CN115799561A - Solid oxide fuel cell cogeneration device - Google Patents
Solid oxide fuel cell cogeneration device Download PDFInfo
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- CN115799561A CN115799561A CN202211360474.8A CN202211360474A CN115799561A CN 115799561 A CN115799561 A CN 115799561A CN 202211360474 A CN202211360474 A CN 202211360474A CN 115799561 A CN115799561 A CN 115799561A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a solid oxide fuel cell cogeneration device, comprising: the system comprises a cogeneration starting system, a reforming system, a fuel cell system, a waste heat recovery system and a desulphurization device; the gas inlet of the sulfur removal device is communicated with the natural gas, and the gas outlet of the sulfur removal device is respectively communicated with the gas inlet of the cogeneration starting system and the gas inlet of the reforming system. The method has the advantages that gaseous hydrocarbons are used as fuel, the SOFC galvanic pile is utilized to generate electric energy, meanwhile, waste heat generated during the power generation of the SOFC galvanic pile is recovered through heat exchange, the energy of the fuel is fully utilized, the effective utilization rate of the fuel energy is improved, and the like.
Description
Technical Field
The present invention relates to a solid oxide fuel cell cogeneration apparatus.
Background
The SOFC can not only use hydrogen as fuel gas, but also is suitable for various gases (shale gas reserves which are known at present and are the first in China), such as liquefied petroleum gas, natural gas and coal gas, and even some liquid hydrocarbons (methane, propane and the like) can be used as fuel. In the present day that mineral resources become poor and ecological environment protection is increasingly important, SOFCs have attracted much attention and become a popular technology for competitive research and development at home and abroad.
Depending on the requirements of the fuel cell application (e.g., energy density, safety, etc.), the fuel cell system may select various fuels (e.g., methanol, etc.) including hydrogen. Although methanol fuel cells are also under study, the conversion of primary fuel into hydrogen for use in fuel cells via fuel reforming processes is still the focus of research. Hydrogen production was initially carried out using micro-scale reformers on low power (e.g. < 100 w) fuel cells only, and the fuel reforming hydrogen production reactor was studied on a laboratory scale in the context of high power fuel cell applications, with reference to an industrial packed bed reactor model. However, it has been found that the reforming process is affected by "cold spots" or "hot spots" and has a slow response to start-up and shut-down and variable conditions, which does not meet the operating conditions required by the fuel cell system, because the heat and mass transfer rates in the packed bed of the reactor are limited and the heat and components required for the reaction cannot be balanced in time, the reaction proceeds at a rate lower than its intrinsic kinetic rate.
For example, steam reforming of Methane (SteamReforming of Methane) is the most industrially applied method with mature technology, and the chemical reaction formula is:
CH 4 + H 2 O →CO + 3H 2 ，ΔH = + 206 kJ /mol
Δ H is the change in enthalpy of the chemical reaction, "+" is the endothermic reaction, and "-" is the exothermic reaction. The reaction is a strong endothermic reaction, requires an additional heat source, and is generally carried out at a high temperature of more than 800 ℃ and the reaction pressure is 1.5-3.1 MPa. The reaction produces CO in addition to H2, the ratio of the amounts of H2 and CO being 3.
Steam reforming is the most commonly used method for obtaining hydrogen from hydrocarbon fuel, and the reformed synthesis gas product has high hydrogen content, which is a relatively ideal fuel supply mode for solid oxide fuel cells, but the disadvantage is that the reaction process is a reaction with strong heat absorption. The endothermic steam reforming process is generally limited by the rate of heat transfer from the boundary to the catalyst, resulting in a large reactor volume. Steam reforming would be a more advantageous way to produce hydrogen if the heat transfer problem could be solved. The on-line hydrogen production reforming technology of the fuel cell system is realized by adopting the hydrocarbon fuel, and the hydrogen production by reforming the liquid hydrocarbon fuel is obviously superior to the hydrogen storage mode.
Meanwhile, at present, the solid oxide fuel cell which uses hydrocarbon as fuel generates electricity, and the SOFC stack tail gas has tail gas with high value-added waste heat. How to recover and reasonably utilize the waste heat in the tail gas of the SOFC electric pile is a difficult problem to be solved urgently at present. If the problem of tail gas recovery of the SOFC galvanic pile can be solved, the effective utilization rate of fuel can be further greatly improved, and the waste of energy in China is reduced.
