CN112186227A - Method for generating electricity by using medium-high temperature fuel cell from low-concentration coal bed gas - Google Patents
Method for generating electricity by using medium-high temperature fuel cell from low-concentration coal bed gas Download PDFInfo
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- CN112186227A CN112186227A CN202011099142.XA CN202011099142A CN112186227A CN 112186227 A CN112186227 A CN 112186227A CN 202011099142 A CN202011099142 A CN 202011099142A CN 112186227 A CN112186227 A CN 112186227A
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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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
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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
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell reactants
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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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- 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 belongs to the technical field of clean and efficient utilization of low-concentration coal bed gas, and particularly relates to a method for generating power from low-concentration coal bed gas by using a high-temperature fuel cell. Aiming at the problems that the power generation efficiency is low because the existing low-concentration coal bed gas is generated by an internal combustion engine, the invention builds a fixed bed catalytic device; then putting a certain amount of catalyst in the middle of the reactor, and putting the reactor in a catalytic furnace, wherein the catalyst is positioned in the middle of the catalytic furnace; then building a medium-high temperature fuel cell power generation device; finally, connecting a gas outlet of the fixed bed catalytic device with an inlet of a high-temperature fuel cell power generation device, and reducing the catalyst in the fixed bed reaction device in situ; the flow of the reaction gas is controlled by the mass flow controller, the total flow of the low-concentration coal bed gas is set, the raw gas is introduced into the catalytic reaction device, and the heating furnace of the fixed bed catalytic device and the heating furnace of the high-temperature fuel cell power generation device are heated, so that the power generation can be realized.
Description
Technical Field
The invention belongs to the technical field of clean and efficient utilization of low-concentration coal bed gas, and particularly relates to a method for generating power from low-concentration coal bed gas by using a high-temperature fuel cell.
Background
The low-concentration coal bed gas is a mixture of methane and air, and the concentration of the methane changes with different extraction modes and different extraction environments. The methane concentration of 5-16% belongs to the explosive range, the pressurization and the transportation are easy to explode, the serious potential safety hazard exists, and the low-concentration coal bed gas can be only converted in situ. At present, low-concentration coal bed gas in coal mines in China is mainly used for combustion power generation. The combustion temperature of methane reaches 1600 ℃, and a large amount of nitrogen oxides and the like are easily generated by high-temperature combustion, so that the frequency of PM2.5 is caused. In addition, the national coal mine safety administration stipulates that the construction conditions of the coal bed gas power station are that the pumping and discharging amount of the coal bed gas is 100 ten thousand cubic meters per year, and the concentration of the coal bed gas is between 6 and 25 percent. The coal bed gas cannot be utilized to generate electricity in mines with scattered geographic positions and small gas flow, and most of the coal bed gas is discharged in an ineffective combustion mode. At present, the power generation of low-concentration coal bed gas below 30% mainly adopts an internal combustion engine to generate power, the conversion of fuel from chemical energy to heat energy and mechanical energy to electric energy is limited by Carnot cycle, and the power generation efficiency is low and is about 27-40%. In addition, due to the influence of the fluctuation of the methane concentration, the blending technology of the coal bed gas with high and low concentrations is required to be utilized. Concentration is also one of the utilization modes of low-concentration coal bed gas, but the low-concentration coal bed gas has low methane content and contains a large amount of oxygen, and if the low-concentration coal bed gas is directly purified and concentrated, explosion hidden troubles exist in the processing process. The method is an effective means for purifying low-concentration coal bed gas by adopting a chemical combustion method for deoxidation, but the method is substituted by sacrificing a certain amount of methane, is only suitable for places with heat energy requirements, has limited improved concentration and cannot completely accord with the 'construction of a clean low-carbon, safe and efficient modern energy system' advocated by our country.
In conclusion, although the low-concentration coal bed gas resources in China are rich, the number and the level of practical utilization are very limited, a large amount of ineffective combustion emission causes serious resource waste and environmental pollution, and a clean and efficient energy utilization technology is urgently needed.
