CN114014269B - Proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production - Google Patents
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- C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
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Abstract
The invention relates to the technical field of resource integration, in particular to a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production. The invention provides a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production, which comprises a methanol reforming hydrogen production system, a hydrogen permeable alloy membrane system and a proton exchange membrane fuel cell system which are sequentially connected. The invention is a novel efficient combined system which takes preparation, storage and utilization of hydrogen energy and a proton exchange membrane fuel cell as the core and combines a hydrogen permeation alloy membrane separation and purification technology, and can realize the co-production of methanol reforming and the fuel cell.
Description
Technical Field
The invention relates to the technical field of resource integration, in particular to a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production.
Background
Because the fuel cell can be matched with the fuel oil and gas system which is widely distributed at present, the fuel cell has wide application prospect in many fields, wherein hydrogen is the most ideal fuel. However, when hydrogen is used as a fuel of a battery, the safety of storing and transporting high-pressure pure hydrogen is very low, and the cost is high, which is one of the important bottlenecks in realizing large-scale application. The methanol is an ideal hydrogen carrier, the aim of hydrogen production can be realized only by methanol steam reforming, and the conventional hydrogen production by reforming needs low temperature, low cost, high hydrogen-carbon ratio and convenient storage and transportation. Based on this, the western countries have invested a lot of efforts to research methanol reforming fuel cells to realize the poly-generation and rational utilization of coal-based methanol. However, the gas generated by reforming methanol also includes a certain amount of impurity gases besides hydrogen, and the proton exchange membrane fuel cell has a severe requirement on the purity of hydrogen, so that the current co-production technology of methanol reforming and fuel cells is not mature enough.
Disclosure of Invention
The invention aims to provide a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production, which can realize the co-production of methanol reforming and a fuel cell.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production, which comprises a methanol reforming hydrogen production system, a hydrogen permeable alloy membrane system and a proton exchange membrane fuel cell system which are sequentially connected;
the hydrogen permeable alloy membrane system includes a heat exchanger 210, a superheater 220, and a hydrogen permeable alloy membrane 230;
the proton exchange membrane fuel cell system comprises an air preheater 310 and a proton exchange membrane fuel cell stack;
the proton exchange membrane fuel cell stack comprises more than or equal to 1 proton exchange membrane fuel cell 320;
the proton exchange membrane fuel cell 320 comprises an anode 321, an electrolyte 323 and a cathode 322;
the methanol reforming hydrogen production system, the heat exchanger 210, the superheater 220 and the hydrogen permeable alloy membrane 230 are sequentially connected through a pipeline to form a methanol synthesis gas passage;
the hydrogen permeable alloy membrane 230, the heat exchanger 210, the air preheater 310 and the anode 321 are connected in sequence through a pipeline to form a hydrogen passage;
the air preheater 310 and the cathode 322 are connected by a pipe to form an air passage.
Preferably, the methanol reforming hydrogen production system comprises a methanol solution preheater 110 and a methanol reforming reactor 120 which are connected in sequence;
the methanol reforming reactor 120 is connected to the heat exchanger 210.
Preferably, the methanol reforming hydrogen production system further comprises a solar heat collector 130;
the solar collector 130 is connected to the methanol solution preheater 110 and the methanol reforming reactor 120, respectively.
Preferably, the hydrogen permeable alloy membrane system further includes a burner 240, a first heat supply unit 250, and a second heat supply unit 260;
the burner 240 is connected with the hydrogen permeable alloy membrane 230 through a pipe to form a gas passage;
the burner 240, the superheater 220 and the first heat supply device 250 are connected through pipes to form a heat path;
the second heating means 260 is located between the heat exchanger 210 and the air preheater 310.
Preferably, the proton exchange membrane fuel cell system further comprises a power generation device 330, an afterburner 340 and a third heat supply device 350;
the proton exchange membrane fuel cell stack, the afterburner 340 and the third heat supply device 350 are connected in sequence;
the afterburner chamber 340 is respectively connected with the cathode 322 and the anode 321 of the proton exchange membrane fuel cell stack through gas pipelines.