Disclosure of Invention
The invention aims to provide a solid oxide fuel cell cogeneration device for overcoming the defects of the prior art.
In order to achieve the above object, the present invention provides a solid oxide fuel cell cogeneration apparatus, comprising a cogeneration starting system, a reforming system, a fuel cell system, a waste heat recovery system, and a sulfur removal device; the gas inlet of the sulfur removal device is communicated with natural gas, and the gas outlet of the sulfur removal device is respectively communicated with the gas inlet of the cogeneration starting system and the gas inlet of the reforming system;
the cogeneration start-up system includes: the device comprises a blower, a first air flow meter, a starting combustion chamber, two catalytic combustion chambers, a first valve and a first mass flow meter, wherein heat exchange interlayers are arranged in the two catalytic combustion chambers, an inlet of the first valve is communicated with an air outlet of a sulfur removal device, an air outlet of the first valve is communicated with a port b of the starting combustion chamber through the first mass flow meter, an air outlet of the blower is communicated with a port a of the starting combustion chamber through the first air flow meter, a port c of the starting combustion chamber is respectively communicated with an air inlet of the heat exchange interlayers of the catalytic combustion chambers, and air outlets of the two heat exchange interlayers are communicated with the outside;
the reforming system includes: the catalytic reformer is a tubular reforming reactor, and the two catalytic combustion chambers and the start-up combustion chamber are respectively positioned at the side edges of the catalytic reformer so as to exchange heat with the catalytic reformer;
the fuel cell system includes: an air pump, a second air flowmeter and an SOFC (solid oxide fuel cell) stack, wherein an air inlet of the air pump is communicated with cathode air, an air outlet of the air pump is communicated with a port b of the stack after passing through the second air flowmeter, an anode fuel interface a of the SOFC stack is communicated with a catalytic reforming synthesis gas outlet d from the catalytic reformer, and an anode tail gas outlet d of the SOFC stack and a cathode tail gas outlet c of the SOFC stack are respectively communicated with air inlets of the two catalytic combustion chambers;
the waste heat recovery system comprises: the device comprises a first heat exchanger, an impurity filter, an ion filter, a third valve, a metering water pump, a water vapor generator, a second heat exchanger, a circulating water pump, a hot water tank and a fourth valve, wherein the first heat exchanger is arranged on a pipe where a second air flow meter is communicated with a port b of an SOFC (solid oxide fuel cell) galvanic pile, an inlet of the impurity filter is communicated with water, a water outlet of the impurity filter is communicated with a water inlet of the ion filter and a water inlet of the fourth valve respectively, a water outlet of the ion filter is communicated with a port c of the water vapor generator after passing through the third valve and the metering water pump in sequence, an outlet of the fourth valve is communicated with a port a of the hot water tank, a port c of the catalytic reformer is communicated with the port b of the water vapor generator, a port b of the catalytic reformer is communicated with a port b of the water vapor generator through the first heat exchanger for heat exchange, a port b of the mixing cavity is communicated with a port a of the water vapor generator, a port c of the second heat exchanger is communicated with a port, a port of the second heat exchanger is communicated with a port d port of the second heat exchanger, a port of the second heat exchanger is communicated with a port c of the hot water tank, and a water outlet of the circulating water pump of the hot water tank are communicated with an external water tank.
In the technical scheme, the port d of the hot water tank is communicated with an inlet of a fifth valve, and an outlet of the fifth valve is communicated with the outside.
In the technical scheme, an electric heater is arranged in the hot water tank.
In the technical scheme, the device also comprises a control panel; the control board is electrically connected with the SOFC stack.
Compared with the prior art, the invention has the advantages that: the gaseous hydrocarbon is used as fuel, the SOFC galvanic pile is utilized to generate electric energy, and simultaneously, the waste heat generated during the power generation of the SOFC galvanic pile is recovered through heat exchange, so that the energy of the fuel is fully utilized, and the effective utilization rate of the energy of the fuel is improved.
Drawings
FIG. 1 is the left side of the schematic of the apparatus of the present invention;
figure 2 is the right side of the schematic of the device of the present invention.