The Solid Oxide Fuel Cell (SOFC) is a novel power generation device, chemical energy of fuel is directly converted into electric energy, the power generation efficiency is over 45 percent, and if cogeneration is adopted, the energy utilization efficiency can be over 80 percent. Because the fuel cell has NO combustion process and NO intermediate medium of mechanical energy and heat energy, the system has low operation noise, high efficiency, low pollution and NOxEmission of less than 4mg/m3(6％O2Standard state of) It is considered as the fourth generation energy source following thermal power, hydroelectric power and nuclear power. The SOFC can be assembled according to the size of an air source and the requirement of a user by a modular assembly mode, and is particularly suitable for distributed energy supply. The existing SOFC based on the nickel-based anode has good power generation performance when hydrogen is directly used as fuel, and a hydrocarbon direct fuel cell (hereinafter referred to as a hydrocarbon direct-combustion cell) is still in the initial stage. If the hydrocarbon is in direct contact with the cell anode, severe carbon deposition can occur at the anode, causing damage to the cell system.
Disclosure of Invention
Aiming at the current situation that the utilization rate of the existing low-concentration coal bed gas is low, the invention provides a method for generating power by utilizing the low-concentration coal bed gas through a medium-high temperature fuel cell, so that clean and efficient utilization of the low-concentration coal bed gas is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for generating power by using medium-high temperature fuel cells from low-concentration coal bed gas comprises the following steps:
step 1, building a fixed bed catalytic device;
step 2, taking a catalyst to be placed in the middle of the reactor, placing the reactor in a catalytic furnace, and placing the catalyst in the middle of the catalytic furnace;
step 3, building a medium-high temperature fuel cell power generation device;
step 4, connecting a gas outlet of the fixed bed catalytic device with an inlet of a high-temperature fuel cell power generation device;
step 5, reducing the catalyst in the fixed bed reaction device in situ; the flow of the reaction gas is controlled by the mass flow controller, the total flow of the low-concentration coal bed gas is set, the raw gas is introduced into the catalytic reaction device, and the heating furnace of the fixed bed catalytic device and the heating furnace of the high-temperature fuel cell power generation device are heated, so that the power generation can be realized.
Further, step 1, a fixed bed catalytic device is built and comprises a heating furnace, a reactor, a catalyst, a thermocouple and a temperature controller. The method comprises the step of building a catalytic oxidation reaction device of the low-concentration coal bed gas. Through the step, methane and air in the low-concentration coal bed gas are converted into carbon monoxide and hydrogen. The two gases can be used as fuel gas for a subsequent solid oxide fuel cell.
Further, the catalyst in the step 2 is Ni-BaO-CeO2-ZrO2。
Further, the high-temperature fuel cell power generation device in the step 3 comprises a solid oxide fuel cell, a heating furnace, a thermocouple and a temperature controller. The step is to build a power generation device. In the step, the gas flowing out of the catalytic oxidation reaction device directly generates electricity by using the solid oxide fuel cell, and the efficiency is high. The fuel gas and the air generate electrochemical reaction in the solid oxide fuel cell device, the process is not limited by Carnot cycle efficiency, and the power generation efficiency is high.
Further, the temperature of the in-situ reduction in the step 5 is 800 ℃; the time for in situ reduction was 2 h.
Further, the temperature raising method of the heating furnace of the fixed bed catalytic device in the step 5 is 10 ℃ min-1The rate of temperature rise of (2) is increased to 750 ℃.
Further, the heating furnace temperature raising method of the high temperature fuel cell power generation device in the step 5 is 10 ℃ min-1The rate of temperature rise to the fuel cell operating temperature.
Compared with the prior art, the invention has the following advantages:
the method of the invention utilizes the solid oxide fuel cell to generate electricity from the low-concentration coal bed gas, has high generating efficiency and has no pollution to the environment in the utilization process. And the solid oxide fuel cell can be operated in a modularized way, and the power generation scale can be adjusted along with the gas quantity.
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 invention, and that for a person skilled in the art, other drawings can be obtained from the provided drawings without inventive effort.