Preferably, the material of the hydrogen permeable alloy membrane (230) is a palladium alloy.
Preferably, when the number of the proton exchange membrane fuel cells 320 in the proton exchange membrane fuel cell stack is greater than or equal to 2, each proton exchange membrane fuel cell is electrically connected in parallel or in series.
The invention provides a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production, which comprises a methanol reforming hydrogen production system, a hydrogen permeable alloy membrane system and a proton exchange membrane fuel cell system which are sequentially connected; the hydrogen permeable alloy membrane system includes a heat exchanger 210, a superheater 220, and a hydrogen permeable alloy membrane 230; the proton exchange membrane fuel cell system comprises an air preheater 310 and a proton exchange membrane fuel cell stack; the proton exchange membrane fuel cell stack comprises more than or equal to 1 proton exchange membrane fuel cell 320; the proton exchange membrane fuel cell 320 comprises an anode 321, an electrolyte 323 and a cathode 322; the methanol reforming hydrogen production system, the heat exchanger 210, the superheater 220 and the hydrogen permeable alloy membrane 230 are sequentially connected through pipelines to form a methanol synthesis gas passage; the hydrogen permeable alloy membrane 230, the heat exchanger 210, the air preheater 310 and the anode 321 are connected in sequence through a pipeline to form a hydrogen passage; the air preheater 310 and the cathode 322 are connected by a pipe to form an air passage. The invention is a novel high-efficiency combined system which takes preparation, storage and utilization of hydrogen energy and a proton exchange membrane fuel cell as the core and combines a hydrogen permeation alloy membrane separation and purification technology, and the system has the following advantages:
1) The reasonable, efficient and clean utilization of the methanol is realized, and the fuel supply of a combined system taking a proton exchange membrane fuel cell and a hydrogen permeable alloy membrane as cores is realized by reforming the methanol;
2) The system is based on the characteristics of high yield of hydrogen production by reforming methanol and hydrogen utilization of a proton exchange membrane fuel cell, and combines the characteristic of good purification performance of a hydrogen permeable alloy membrane, so that the combined system has the characteristics of better energy conservation, economy and the like, and is a high-efficiency power generation system capable of outputting more electric power;
3) The combined system is combined with a hydrogen permeable alloy membrane subsystem, can improve the purity of hydrogen, is used for generating electricity of a proton exchange membrane fuel cell, has the characteristics of flexible control, compact structure and capability of coupling the requirements of different industrial productions on energy supply and energy consumption, and realizes the purpose of co-production;
4) The combined system fundamentally solves the problems of transportation of pure hydrogen and fuel cost, improves the energy density of fuel, and can effectively prolong the service life of electrode materials.
Drawings
FIG. 1 is a proton exchange membrane fuel cell integrated system for hydrogen production based on solar thermochemical methanol reforming according to the invention;
wherein, 110 methanol solution preheater, 120 methanol reforming reactor, 130 solar heat collector, 210 heat exchanger, 220 superheater, 230 hydrogen permeable alloy membrane, 240 burner, 250 first heat supply device, 260 second heat supply device, 310 air preheater, 320 proton exchange membrane fuel cell, 321 anode, 322 cathode, 323 electrolyte, 330 power generation device, 340 afterburner, 350 third heat supply device, 210-1 first methanol synthetic gas inlet, 210-2 first methanol synthetic gas outlet, 210-3 first hydrogen inlet, 210-4 first hydrogen outlet, 220-1 second methanol synthesis gas inlet, 220-2 second methanol synthesis gas outlet, 220-3 first heat inlet, 220-4 first heat outlet, 230-1 third methanol synthesis gas inlet, 230-2 second hydrogen outlet, 230-3 impurity gas outlet, 310-1 first air inlet, 310-2 first air outlet, 310-3 third hydrogen inlet, 310-4 third hydrogen outlet, 322-1 second air inlet, 322-2 second air outlet, 321-1 fourth hydrogen inlet, 321-2 fourth hydrogen outlet, 340-1 fourth hydrogen inlet, and 340-2 third air inlet.