Detailed description of the preferred embodiments
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the description of the present invention, the terms "upper" and "lower" and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present invention but do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
As shown in fig. 1 and 2, the co-generation apparatus for solid oxide fuel cell includes: a cogeneration starting system, a reforming system, a fuel cell system, a waste heat recovery system, and a sulfur removal device 10; the gas inlet of the sulfur removal device 10 is communicated with natural gas, and the gas outlet of the sulfur removal device 10 is respectively communicated with the gas inlet of the cogeneration starting system and the gas inlet of the reforming system;
the cogeneration start-up system includes: the device comprises an air blower 1, a first air flow meter 2, a starting combustion chamber 3, two catalytic combustion chambers 4, a first valve 11 and a first mass flow meter 12, wherein a heat exchange interlayer 41 is arranged in each of the two catalytic combustion chambers 4, an inlet of the first valve 11 is communicated with an air outlet of a sulfur removal device 10, an air outlet of the first valve 11 is communicated with a port b of the starting combustion chamber 3 through the first mass flow meter 12, an air outlet of the air blower 1 is communicated with a port a of the starting combustion chamber 3 through the first air flow meter 2, a port c of the starting combustion chamber 3 is respectively communicated with an air inlet of the heat exchange interlayer 41 of the catalytic combustion chamber 4, and air outlets of the two heat exchange interlayers 41 are converged to a tail gas port through a pipeline and then are discharged;
the reforming system includes: the catalytic reformer 5, a second valve 13, a second mass flow meter 14 and a mixing cavity 15, wherein an air inlet of the second valve 13 is communicated with an air outlet of the sulfur removal device 10, an air outlet of the second valve 13 is communicated with an a port of the catalytic reformer 5 through a c port of the mixing cavity 15 after sequentially passing through the a ports of the second mass flow meter 14 and the mixing cavity 15, combustion tail gas air outlets of the two catalytic combustion chambers 4 are communicated with a b port of the catalytic reformer 5, the catalytic reformer 5 is a tubular reforming reactor, and the two catalytic combustion chambers 4 and the start-up combustion chamber 3 are respectively positioned on the side edge of the catalytic reformer 5 so as to exchange heat with the catalytic reformer 5;
the fuel cell system includes: the system comprises an air pump 16, a second air flow meter 18 and an SOFC electric pile 9, wherein an air inlet of the air pump 16 is communicated with cathode air, an air outlet of the air pump 16 is communicated with a port b of the electric pile 9 after passing through the second air flow meter 18, an anode fuel interface a of the SOFC electric pile 9 is communicated with a synthesis gas outlet d of a catalytic reforming synthesis gas from a catalytic reformer 5, and an anode tail gas outlet d of the SOFC electric pile 9 and a cathode tail gas outlet c of the SOFC electric pile 9 are respectively communicated with air inlets of two catalytic combustion chambers 4;
the waste heat recovery system comprises: a first heat exchanger 7, an impurity filter 17, an ion filter 19, a third valve 20, a metering water pump 21, a steam generator 22, a second heat exchanger 23, a circulating water pump 24, a hot water tank 25 and a fourth valve 28, wherein the first heat exchanger 7 is arranged on a pipe of a second air flow meter 18 communicated with a port b of the SOFC pile 9, an inlet of the impurity filter 17 is communicated with water, a water outlet of the impurity filter 17 is respectively communicated with a water inlet of the ion filter 19 and a water inlet of the fourth valve 28, a water outlet of the ion filter 19 is communicated with a port c of the steam generator 22 after passing through the third valve 20 and the metering water pump 21 in sequence, an outlet of the fourth valve 28 is communicated with a port a of the hot water tank 25, and a port c of the catalytic reformer 5 is communicated with a port b of the steam generator 22, and the pipeline of the port c of the catalytic reformer 5 communicated with the port b of the water vapor generator 22 is subjected to heat exchange through the first heat exchanger 7, the port b of the mixing chamber 15 is communicated with the port a of the water vapor generator 22, the port c of the second heat exchanger 23 is communicated with the port a, the port b of the second heat exchanger 23 is communicated with the port d, the port c of the second heat exchanger 23 is communicated with the port d of the water vapor generator 22, the port d of the second heat exchanger 23 is communicated with the water outlet of the circulating water pump 24, the port b of the second heat exchanger 23 is communicated with the port c of the hot water tank 25, the port b of the hot water tank 25 is communicated with the water inlet of the circulating water pump 24, and the port a of the second heat exchanger 23 is communicated with the outside atmosphere, namely, the second path of system tail gas enters the second heat exchanger 23 through the port c to perform heat exchange and is discharged from the port a.