FIG. 1 is a schematic diagram of power generation of low-concentration coal bed gas by an external reformer catalytic oxidation-solid oxide fuel cell provided by an embodiment of the invention;
FIG. 2 is a graph showing the catalytic oxidation performance of NBCZ catalyst in an example of the present invention in a range of 30% methane to 70% air;
FIG. 3 is a graph of the catalytic oxidation stability test of NBCZ catalyst for 30% methane-70% air in an example of the present invention;
FIG. 4 is a graph of performance testing of 30% low concentration coal bed methane generated by solid oxide fuel cells in an embodiment of the present invention;
FIG. 5 is a graph illustrating a test of power generation stability of 30% low-concentration coal bed gas using a solid oxide fuel cell in an embodiment of the present invention;
FIG. 6 is a graph showing the catalytic oxidation performance of NBCZ catalyst in the example of the present invention against 25% methane-75% air;
fig. 7 is a graph of performance tests of 25% low concentration coal bed gas power generation using solid oxide fuel cells in an example of the present invention.
Detailed Description
Example 1
Taking a quartz tube as a reactor, and Ni-BaO-CeO2-ZrO2(NBCZ) is a low-concentration coal-bed gas catalytic oxidation catalyst, and the solid oxide fuel cell (the cell structure is Ni-Ce)0.8Sm0.2O1.9(SDC)/SDC /Ba0.5Sr0.5Co0.8Fe0.2O3-ζSDC) for medium and high temperature fuel cells, low concentration coal bed gas with 30% methane-70% air analog concentration.
Firstly, building a fixed bed reaction device;
secondly, weighing 0.2g of catalyst with 40-60 meshes and 0.4g of quartz sand, uniformly mixing and loading the mixture in the middle of a reactor;
thirdly, building a solid oxide fuel cell device;
fourthly, connecting a gas outlet of the fixed bed catalytic device with an inlet of a high-temperature fuel cell power generation device;
fifthly, the catalyst in the fixed bed reaction device is reacted with H at 800 DEG C2And reducing in situ for 2 h. The flow rate of the reaction gas was controlled by a mass flow controller, and the total flow rate of the low-concentration coalbed methane gas containing 30% methane was set to 60 mL-min-1. Introducing the raw material gas into a catalytic reaction device at 10 ℃ per minute-1The temperature rise rate is increased to 750 ℃, the concentrations of methane, carbon monoxide, carbon dioxide and hydrogen in tail gas at different temperatures are tested by using a gas chromatograph, and the conversion efficiency of the catalyst on low-concentration coal bed gas is analyzed;
and sixthly, testing the electrochemical performance of the solid oxide fuel cell by adopting a four-electrode method. Before the test, H was continuously introduced2Gas flow rate of 80 mL/min-1At 10 ℃ min-1The temperature rise rate is increased to 650 ℃, and 100 mL/min is used after the gas flow rate and the temperature are stable-1Purging with Ar for 10min, and introducing 30% of the tail gas low-concentration coal bed gas reformed in the catalytic reaction device into a battery for electrochemical performance test.
Example 2
Taking a quartz tube as a reactor, and Ni-BaO-CeO2-ZrO2(NBCZ) is a low-concentration coal-bed gas catalytic oxidation catalyst, and the solid oxide fuel cell (the cell structure is Ni-Ce)0.8Sm0.2O1.9(SDC)/SDC /Ba0.5Sr0.5Co0.8Fe0.2O3-ζSDC) for medium and high temperature fuel cells, simulating low concentration coal bed gas with 25% methane-75% air concentration.