Detailed Description
The invention provides a proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production, which comprises a methanol reforming hydrogen production system, a hydrogen permeable alloy membrane system and a proton exchange membrane fuel cell system which are sequentially connected;
the hydrogen permeable alloy membrane system includes a heat exchanger 210, a superheater 220, and a hydrogen permeable alloy membrane 230;
the proton exchange membrane fuel cell system comprises an air preheater 310 and a proton exchange membrane fuel cell stack;
the proton exchange membrane fuel cell stack comprises more than or equal to 1 proton exchange membrane fuel cell 320;
the proton exchange membrane fuel cell 320 comprises an anode 321, an electrolyte 323 and a cathode 322;
the methanol reforming hydrogen production system, the heat exchanger 210, the superheater 220 and the hydrogen permeable alloy membrane 230 are sequentially connected through pipelines to form a methanol synthesis gas passage;
the hydrogen permeable alloy membrane 230, the heat exchanger 210, the air preheater 310 and the anode 321 are connected in sequence through a pipeline to form a hydrogen passage;
the air preheater 310 and the cathode 322 are connected by a pipe to form an air passage.
In the present invention, the supply of syngas, hydrogen and air through the hydrogen permeable alloy membrane 230 and the pem fuel cell 320 is preferably performed in a top-layer cycle or a bottom-layer cycle.
In the present invention, the material of the hydrogen permeable alloy membrane (230) is preferably a palladium alloy; the palladium alloy used in the present invention is not particularly limited, and a palladium alloy having a hydrogen permeation function, which is well known to those skilled in the art, may be used.
As one embodiment of the present invention, the methanol reforming hydrogen production system includes a methanol solution preheater 110 and a methanol reforming reactor 120 connected in sequence;
the methanol reforming reactor 120 is connected to the heat exchanger 210.
As a specific embodiment of the present invention, the methanol reforming hydrogen production system further includes a solar heat collector 130;
the solar collector 130 is connected to the methanol solution preheater 110 and the methanol reforming reactor 120, respectively.
In the invention, in the methanol reforming hydrogen production system, a methanol aqueous solution firstly enters the methanol solution preheater 110 for heating, and then the methanol aqueous solution after temperature rise is conveyed to the methanol reforming reactor 120 for methanol steam reforming to obtain a synthesis gas; in the methanol steam reforming process, the medium-low temperature energy provided by the solar heat collector 130 is effectively utilized to prepare hydrogen, so that the benefit is maximized; meanwhile, the whole combined system cannot be influenced by the problems of poor solar reliability, discontinuity and the like in operation. The synthesis gas comprises carbon dioxide, carbon monoxide, hydrogen and water. The source of methanol in the aqueous methanol solution is not particularly limited, and industrial methanol (i.e., methanol prepared from fossil fuels such as coal-based fuels), natural gas, atomized fuel oil, or the like, which is well known to those skilled in the art, may be used.
As a specific embodiment of the present invention, the hydrogen permeable alloy membrane system further includes a burner 240, a first heat supplying means 250, and a second heat supplying means 260;
the burner 240 is connected with the hydrogen permeable alloy membrane 230 through a pipe to form a gas passage;
the burner 240, the superheater 220 and the first heat supply device 250 are connected through pipes to form a heat path;
the second heating means 260 is located between the heat exchanger 210 and the air preheater 310.
