CN112864432A - System and method for generating power by using synthesis gas high-temperature fuel cell - Google Patents
System and method for generating power by using synthesis gas high-temperature fuel cell Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- 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
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- 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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
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- 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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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
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Abstract
The invention relates to the field of battery power generation, and discloses a synthetic gas fuel cell power generation system which comprises a synthetic gas source, a heat exchange device, a fuel cell and a combustion device, wherein the synthetic gas source is used for providing synthetic gas; the heat exchange device comprises a heat exchange conversion device, a first heat exchange device and a second heat exchange device; the heat exchange conversion device is connected with the anode of the fuel cell through a first heat exchange device; the cathode of the fuel cell is connected with the combustion device; the combustion device is connected with the cathode of the fuel cell through a second heat exchange device. The power generation system of the synthetic gas fuel cell provided by the invention has simple flow, improves the hydrogen partial pressure, reduces the heat productivity of the synthetic gas fuel cell in the power generation process, reasonably utilizes the heat of the system and improves the power generation efficiency of the fuel cell when the system is used for power generation.
Description
Technical Field
The invention relates to the field of battery power generation, in particular to a synthesis gas high-temperature fuel cell power generation system and a method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) power generation system is a clean and efficient energy conversion system, which uses gaseous hydrocarbons such as natural gas or hydrogen, carbon monoxide and the like as raw materials and can convert chemical energy in Fuel into electric energy. By means of a natural gas pipe network which is widely distributed, the SOFC power generation system can be integrated into a distributed power station which takes natural gas as a raw material in a large scale, so that the power demand of buildings, plants, communities and the like is met, and the commercial prospect is good.
In the prior art, a solid oxide fuel cell generally uses natural gas as a raw material, and generates gas such as hydrogen, carbon monoxide gas and the like through reforming, the gas enters a cell stack anode, cathode air enters a cell stack cathode, and under a certain condition, the anode gas and the cathode gas react to generate water and generate electricity. To accomplish these processes, various kit components such as a reformer, a start-up burner, an anode tailgas burner, a heat exchanger, etc. are required. The components need to be well combined to form an organic whole so that the flow of the material flow and the energy flow can be carried out. For example, CN106784940A discloses a solid oxide fuel cell power generation system, which includes a hot zone, a reformer, a start-up burner, an anode tail gas burner, a mixer, and a heat exchange component, wherein the hot zone includes a stack array and corresponding gas distribution pipelines, the reformer, the heat exchange component and the hot zone are separately disposed and connected to each other through pipelines, the heat exchange component includes a reforming feed preheater, an air primary preheater, an air secondary preheater, a gasifier and a condenser, and a reforming reserved air inlet is disposed on the mixer. The invention separately sets each main component instead of concentrating in the hot area, reduces the difficulty of combining each component, is convenient for overall layout, reduces the possibility of mutual cross influence, and is convenient for each component to stably exert the function; the device has the advantages of reasonable structural layout, convenience in assembly, convenience in disassembly, proper layout, stable function, reasonable heat exchange and the like, and is suitable for building a single hundred-kilowatt-level solid oxide fuel cell power generation system.
However, since the conventional solid oxide fuel cell power generation system mainly uses natural gas as a raw material, a methane reformer or the like needs to be provided, and thus it is not applicable to an inexpensive synthesis gas.
Disclosure of Invention
The invention aims to solve the problem of low power generation efficiency of a solid oxide fuel cell power generation system used for synthesis gas in the prior art, and provides a synthesis gas fuel cell power generation system and a synthesis gas fuel cell power generation method.
In order to achieve the above object, a first aspect of the present invention provides a synthesis gas fuel cell power generation system, which includes a synthesis gas source, a heat exchange device, a fuel cell, and a combustion device, wherein the synthesis gas source is used for providing synthesis gas; the heat exchange device comprises a heat exchange conversion device, a first heat exchange device and a second heat exchange device; the heat exchange conversion device is connected with the anode of the fuel cell through a first heat exchange device; the cathode of the fuel cell is connected with the combustion device; the combustion device is connected with the cathode of the fuel cell through a first heat exchange device.
