CN113054229A - Solid oxide fuel cell power generation system and method based on ethanol fuel - Google Patents
Solid oxide fuel cell power generation system and method based on ethanol fuel Download PDFInfo
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- CN113054229A CN113054229A CN202110266630.3A CN202110266630A CN113054229A CN 113054229 A CN113054229 A CN 113054229A CN 202110266630 A CN202110266630 A CN 202110266630A CN 113054229 A CN113054229 A CN 113054229A
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04701—Temperature
- H01M8/04738—Temperature of auxiliary devices, e.g. reformer, compressor, burner
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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
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
Abstract
The invention discloses a solid oxide fuel cell power generation system and a method based on ethanol fuel, the system comprises a fuel storage heating bin provided with a water bath heating system, an air source communicated with an air pipe, a reformer used for carrying out partial oxidation reforming reaction, a cell stack consisting of tubular solid oxide fuel cells and a power converter electrically connected with the cell stack, wherein the fuel storage heating bin is filled with ethanol-water mixed liquid, the air pipe extends into the bottom of the mixed liquid, the interior of the fuel storage heating bin is communicated with an inlet of the reformer through a first pipeline, an outlet of the reformer is communicated with an anode air passage in the cell stack through a second pipeline, a cathode air passage of the reformer is communicated with external air, and the cell stack outputs direct current outwards and supplies power to an external load after being converted by the power converter; the ethanol fuel cell can directly convert chemical energy of ethanol into electric energy, is not limited by Carnot cycle efficiency, and is high in power generation efficiency, noiseless in power generation process, portable, environment-friendly and high in fuel utilization rate.
Description
Technical Field
The invention relates to the field of ethanol utilization, in particular to a solid oxide fuel cell power generation system and method based on ethanol fuel.
Background
With the increasingly prominent contradiction between the development of economic society and the shortage of energy, environmental pollution and the like, fuel cells gradually enter our lives as a green power supply with high energy density and little pollution. The conventional batteries such as lithium ion batteries and zinc-air batteries have long charging time, low energy density, short service life, environmental pollution and can not meet the requirements of the development of portable electronic products, so that the research on portable small-sized fuel cells has important significance in various fields of ecological environment and life. The small fuel cell is light and has high energy density, but the small fuel cell has poor integration compatibility with electrical appliances, and besides meeting the output high power density, how to organically integrate the fuel cell stack and the energy unit of the fuel device to form a small power supply is a difficult problem which needs to be solved at present, and how to improve the electrical performance of the fuel cell is one of the most concerned problems.
The solid oxide fuel cell is an all-solid-state clean and efficient energy conversion device, can directly convert chemical energy in fuel into electric energy, has high power generation efficiency (more than 50 percent), does not generate gas pollutants such as nitrogen oxides and noise pollution, has higher energy efficiency and higher specific energy compared with lithium batteries, zinc batteries, lead-acid batteries and the like, does not need to be charged for a long time, has clean energy, no pollution and light weight and small volume, and is called one of the most promising new energy materials. Compared with other types of fuel cells, the fuel cell does not need noble metals as catalysts, has no advantages of osmotic corrosion and the like, and particularly can directly use hydrocarbons such as natural gas, water gas, biomass gas and the like as fuels, thereby avoiding the problems of difficult storage and transportation, high safety and high cost requirements and the like caused by using hydrogen as a single fuel source. As a renewable energy source, the biomass is an ideal alternative energy source of coal, petroleum, natural gas and the like, and can relieve the problems of fossil energy shortage, environmental pollution and the like. Ethanol, as one of the biomass, has the advantages of high energy density, environmental friendliness, abundant resources, renewability and the like. Therefore, the combination of the ethanol fuel and the tubular solid oxide fuel cell can realize the construction of a small-sized fuel power supply cell, and is an ideal green energy source.
Disclosure of Invention
In view of the technical deficiencies, the present invention provides a solid oxide fuel cell power generation system and method based on ethanol fuel, which directly converts the chemical energy of ethanol into electric energy, is not limited by carnot cycle efficiency, has high power generation efficiency, generates no noise in the power generation process, is portable and environment-friendly, and has high fuel utilization rate.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a solid oxide fuel cell power generation system based on ethanol fuel, which comprises a fuel storage heating bin provided with a water bath heating system, an air source communicated with an air pipe, a reformer used for carrying out partial oxidation reforming reaction, a cell stack consisting of tubular solid oxide fuel cells and a power converter electrically connected with the cell stack, the fuel storage heating bin is filled with mixed liquid of ethanol and water, the air pipe penetrates through the upper end cover of the fuel storage heating bin and extends into the bottom of the mixed liquid, the interior of the fuel storage heating bin is also communicated with an inlet of a reformer through a first pipeline, an outlet of the reformer is communicated with an anode air passage in the cell stack through a second pipeline, the cathode air flue of the reformer is communicated with the outside air, and the cell stack outputs direct current outwards, converts the direct current through the power converter and supplies power to an external load for operation.