As an embodiment of the present invention, the heat exchanger 210 comprises a first methanol synthesis gas inlet 210-1, a first methanol synthesis gas outlet 210-2, a first hydrogen inlet 210-3, and a first hydrogen outlet 210-4;
the superheater 220 comprises a second methanol syngas inlet 220-1, a second methanol syngas outlet 220-2, a first heat inlet 220-3, and a first heat outlet 220-4;
the hydrogen permeable alloy membrane 230 includes a third methanol synthesis gas inlet 230-1, a second hydrogen outlet 230-2, and an impurity gas outlet 230-3;
in the invention, the path of the methanol synthesis gas enters a heat exchanger 210 through a first methanol synthesis gas inlet 210-1 for heat exchange, then enters the superheater 220 through a first methanol synthesis gas outlet 210-2 and a second methanol synthesis gas inlet 220-1 for continuous heat absorption, enters a hydrogen permeable alloy membrane 230 through a second methanol synthesis gas outlet 220-2 and a third methanol synthesis gas inlet 230-1 for hydrogen separation, the separated hydrogen enters the heat exchanger 210 through a second hydrogen outlet 230-2 and a first hydrogen inlet 210-3 for heat exchange by utilizing the temperature difference between the hydrogen and the methanol synthesis gas, and provides partial heat for separating the methanol synthesis gas; the impure gas separated by the hydrogen permeable alloy membrane 230 enters the burner 240 through the impure gas outlet 230-3 to be burnt to provide heat for absorbing heat of the methanol synthesis gas in the superheater 220, and the residual heat is output by the first heat supply device 250. In the present invention, the burner 240 and the first heat supply device 250 are arranged to provide heat for maintaining the operating temperature of the hydrogen permeable alloy membrane, and can be further used for supplying heat to realize cogeneration, thereby improving the energy utilization efficiency of the system.
As an embodiment of the present invention, the air preheater 310 includes a first air inlet 310-1, a first air outlet 310-2, a third hydrogen inlet 310-3, and a third hydrogen outlet 310-4;
the cathode 322 includes a second air inlet 322-1 and a second air outlet 322-2;
the anode 321 includes a fourth hydrogen inlet 321-1 and a fourth hydrogen outlet 321-2.
In the present invention, after the hydrogen gas heat-exchanged by the heat exchanger 210 enters the second heat supply device 260 through the first hydrogen outlet 210-4, enters the air preheater 310 through the third hydrogen inlet 310-4 and preheats the air by heat-exchanging with the air entering through the first air inlet 310-1, the hydrogen gas heat-exchanged sequentially enters the anode 321 through the third hydrogen outlet 310-4 and the fourth air inlet 321-1, the air heat-exchanged sequentially enters the cathode 322 through the first air outlet 310-2 and the second air inlet 322-1, and an electrochemical reaction occurs in the pem fuel cell 320 to generate a current.
In the invention, when the number of the proton exchange membrane fuel cells 320 in the proton exchange membrane fuel cell stack is not less than 2, each proton exchange membrane fuel cell is electrically connected in parallel or in series.
As an embodiment of the present invention, the pem fuel cell system further includes a power generation unit 330, an afterburner 340 and a third heat supply unit 350;
the proton exchange membrane fuel cell stack, the afterburner 340 and the third heat supply device 350 are connected in sequence;
the afterburner chamber 340 is respectively connected with the cathode 322 and the anode 321 of the proton exchange membrane fuel cell stack through gas pipelines. In the present invention, the post-combustion chamber 340 and the third heating device 350 are arranged to realize further heat release and utilization of the anode tail gas. The present invention does not have any particular limitation on the power generation device 330, and a power generation set known to those skilled in the art may be used, so that the power generation device 330 realizes the output of electric energy.
As an embodiment of the present invention, the power generation device is electrically connected to the pem fuel cell 320.
As a specific embodiment of the present invention, the afterburner chamber 340 comprises a fourth air inlet 340-1 and a third air inlet 340-2;
the fourth hydrogen outlet 321-2 is connected to the fourth hydrogen inlet 340-1;
the second air outlet 322-2 is connected to the third air inlet 340-2.