A second aspect of the invention provides a method of generating electricity from a syngas fuel cell, wherein the method comprises the steps of:
mixing synthesis gas provided by a synthesis gas source with steam, preheating the mixture to a first temperature by a heat exchange conversion device, and then carrying out water gas conversion reaction to prepare mixed fuel gas containing hydrogen and carbon monoxide;
the mixed fuel gas is heated to a second temperature by the first heat exchange device, enters the anode of the fuel cell, reacts with air which is heated by the second heat exchange device and enters the cathode of the fuel cell, generates power and respectively generates anode tail gas and cathode tail gas;
and the cathode tail gas enters a combustion device to be combusted to generate combustion tail gas.
Through the technical scheme, the synthesis gas fuel cell power generation system and the power generation method provided by the invention have the following beneficial effects:
the battery power generation system provided by the invention does not need to be cooled, condensed and dewatered, is directly mixed and combusted with high-temperature cathode air at a higher temperature, ensures the combustion stability, and simultaneously does not need to be additionally provided with a starting burner, thereby simplifying the system flow.
To achieve efficient syngas generation. The invention converts CO in the synthesis gas into H through water gas shift reaction2Meanwhile, carbon dioxide is separated and then sent to the high-temperature fuel cell for power generation, so that the hydrogen partial pressure in the power generation process of the synthesis gas fuel cell is improved, the heat productivity in the power generation process of the synthesis gas fuel cell is reduced, the heat of the system is reasonably utilized, and the power generation efficiency of the fuel cell is improved.
Drawings
FIG. 1 is a syngas fuel cell power generation system according to the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a synthesis gas fuel cell power generation system, which comprises a synthesis gas source, a heat exchange device, a fuel cell and a combustion device, wherein the synthesis gas source is used for providing synthesis gas; the heat exchange device comprises a heat exchange conversion device, a first heat exchange device and a second heat exchange device; the heat exchange conversion device is connected with the anode of the fuel cell through a first heat exchange device; the cathode of the fuel cell is connected with the combustion device; the combustion device is connected with the cathode of the fuel cell through a second heat exchange device.
In the invention, the inventor researches and discovers that as the carbon-hydrogen ratio in the synthesis gas is far larger than that of the natural gas, the heat generated in the power generation process of the solid oxide fuel cell is higher than that of the natural gas by more than 50%, so that the power generation efficiency of the solid oxide fuel cell system taking the natural gas as the raw material gas is low when the solid oxide fuel cell system is directly applied to the synthesis gas.
The invention takes the synthesis gas as the raw material gas, improves the solid oxide fuel cell system and provides the solid oxide fuel cell system suitable for the synthesis gas. In the solid oxide fuel cell system provided by the invention, a starting burner is not required to be additionally arranged, and the flow of the system is greatly simplified.
According to the invention, the heat exchange device further comprises a third heat exchange device which is respectively connected with the second heat exchange device and the heat exchange conversion device and used for supplying low-pressure steam to the heat exchange conversion device.
According to the invention, the heat exchange conversion device is internally provided with a conversion reaction catalyst for converting carbon monoxide in the synthesis gas into hydrogen.
Because the shift reaction of the synthesis gas can generate a large amount of heat, the invention carries out the shift reaction in the heat exchange shift device before the synthesis gas enters the anode of the fuel cell, and releases the heat generated by the shift reaction of the synthesis gas outside the fuel cell in advance, thereby obviously reducing the heat release of the fuel cell, simultaneously reducing the air input of the cathode of the fuel cell and obviously improving the power generation power of the fuel cell.
In the invention, the synthesis gas is subjected to water gas shift reaction to convert CO in the synthesis gas into H2And meanwhile, the heat generated by the reaction is utilized to further realize the heating treatment of the gas, and compared with the prior art, the load and the cost of a heat exchange device in the synthesis gas fuel cell power generation system are reduced.
According to the invention, the system further comprises CO2A separator connected with the heat exchange conversion device and the first heat exchange device respectively for reducing CO in the anode feed gas2The content of (a).
According to the invention, the third heat exchange device is a steam generator.