Preferably, the cell stack comprises 5-10 single cell tubes arranged in parallel, and the operation temperature of the cell stack is 650-800 ℃.
Preferably, the support anode of the tubular solid oxide fuel cell in the cell stack is NiO-YSZ, and the thickness of the support anode layer is 500-2000 μm; the electrolyte is YSZ, and the thickness of the electrolyte is 10-20 μm; the support cathode is LSCF-GDC, and the thickness of the support cathode is 40-50 μm; the length of the tubular solid oxide fuel cell is more than or equal to 100mm, and the outer diameter of the tubular solid oxide fuel cell is more than or equal to 8 mm.
The invention also provides a power generation method of the solid oxide fuel cell based on the ethanol fuel, which comprises the following steps:
s1, firstly, mixing ethanol and water in the fuel storage heating bin according to a certain proportion to form a mixed solution, and reserving a certain space between the mixed solution and an upper end cover of the fuel storage heating bin; the molar ratio of the ethanol to the water in the mixed solution is 1:1-3: 1;
s2, heating the mixed liquid in the fuel storage heating bin by using a water bath heating system to maintain the temperature of the mixed liquid at 42.69-61.86 ℃, wherein the partial pressure proportion of ethanol steam is 20-50%;
s3, connecting an air pipe, enabling outside air to enter mixed liquid along the air pipe, enabling fuel steam in the fuel storage heating bin to enter the reformer along a first pipeline by taking the air as a carrier, and further performing partial oxidation reforming reaction to generate fuel mixed by H2, CO and CH 4; the reformer obtains fuel and releases heat to maintain the working temperature of the reformer;
the reformer adopts Ni-Al2O3 as a catalyst, and the partial oxidation reforming reaction of ethanol steam under the action of the catalyst is as follows:
CH3CH2OH+3H2O→2CO2+6H2
CH3CH2OH+H2O→2CO+4H2
CH3CH2OH+3O2→2CO2+3H2O
with simultaneous water gas shift reaction: CO + H2O→CO2+H2；
S4, enabling the fuel to enter an anode air passage in the cell stack through a second pipeline to participate in the electrochemical reaction, and meanwhile, conveying outside air to a cathode air passage of the cell stack to participate in the electrochemical reaction;
and S5, generating electric energy by the cell stack, outputting direct current outwards, converting the direct current by the power converter and supplying power to an external load for operation.
Preferably, in step S3, the air flow of the trachea is 50-70 mL-min-1In the meantime.
Preferably, in step S3, the reformer is operated at a temperature of 500 ± 50 ℃.
The invention has the beneficial effects that:
(1) the invention directly converts the chemical energy of ethanol into electric energy, is not limited by Carnot cycle efficiency, has high power generation efficiency and no noise in the power generation process, and obtains the tail gas of H2O and CO2And almost no pollution is caused.
(2) The invention directly uses the heat released when ethanol is partially oxidized and reformed to maintain the working temperature of the tubular solid oxide fuel cell, does not use an external power supply, reduces the complexity of the system, reduces the cost, is convenient for integrating a cell stack with higher power density, supplies power to a load through the power converter, and realizes portability and environmental protection.
(3) The tubular solid oxide fuel cell has the advantages of high temperature rise, high starting speed, good lifting and heating stability and simple sealing, and a single solid oxide fuel cell tube is sealed into a small electric pile to realize the portable movement of a small power station.
(4) The reformer of the present invention uses Ni-Al2O3The catalyst can promote partial oxidation reforming of ethanol to generate CO and H2、CH4And the like, which are easy to participate in the electrochemical reaction, and improve the fuel utilization rate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic connection diagram of an ethanol fuel-based solid oxide fuel cell power generation system according to an embodiment of the present invention.
FIG. 2 is a graph of InP-1/T in step S2 of an ethanol fuel-based solid oxide fuel cell power generation method provided by an embodiment of the invention.
Description of reference numerals:
1. an air tube; 2. a fuel storage heating bin; 3. a reformer; 4. a cell stack; 5. a power converter.
Detailed Description
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.
As shown in FIG. 1, a solid oxide fuel cell power generation system based on ethanol fuel comprises a fuel storage heating bin 2 provided with a water bath heating system, an air source 1 communicated with an air pipe, a reformer 3 used for carrying out partial oxidation reforming reaction, a cell stack 4 composed of tubular solid oxide fuel cells and a power converter 5 electrically connected with the cell stack 4, the fuel storage heating bin 2 is filled with mixed liquid of ethanol and water, the air pipe penetrates through the upper end cover of the fuel storage heating bin 2 and extends into the bottom of the mixed liquid, the interior of the fuel storage heating bin 2 is also communicated with an inlet of a reformer 3 through a first pipeline, an outlet of the reformer 3 is communicated with an anode air passage in a cell stack 4 through a second pipeline, the cathode air passage of the reformer 3 is communicated with the outside air, and the cell stack 4 outputs direct current to the outside, converts the direct current by the power converter 5 and supplies power to an external load for operation.