In the present invention, the unreacted hydrogen in the anode 321 sequentially passes through the fourth hydrogen outlet 321-2 and the fourth hydrogen inlet 340-1 to enter the post-combustion chamber 340, the unreacted air in the cathode 322 sequentially passes through the second air outlet 322-2 and the third air inlet 340-2 to enter the post-combustion chamber 340 for mixed combustion, and the generated heat is output through the third heat supply device 350.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A proton exchange membrane fuel cell combined system based on solar thermochemical methanol reforming hydrogen production is characterized by comprising a methanol reforming hydrogen production system, a hydrogen permeable alloy membrane system and a proton exchange membrane fuel cell system which are sequentially connected;
the hydrogen permeable alloy membrane system comprises a heat exchanger (210), a superheater (220), and a hydrogen permeable alloy membrane (230);
the proton exchange membrane fuel cell system comprises an air preheater (310) and a proton exchange membrane fuel cell stack;
the proton exchange membrane fuel cell group comprises more than or equal to 1 proton exchange membrane fuel cell (320);
the proton exchange membrane fuel cell (320) comprises an anode (321), an electrolyte (323) and a cathode (322);
the methanol reforming hydrogen production system, the heat exchanger (210), the superheater (220) and the hydrogen permeable alloy membrane (230) are sequentially connected through pipelines to form a methanol synthesis gas passage;
the hydrogen permeable alloy membrane (230), the heat exchanger (210), the air preheater (310) and the anode (321) are connected in sequence through pipelines to form a hydrogen passage;
the air preheater (310) and the cathode (322) are connected through a pipeline to form an air passage;
the hydrogen permeable alloy membrane system further comprises a burner (240), a first heat supply means (250), and a second heat supply means (260);
the burner (240) is connected with the hydrogen permeable alloy membrane (230) through a pipeline to form a gas passage;
the burner (240), the superheater (220) and the first heat supply device (250) are connected through pipelines to form a heat path;
the second heating device (260) is disposed between the heat exchanger (210) and the air preheater (310).
2. A proton exchange membrane fuel cell combined system for solar thermochemical methanol reforming to produce hydrogen according to claim 1, wherein the methanol reforming hydrogen production system comprises a methanol solution preheater (110) and a methanol reforming reactor (120) which are connected in sequence;
the methanol reforming reactor (120) is connected to the heat exchanger (210).
3. A pem fuel cell integrated system based on solar thermo-chemical methanol reforming for hydrogen production according to claim 1, wherein said methanol reforming hydrogen production system further comprises a solar collector (130);
the solar heat collector (130) is respectively connected with the methanol solution preheater (110) and the methanol reforming reactor (120).
4. A pem fuel cell integrated system based on solar thermo-chemical methanol reforming for hydrogen production according to claim 1 further comprising a power generation device (330), an afterburner (340) and a third heat supply device (350);
the proton exchange membrane fuel cell stack, the afterburner (340) and the third heat supply device (350) are connected in sequence;
and the afterburner (340) is respectively connected with a cathode (322) and an anode (321) in the proton exchange membrane fuel cell stack through gas pipelines.
5. A pem fuel cell integrated system based on solar thermo-chemical methanol reforming for hydrogen production according to claim 1 where the hydrogen permeable alloy membrane (230) is made of palladium alloy.
6. The proton exchange membrane fuel cell combination system for hydrogen production by solar thermochemical methanol reforming as claimed in claim 1, wherein when the number of proton exchange membrane fuel cells 320 in the proton exchange membrane fuel cell stack is greater than or equal to 2, each proton exchange membrane fuel cell is electrically connected in parallel or in series.
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| CN114538375B (en) * | 2022-04-22 | 2022-08-09 | 河北氢联新能源科技有限公司 | Methanol liquid phase reforming hydrogen production device and method and power supply system |
| CN115477281A (en) * | 2022-10-25 | 2022-12-16 | 浙江本源醇氢科技有限公司 | Combined cooling heating and power device based on methanol hydrogen production |
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| US6541142B1 (en) * | 2000-10-04 | 2003-04-01 | General Motors Corporation | Fuel cell system having a methanol decomposition reactor |
| CN205944261U (en) * | 2016-08-25 | 2017-02-08 | 晋城市阿邦迪能源有限公司 | Methanol reforming reactor and small -size fuel cell power generation system |
| CN109004244A (en) * | 2018-07-09 | 2018-12-14 | 中国石油大学(北京) | Solid oxide fuel cell association system based on solar energy preparing hydrogen by reforming methanol |
| CN211719720U (en) * | 2020-04-09 | 2020-10-20 | 宁波洁程汽车科技有限公司 | Universal reforming fuel cell system |
| CN113285093A (en) * | 2021-05-14 | 2021-08-20 | 中国人民解放军海军工程大学 | Fuel cell-solar power generation system based on methanol steam reforming |
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