | 2017-10-11 | 2020-07-31 | 沙特***石油公司 | For capturing high purity CO in hydrocarbon facilities2Method and system of |
| CN111613819A (en) * | 2020-06-22 | 2020-09-01 | 中国华能集团清洁能源技术研究院有限公司 | Composite fuel cell power generation system with near zero emission of carbon dioxide and power generation method thereof |
| CN111916789A (en) * | 2020-07-17 | 2020-11-10 | 哈尔滨锅炉厂有限责任公司 | Molten carbonate fuel cell and biomass gasification coupling power generation system and method |
-
2021
- 2021-04-25 CN CN202110449702.8A patent/CN113224359A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09330731A (en) * | 1996-04-11 | 1997-12-22 | Mitsui Petrochem Ind Ltd | Method for recovering and fixing carbon dioxide gas, nitrogen gas and argon gas in fuel cell power generation |
| CN104377375A (en) * | 2014-11-03 | 2015-02-25 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification molten carbonate fuel cell power generating system |
| CN106025313A (en) * | 2016-07-15 | 2016-10-12 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification fuel cell power generation system capable of realizing CO2 trapping before combustion |
| CN111480254A (en) * | 2017-10-11 | 2020-07-31 | 沙特***石油公司 | For capturing high purity CO in hydrocarbon facilities2Method and system of |
| CN107829826A (en) * | 2017-11-21 | 2018-03-23 | 中国华能集团清洁能源技术研究院有限公司 | One kind three circulates type coal gasification melting carbonate fuel cell generation system and method |
| CN109301283A (en) * | 2018-09-28 | 2019-02-01 | 中国华能集团清洁能源技术研究院有限公司 | A kind of band CO2The integral coal gasification fuel cell system of trapping |
| CN111613819A (en) * | 2020-06-22 | 2020-09-01 | 中国华能集团清洁能源技术研究院有限公司 | Composite fuel cell power generation system with near zero emission of carbon dioxide and power generation method thereof |
| CN111916789A (en) * | 2020-07-17 | 2020-11-10 | 哈尔滨锅炉厂有限责任公司 | Molten carbonate fuel cell and biomass gasification coupling power generation system and method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114142583A (en) * | 2021-10-29 | 2022-03-04 | 西安交通大学 | Hybrid power supply system |
| CN115466637A (en) * | 2022-09-15 | 2022-12-13 | 西安交通大学 | Fuel cell power generation system and method for coupling biomass energy and solar energy |
| CN115466637B (en) * | 2022-09-15 | 2024-03-22 | 西安交通大学 | Fuel cell power generation system and method for coupling biomass energy and solar energy |
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