Firstly, building a fixed bed reaction device;
secondly, weighing 0.2g of catalyst with 40-60 meshes and 0.4g of quartz sand, uniformly mixing and loading the mixture in the middle of a reactor;
thirdly, building a solid oxide fuel cell device;
fourthly, connecting a gas outlet of the fixed bed catalytic device with an inlet of a high-temperature fuel cell power generation device;
fifthly, the catalyst in the fixed bed reaction device is reacted with H at 800 DEG C2And reducing in situ for 2 h. The flow rate of the reaction gas was controlled by a mass flow controller, and the total flow rate of the 25% methane low-concentration coal bed gas was set to 60 mL-min-1. Introducing the raw material gas into a catalytic reaction device at 10 ℃ per minute-1The temperature rise rate is increased to 750 ℃, the concentrations of methane, carbon monoxide, carbon dioxide and hydrogen in tail gas at different temperatures are tested by using a gas chromatograph, and the conversion efficiency of the catalyst on low-concentration coal bed gas is analyzed.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all inventions utilizing the inventive concept are protected.
Claims (7)
1. A method for generating power by using medium-high temperature fuel cells from low-concentration coal bed gas is characterized by comprising the following steps: the method comprises the following steps:
step 1, building a fixed bed catalytic device;
step 2, taking a catalyst to be placed in the middle of the reactor, placing the reactor in a catalytic furnace, and placing the catalyst in the middle of the catalytic furnace;
step 3, building a medium-high temperature fuel cell power generation device;
step 4, connecting a gas outlet of the fixed bed catalytic device with an inlet of a high-temperature fuel cell power generation device;
step 5, reducing the catalyst in the fixed bed reaction device in situ; the flow of the reaction gas is controlled by the mass flow controller, the total flow of the low-concentration coal bed gas is set, the raw gas is introduced into the catalytic reaction device, and the heating furnace of the fixed bed catalytic device and the heating furnace of the high-temperature fuel cell power generation device are heated, so that the power generation can be realized.
2. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: and step 1, building a fixed bed catalytic device, wherein the fixed bed catalytic device comprises a heating furnace, a reactor, a catalyst, a thermocouple and a temperature controller.
3. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: the catalyst in the step 2 is Ni-BaO-CeO2-ZrO2。
4. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: and the high-temperature fuel cell power generation device in the step 3 comprises a solid oxide fuel cell, a heating furnace, a thermocouple and a temperature controller.
5. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: the temperature of the in-situ reduction in the step 5 is 800 ℃; the time for in situ reduction was 2 h.
6. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: the heating method of the heating furnace of the fixed bed catalytic device in the step 5 is 10 ℃ min-1The rate of temperature rise of (2) is increased to 750 ℃.
7. The method for generating power by using the medium-high temperature fuel cell from the low-concentration coal bed gas according to claim 1, characterized by comprising the following steps: the heating furnace temperature rising method of the high-temperature fuel cell power generation device in the step 5 is 10 ℃ per minute-1The rate of temperature rise to the fuel cell operating temperature.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201789030U (en) * | 2010-08-02 | 2011-04-06 | 无锡诚信碳材料科技有限公司 | Zero emission hydrogen manufacturing, power generating and carbon producing device |
| CN104064788A (en) * | 2014-06-18 | 2014-09-24 | 河南理工大学 | Fuel battery thermoelectric cascade system capable of increasing energy utilization rate of coal bed gas |
| CN208062174U (en) * | 2018-02-08 | 2018-11-06 | 上海中弗新能源科技有限公司 | A kind of coal bed gas distribution SOFC electricity generation systems |
| CN110600766A (en) * | 2019-08-20 | 2019-12-20 | 上海竣铭化工工程设计有限公司 | Cogeneration method and device for solid oxide fuel cell and process heating furnace |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201789030U (en) * | 2010-08-02 | 2011-04-06 | 无锡诚信碳材料科技有限公司 | Zero emission hydrogen manufacturing, power generating and carbon producing device |
| CN104064788A (en) * | 2014-06-18 | 2014-09-24 | 河南理工大学 | Fuel battery thermoelectric cascade system capable of increasing energy utilization rate of coal bed gas |
| CN208062174U (en) * | 2018-02-08 | 2018-11-06 | 上海中弗新能源科技有限公司 | A kind of coal bed gas distribution SOFC electricity generation systems |
| CN110600766A (en) * | 2019-08-20 | 2019-12-20 | 上海竣铭化工工程设计有限公司 | Cogeneration method and device for solid oxide fuel cell and process heating furnace |
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