A second aspect of the invention provides a method of generating electricity from a syngas fuel cell, wherein the method comprises the steps of:
mixing synthesis gas provided by a synthesis gas source with steam, preheating the mixture to a first temperature by a heat exchange conversion device, and carrying out water gas conversion reaction to prepare mixed fuel gas containing hydrogen and carbon monoxide;
the mixed fuel gas is heated to a second temperature by the first heat exchange device, enters the anode of the fuel cell, reacts with air which is heated by the second heat exchange device and enters the cathode of the fuel cell, generates power and respectively generates anode tail gas and cathode tail gas;
and the cathode tail gas enters a combustion device to be combusted to generate combustion tail gas.
In the fuel cell, the anode tail gas generated at the anode of the fuel cell by the chemical reaction of the mixed fuel gas and the air does not need to be subjected to the steps of cooling, condensation, dehydration and the like, and can be directly mixed and combusted with high-temperature cathode air at higher temperature, so that the combustion stability is ensured, and the system flow is greatly simplified.
In the invention, the synthesis gas is subjected to water gas shift reaction to convert CO in the synthesis gas into H2The partial pressure of hydrogen in the anode gas entering the fuel cell is obviously improved, and compared with the prior art, the method can improve the power generation efficiency of the fuel cell, simultaneously reduce the risk of carbon deposition of the fuel cell, and further prolong the service life of the fuel cell.
According to the invention, the anode tail gas sequentially enters the first heat exchange device and the heat exchange conversion device to be used for heating the mixed fuel gas and the synthesis gas, and then enters the combustion device to be combusted.
According to the invention, the combustion tail gas enters the second heat exchange device and the third heat exchange device in sequence to be used for heating air and water so as to obtain high-temperature air and water vapor.
According to the invention, the steam is mixed with the synthesis gas and then enters the heat conversion device.
According to the present invention, the mixed fuel gas further contains carbon dioxide.
According to the invention, the method further comprises passing the mixed fuel gas through CO2A separator to remove carbon dioxide from the mixed fuel gas.
In the invention, the amount of carbon dioxide entering the anode of the fuel cell is strictly controlled through the step of removing the carbon dioxide in the mixed fuel gas, and researches show that when the molar content of the carbon dioxide in the mixed fuel gas is less than 30%, the power generation efficiency of the carbon dioxide to the fuel cell can be obviously reduced, the risk of carbon deposition of the fuel cell can be obviously reduced, and the service life of the fuel cell is prolonged.
Further, the molar content of carbon dioxide in the mixed fuel gas is less than 15%.
According to the invention, the first temperature is 100-400 ℃, preferably 200-300 ℃;
according to the invention, the second temperature is 500-800 ℃, preferably 600-700 ℃;
according to the invention, the temperature of the anode tail gas is 600-900 ℃, preferably 700-800 ℃;
according to the invention, the temperature of the cathode tail gas is 600-900 ℃, preferably 700-800 ℃;
according to the invention, the working temperature of the fuel cell is 500-900 ℃, preferably 600-800 ℃;
according to the invention, the operating pressure of the fuel cell is between 0.05 and 0.5MPa, preferably between 0.1 and 0.2 MPa.
According to the invention, the molar ratio of hydrogen to carbon monoxide in the synthesis gas is between 0.2 and 6, preferably between 0.5 and 4.
According to the invention, the molar ratio of water vapor to CO is between 0.2 and 2.5, preferably between 0.5 and 1.5.
According to the invention, the temperature of the combustion tail gas is 700-1000 ℃, and preferably 800-900 ℃.
According to the invention, the temperature of the combustion tail gas is reduced to 400 ℃ below zero after passing through the second heat exchange device, and preferably to 300 ℃ below zero at 200 ℃.
Mode for carrying out the invention
Mixing synthesis gas provided by a synthesis gas source with steam, preheating the mixture to a first temperature by a heat exchange conversion device, and carrying out water gas conversion reaction to prepare mixed fuel gas containing hydrogen and carbon monoxide;
the mixed fuel gas is heated to a second temperature by the first heat exchange device, enters the anode of the fuel cell, and chemically reacts with air which is heated by the second heat exchange device and enters the cathode of the fuel cell to respectively generate anode tail gas containing carbon dioxide and water and cathode tail gas containing nitrogen and oxygen;
after the anode tail gas sequentially passes through the first heat exchange device and the heat exchange conversion device and is used for heating mixed fuel gas and synthesis gas, the tail gas enters the combustion device and is mixed with cathode tail gas from the cathode of the fuel cell for combustion;
combustion tail gas generated by combustion sequentially passes through the second heat exchange device and the third heat exchange device to be used for heating air and water so as to obtain high-temperature air and water vapor;
the high-temperature air enters the cathode of the fuel cell;
and the steam and the synthesis gas are mixed and then enter the heat exchange conversion device.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the battery power generation power parameter is measured by a battery voltage and battery current method;
the fuel utilization rate parameter is measured by a fuel flow and cell current method, and the specific calculation formula is as follows:
fuel utilization,% [ current (a) × 3600 ] number of cells of the stack]/[96485 × 2 electric stack inlet fuel flow (Nm)3/h)/0.0224]×100％。
The raw materials used in the examples and comparative examples are all commercially available products.