The cell stack 4 comprises 5-10 single cell tubes which are arranged in parallel, and the operating temperature of the cell stack 4 is 650-800 ℃.
The support anode of the tubular solid oxide fuel cell in the cell stack 4 is NiO-YSZ, and the thickness of the support anode layer is 500-2000 μm; the electrolyte is YSZ, and the thickness of the electrolyte is 10-20 μm; the support cathode is LSCF-GDC, and the thickness of the support cathode is 40-50 μm; the length of the tubular solid oxide fuel cell is more than or equal to 100mm, and the outer diameter of the tubular solid oxide fuel cell is more than or equal to 8 mm.
The embodiment of the invention also provides a power generation method of the solid oxide fuel cell based on the ethanol fuel, which comprises the following steps:
s1, firstly, mixing ethanol and water in the fuel storage heating bin 2 according to a certain proportion to form a mixed solution, and reserving a certain space between the mixed solution and an upper end cover of the fuel storage heating bin 2; avoiding the water-alcohol ratio of carbon deposition according to a ternary C-H-O diagram, wherein the range is 1:1-10:1, and considering that products of oxidation reforming of ethanol can change due to different ratios and the requirements of SOFC (solid oxide fuel cell) on fuel, the molar ratio of ethanol to water in the mixed solution is set to be 1:1-3: 1;
s2, heating the mixed liquid in the fuel storage heating bin 2 by using a water bath heating system, and keeping the temperature of the mixed liquid between 42.69 and 61.86 ℃ and the partial pressure proportion of ethanol steam between 20 and 50 percent; the integration of InP- Δ H is performed according to the Clapelon-Clausis equationmSelecting the temperature and the saturated vapor pressure of a plurality of experimental points, drawing an InP-1/T image, referring to a figure 2, and fitting to obtain the saturated vapor pressure of the ethanol vapor at each temperature;
s3, connecting the trachea, wherein the air flow of the trachea is 50-70 mL/min-1Meanwhile, the outside air enters the mixed liquid along the air pipe, the fuel steam in the fuel storage heating bin 2 enters the reformer 3 along the first pipeline by taking the air as a carrier, and the partial oxidation reforming reaction is further carried out to generate the fuel mixed by H2, CO and CH 4; the reformer 3 receives fuel and simultaneously emits heat for maintaining its own operating temperature; the reformer 3 was operated at a temperature of 500 ± 50 ℃.
The reformer 3 adopts Ni-Al2O3As a catalyst, the partial oxidation reforming reaction of ethanol steam under the action of the catalyst is as follows:
CH3CH2OH+3H2O→2CO2+6H2
CH3CH2OH+H2O→2CO+4H2
CH3CH2OH+3O2→2CO2+3H2O
with simultaneous water gas shift reaction: CO + H2O→CO2+H2；
S4, the fuel enters the anode air passage in the cell stack 4 through the second pipeline to participate in the electrochemical reaction, and meanwhile, the external air is conveyed to the cathode air passage of the cell stack 4 to participate in the electrochemical reaction;
and S5, generating electric energy by the cell stack 4, outputting direct current outwards, converting the direct current by the power converter 5 and supplying power to an external load for operation.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A solid oxide fuel cell power generation system based on ethanol fuel is characterized by comprising a fuel storage heating bin (2) provided with a water bath heating system, an air source (1) communicated with an air pipe, a reformer (3) used for carrying out partial oxidation reforming reaction, a cell stack (4) composed of tubular solid oxide fuel cells and a power converter (5) electrically connected with the cell stack (4), wherein the fuel storage heating bin (2) is filled with mixed liquid of ethanol and water, the air pipe penetrates through the upper end cover of the fuel storage heating bin (2) and extends into the bottom of the mixed liquid, the interior of the fuel storage heating bin (2) is also communicated with an inlet of the reformer (3) through a first pipeline, an outlet of the reformer (3) is communicated with an anode air passage in the cell stack (4) through a second pipeline, and a cathode air passage of the reformer (3) is communicated with outside air, the battery stack (4) outputs direct current outwards, and the direct current is converted by the power converter (5) and then supplies power to an external load for operation.
2. An ethanol fuel based solid oxide fuel cell power generation system according to claim 1, wherein the cell stack (4) comprises 5-10 single cell tubes arranged in parallel, and the operating temperature of the cell stack (4) is 650-800 ℃.