During operation, after sulfur removal, natural gas is divided into two paths of fuel supply, the first path enters a cogeneration starting system, the second path enters a reforming system, water is filtered by impurities and then divided into two paths, the first path passes through an ion filter 19, a third valve 20, a metering water pump 21 and a steam generator 22 and then enters the reforming system, and the second path passes through a fourth valve 28 and enters a hot water tank 25;
in the cogeneration starting system, natural gas and air are introduced into a starting combustion chamber 3 and then ignited for combustion, the bottom of a catalytic reformer 5 is heated, the combusted tail gas is introduced into heat exchange interlayers 41 of catalytic combustion chambers 4 at two sides of the reformer, the catalytic combustion chambers 4 are heated by utilizing the waste heat of the combusted tail gas, the combustion air of the cogeneration starting system is provided by an air blower 1, a first flowmeter 2 is arranged behind the air blower 1, and the air flow entering the cogeneration starting system after the air blower 1 can be detected;
in the reforming system, tail gas of a cathode and an anode of an SOFC (solid oxide fuel cell) stack 9 respectively enters two catalytic combustion chambers 4 for catalytic combustion, generated heat can heat a catalytic reformer 5, the catalytic reformer 5 is a tubular reforming reactor, high-temperature waste heat of the catalytic combustion tail gas can exchange heat with the tubular catalytic reformer to maintain the temperature of a reforming reactant and keep the uniformity of a temperature field, the tail gas entering from a port b of the catalytic reformer 5 is subjected to heat exchange with a tubular pipe of the tubular reforming reactor and then discharged from a port c of the catalytic reformer 5, a mixed reaction raw material of natural gas and steam enters the reactor from a port a of the catalytic reformer 5, and a synthesis gas generated by reaction is discharged from a port d;
in the fuel cell system, cathode air passes through an air pump 16, a second flowmeter 18 and a first heat exchanger 7 and then enters a cathode air inlet b port of the SOFC (solid oxide fuel cell) galvanic pile, a cathode tail gas outlet d port and an anode tail gas c port of the SOFC galvanic pile respectively and independently enter catalytic combustion chambers 4 at two sides in the reforming system, and residual anode fuel and cathode oxygen are utilized for catalytic combustion to provide a heat source for the reforming system;
in the waste heat recovery system, after the tail gas of the SOFC galvanic pile 9 is subjected to catalytic combustion in the catalytic combustion chamber 4, the high-temperature waste heat tail gas is subjected to heat exchange with the catalytic reformer 5 and cathode air in sequence respectively to provide a heat source for the tubular reactor and the galvanic pile, the tail gas of the catalytic reformer 5 enters the water vapor generator 22 after passing through the heat exchanger of the cathode air, the heat exchange is carried out on the tail gas in the water vapor generator 22 to provide a water vapor reaction raw material for methane reforming, the tail gas enters the second heat exchanger 23 after passing through the steam generator 22, and water in the hot water tank 25 continuously enters the heat exchanger 23 through the circulating pump 24 to exchange heat with the tail gas to generate hot water.
The first specific operation method comprises the following steps: loading a natural gas steam reforming catalyst in a catalytic reformer 5, selecting an SOFC electric pile 9 with power of 350W to be installed in a fuel cell system, connecting a pipeline, detecting air tightness, opening a fifth valve 28, filling water into a hot water tank 25, starting a hot water circulating pump 24, starting a blower 1 of a starting burner 3 and an air pump 16 of fuel cell cathode air, introducing natural gas into the starting burner 3, igniting immediately, igniting the natural gas in the starting burner 3, introducing steam and natural gas into the catalytic reformer 5 along with the combustion of the starting burner 3, wherein the temperature of the SOFC electric pile 9 is increased rapidly to 700 ℃ under the condition of a preheated cathode air source, and then controlling the flow of the natural gas, the steam and the cathode air to maintain the temperature of the catalytic reformer 5 at 750 ℃, the temperature of the SOFC electric pile 9 is more than 700 ℃ after the temperature of the SOFC electric pile 9 is more than 500 ℃, opening a stable hot water circuit to obtain a stable hot water temperature of 54.0V, and outputting a hot water tank with power of 50.W after the whole system is stabilized at 50 ℃.