Example 1
In a set of MWthA staged syngas fuel cell power generation system is an example:
290Nm3synthesis gas (H)/H2Molar ratio to CO of 1.68) to 103Nm3H steam mixing, wherein the molar ratio of the steam to the CO is 1: 1. Preheating to 220 deg.C by heat exchange conversion device, performing water gas conversion reaction, and converting 70% of CO into H2And the outlet temperature reaches 400 ℃ to obtain mixed fuel gas containing hydrogen and carbon monoxide, wherein the content of carbon dioxide in the mixed fuel gas is 20%, the mixed fuel gas is further preheated to 700 ℃ through a first heat exchange device and enters a solid oxide fuel cell for anode reaction, the fuel utilization rate is 85%, the power generation power is 550kW, the temperature of tail gas at the outlet of the anode is 800 ℃, the mixed fuel gas and the synthesis gas which sequentially pass through the first heat exchange device and a heat exchange conversion device and are used for heating the anode feeding material are cooled to 450 ℃, the mixed fuel gas and the synthesis gas are sent to a gas burner to be mixed and combusted with cathode tail gas (800 ℃), the temperature of the combustion tail gas is controlled by fresh air, and the cathode feeding air is heated (the3Heating to 700 deg.C, cooling to 300 deg.C, generating 0.5MPa steam by steam generator, supplying to anode, cooling to 200 deg.C, and discharging.
Example 2
The procedure is as in example 1, except that: the molar ratio of hydrogen to carbon monoxide in the synthesis gas was 0.5. The fuel utilization rate of the fuel cell was 80%, and the power generation power was 500 kW.
Example 3
The procedure is as in example 1, except that: the molar ratio of hydrogen to carbon monoxide in the synthesis gas was 3. The fuel utilization of the fuel cell was 90%, and the power generation power was 600 kW.
Example 4
The procedure is as in example 1, except that: the molar ratio of hydrogen to carbon monoxide in the synthesis gas was 0.2. The fuel utilization of the fuel cell was 70%, and the generated power was 450 kW.
Example 5
The procedure is as in example 1, except that: the molar ratio of water vapor to CO was 1.5. The fuel utilization of the fuel cell was 85%, and the power generation power was 530 kW.
Example 6
The procedure is as in example 1, except that: the molar ratio of water vapor to CO was 0.5, the fuel utilization of the fuel cell was 83%, and the power generation power was 520 kW.
Example 7
The procedure is as in example 1, except that: the molar ratio of water vapor to CO was 2.5. The fuel utilization of the fuel cell was 85%, and the generated power was 520 kW.
Example 8
The procedure is as in example 1, except that: the content of carbon dioxide in the fuel mixed gas was 45%. The fuel utilization of the fuel cell was 65%, and the power generation power was 400 kW.
Example 9
The procedure is as in example 1, except that: in the first preheating device, the mixed fuel gas containing hydrogen and carbon monoxide obtained by the water gas shift reaction is subjected to CO2A separator to remove carbon dioxide from the mixed fuel gas. After the separation treatment, the content of carbon dioxide in the mixed fuel gas is 5%. The fuel utilization of the fuel cell was 90%, and the power generation power was 600 kW.