3. The ethanol fuel-based solid oxide fuel cell power generation system of claim 1, wherein the support anode of the tubular solid oxide fuel cell in the stack (4) is NiO-YSZ, and the thickness of the support anode layer is 500-2000 μm; the electrolyte is YSZ, and the thickness of the electrolyte is 10-20 μm; the support cathode is LSCF-GDC, and the thickness of the support cathode is 40-50 μm; the length of the tubular solid oxide fuel cell is more than or equal to 100mm, and the outer diameter of the tubular solid oxide fuel cell is more than or equal to 8 mm.
4. The solid oxide fuel cell power generation method based on the ethanol fuel is characterized by comprising the following steps:
s1, firstly, mixing ethanol and water in the fuel storage heating bin (2) according to a certain proportion to form a mixed solution, wherein a certain space is reserved between the mixed solution and the upper end cover of the fuel storage heating bin (2), and the molar ratio of the ethanol to the water in the mixed solution is 1:1-3: 1;
s2, heating the mixed liquor in the fuel storage heating bin (2) by using a water bath heating system, and keeping the temperature of the mixed liquor between 42.69 and 61.86 ℃ and the partial pressure proportion of ethanol steam between 20 and 50 percent;
s3, connecting an air pipe, enabling outside air to enter mixed liquid along the air pipe, enabling fuel steam in the fuel storage heating bin (2) to enter the reformer (3) along a first pipeline by taking the air as a carrier, and further performing partial oxidation reforming reaction to generate H2、CO、CH4A mixed fuel; the reformer (3) receives fuel while emitting heat for maintaining its own operating temperature;
the reformer (3) adopts Ni-Al2O3As a catalyst, the partial oxidation reforming reaction of ethanol steam under the action of the catalyst is as follows:
CH3CH2OH+3H2O→2CO2+6H2
CH3CH2OH+H2O→2CO+4H2
CH3CH2OH+3O2→2CO2+3H2O
with simultaneous water gas shift reaction: CO + H2O→CO2+H2；
S4, enabling the fuel to enter an anode air passage in the cell stack (4) through a second pipeline to participate in the electrochemical reaction, and meanwhile, conveying outside air to a cathode air passage of the cell stack (4) to participate in the electrochemical reaction;
s5, the battery stack (4) generates electric energy and outputs direct current outwards, and the direct current is converted by the power converter (5) and then supplies power to an external load for operation.
5. The power generation method of the ethanol fuel-based solid oxide fuel cell as claimed in claim 4, wherein in step S3, the air flow of the air pipe is 50-70 mL-min-1In the meantime.
6. The power generation method of the ethanol fuel-based solid oxide fuel cell as claimed in claim 4, wherein the operation temperature of the reformer (3) in step S3 is 500 ± 50 ℃.
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Citations (5)
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| JP2001080904A (en) * | 1999-09-08 | 2001-03-27 | Fuji Electric Co Ltd | Fuel reformer |
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| BRPI0901921A2 (en) * | 2009-06-17 | 2011-02-22 | Inst Alberto Luiz De Coimbra De Pos Graduacao E Pesquisas De Engenharia Coppe Ufrj | process for direct oxidation and / or internal ethanol reforming, solid oxide fuel cell used for direct oxidation and / or internal ethanol reforming, catalyst and multifunctional electrocatalyst anode for direct oxidation and / or internal ethanol reforming |
| CN107302100A (en) * | 2017-07-31 | 2017-10-27 | 北京理工大学 | A kind of hydrogen fuel cell system and its electricity-generating method based on hydrogen from ethanol reforming |
| CN109546189A (en) * | 2018-10-29 | 2019-03-29 | 南京航空航天大学 | It is a kind of to reform electricity generation system by the multistage of fuel cell hydrogen source of liquid fuel |
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2021
- 2021-03-11 CN CN202110266630.3A patent/CN113054229B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001080904A (en) * | 1999-09-08 | 2001-03-27 | Fuji Electric Co Ltd | Fuel reformer |
| CN101771161A (en) * | 2008-12-29 | 2010-07-07 | 中国科学院宁波材料技术与工程研究所 | Portable power generation device for solid oxide fuel cell |
| BRPI0901921A2 (en) * | 2009-06-17 | 2011-02-22 | Inst Alberto Luiz De Coimbra De Pos Graduacao E Pesquisas De Engenharia Coppe Ufrj | process for direct oxidation and / or internal ethanol reforming, solid oxide fuel cell used for direct oxidation and / or internal ethanol reforming, catalyst and multifunctional electrocatalyst anode for direct oxidation and / or internal ethanol reforming |
| CN107302100A (en) * | 2017-07-31 | 2017-10-27 | 北京理工大学 | A kind of hydrogen fuel cell system and its electricity-generating method based on hydrogen from ethanol reforming |
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| WENCHAOSONG ET AL.: "Characterization and polarization DRT analysis of direct ethanol solid oxide fuel cells using low fuel partial pressures", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
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