Comparative example 1
The procedure is as in example 1, except that: the synthesis gas directly enters the anode of the fuel cell after secondary heating without carrying out water gas change reaction. The content of carbon dioxide in the fuel mixed gas was 45%. The fuel utilization of the fuel cell was 65%, and the power generation power was 400 kW.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A synthesis gas fuel cell power generation system comprises a synthesis gas source, a heat exchange device, a fuel cell and a combustion device, wherein the synthesis gas source is used for providing synthesis gas; the heat exchange device comprises a heat exchange conversion device, a first heat exchange device and a second heat exchange device; the heat exchange conversion device is connected with the anode of the fuel cell through a first heat exchange device; the cathode of the fuel cell is connected with the combustion device; the combustion device is connected with the cathode of the fuel cell through a second heat exchange device.
2. The syngas fuel cell power generation system of claim 1, wherein the heat exchange device further comprises a third heat exchange device coupled to the second heat exchange device and the heat exchange reformer, respectively, to provide low pressure steam to the heat exchange reformer.
3. The syngas fuel cell power generation system of claim 1 or 2, wherein the heat exchange shift unit is loaded with a shift reaction catalyst for converting carbon monoxide in the syngas to hydrogen;
the system further comprises CO2A separator connected with the heat exchange conversion device and the first heat exchange device respectively for reducing CO in the anode feed gas2The content of (A);
the third heat exchange device is a steam generator.
4. A method of generating electricity from a syngas fuel cell, wherein the method comprises the steps of:
mixing synthesis gas provided by a synthesis gas source with steam, preheating the mixture to a first temperature by a heat exchange conversion device, and then carrying out water gas conversion reaction to prepare mixed fuel gas containing hydrogen and carbon monoxide;
the mixed fuel gas is heated to a second temperature by the first heat exchange device, enters the anode of the fuel cell, reacts with air which is heated by the second heat exchange device and enters the cathode of the fuel cell, generates power and respectively generates anode tail gas and cathode tail gas;
and the cathode tail gas enters a combustion device to be combusted to generate combustion tail gas.
5. The method of claim 4, wherein the anode tail gas enters the first heat exchange device and the heat exchange conversion device in sequence for heating the mixed fuel gas and the synthesis gas, and then enters the combustion device for combustion.
6. The method according to claim 4 or 5, wherein combustion tail gas generated by combustion enters the second heat exchange device and the third heat exchange device in sequence for heating air and water so as to obtain high-temperature air and water vapor;
preferably, the steam is mixed with the synthesis gas and then enters the heat exchange conversion device.
7. The method according to any one of claims 4 to 6, wherein the mixed fuel gas further comprises carbon dioxide;
preferably, the method further comprises passing the mixed fuel gas through CO2A separator to remove carbon dioxide from the mixed fuel gas;
preferably, the molar content of carbon dioxide in the mixed fuel gas is less than 30%, preferably less than 15%.
8. The method according to any one of claims 4-7, wherein the first temperature is 100-;
preferably, the second temperature is 500-800 ℃, preferably 600-700 ℃;
preferably, the temperature of the anode tail gas is 600-900 ℃, preferably 700-800 ℃;
preferably, the temperature of the cathode tail gas is 600-900 ℃, preferably 700-800 ℃;
preferably, the operating temperature of the fuel cell is 500-900 ℃, preferably 600-800 ℃;
preferably, the operating pressure of the fuel cell is 0.05 to 0.5MPa, preferably 0.1 to 0.2 MPa.
9. A process according to any one of claims 4 to 8, wherein the molar ratio of hydrogen to carbon monoxide in the synthesis gas is in the range of from 0.2 to 6, preferably from 0.5 to 4;
preferably, the molar ratio of water vapour to CO is in the range of 0.2 to 2.5, preferably 0.5 to 1.5.
10. The method according to any one of claims 4-9, wherein the temperature of the combustion off-gas is 700-;
preferably, the temperature of the combustion tail gas is reduced to 400 ℃ below zero after passing through the second heat exchange device, and preferably to 300 ℃ below zero at 200 ℃.
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| CN114639843A (en) * | 2022-03-09 | 2022-06-17 | 上海电力大学 | Fuel cell and double-gas turbine coupling system |
| WO2024027073A1 (en) * | 2022-08-05 | 2024-02-08 | 中国石油天然气股份有限公司 | Method and system for co-producing steam in power generation process |
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| WO2024027073A1 (en) * | 2022-08-05 | 2024-02-08 | 中国石油天然气股份有限公司 | Method and system for co-producing steam in power generation process |
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