The second specific operation method comprises the following steps: a propane steam reforming catalyst is loaded in a catalytic reformer 5, an SOFC electric stack 9 with power of 350W is selected to be loaded in a fuel cell system, a pipeline is connected, air tightness is detected, a fifth valve 28 is opened, water is filled in a hot water tank 25, a hot water circulating pump 24 is started, an air blower 1 of a starting combustor 3 and an air pump 16 of fuel cell cathode air are started, natural gas is introduced into the starting combustor 3 and is ignited immediately, the natural gas in the starting combustor 3 is ignited, the temperatures of the catalytic reformer 5 and a catalytic combustion chamber 4 are gradually increased along with the combustion of the starting combustor 3, meanwhile, under the condition of a preheated cathode air stripping source, the temperature of the SOFC electric stack 9 is increased, when the temperature of the catalytic reformer 5 is increased to be more than 700 ℃ and the temperature of the SOFC electric stack 9 is more than 500 ℃, steam and propane are introduced into the catalytic reformer 5, the temperature of the SOFC electric stack 9 is rapidly increased to 700 ℃, then the temperature of the catalytic reformer 5 is maintained at 750 ℃, the temperature of the SOFC electric stack 9 is stabilized at 700 ℃, the temperature of the whole SOFC electric stack 9 is measured and the temperature of the hot water tank is measured to be more than 50.50.V.
In this embodiment, the d port of the hot water tank is communicated with the inlet of the fifth valve 26, and the outlet of the fifth valve 26 is communicated with the outside.
In the present embodiment, an electric heater 27 is provided in the hot water tank 25.
In the present embodiment, a control panel 8 is further included; the control board 8 is electrically connected to the SOFC stack 9.
The embodiments of the present invention are described in detail above with reference to the drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention.
Claims (4)
1. A solid oxide fuel cell cogeneration device, characterized by comprising: a cogeneration starting system, a reforming system, a fuel cell system, a waste heat recovery system and a desulphurization device (10); the gas inlet of the sulfur removal device (10) is communicated with natural gas, and the gas outlet of the sulfur removal device (10) is respectively communicated with the gas inlet of the cogeneration starting system and the gas inlet of the reforming system;
the cogeneration start-up system includes: the device comprises an air blower (1), a first air flow meter (2), a starting combustion chamber (3), two catalytic combustion chambers (4), a first valve (11) and a first mass flow meter (12), wherein a heat exchange interlayer (41) is arranged in each of the two catalytic combustion chambers (4), an inlet of the first valve (11) is communicated with an air outlet of a sulfur removal device (10), an air outlet of the first valve (11) is communicated with a port b of the starting combustion chamber (3) through the first mass flow meter (12), an air outlet of the air blower (1) is communicated with a port a of the starting combustion chamber (3) through the first air flow meter (2), a port c of the starting combustion chamber (3) is respectively communicated with an air inlet of the heat exchange interlayer (41) of the catalytic combustion chamber (4), and air outlets of the two heat exchange interlayers (41) are communicated with the outside;
the reforming system includes: the catalytic reformer (5) is a tubular reforming reactor, and the two catalytic combustion chambers (4) and the start-up combustion chamber (3) are respectively positioned on the side edges of the catalytic reformer (5) to exchange heat with the catalytic reformer (5);
the fuel cell system includes: the fuel cell comprises an air pump (16), a second air flow meter (18) and an SOFC electric stack (9), wherein an air inlet of the air pump (16) is communicated with cathode air, an air outlet of the air pump (16) is communicated with a port b of the electric stack (9) through the second air flow meter (18), an anode fuel interface a of the SOFC electric stack (9) is communicated with a synthesis gas outlet d of a catalytic reforming synthesis gas from a catalytic reformer (5), and an anode tail gas outlet d of the SOFC electric stack (9) and a cathode tail gas outlet c of the SOFC electric stack (9) are respectively communicated with air inlets of two catalytic combustion chambers (4);
the waste heat recovery system comprises: a first heat exchanger (7), an impurity filter (17), an ion filter (19), a third valve (20), a metering pump (21), a water vapor generator (22), a second heat exchanger (23), a circulating water pump (24), a hot water tank (25) and a fourth valve (28), wherein the first heat exchanger (7) is arranged on a pipe of a second air flow meter (18) communicated with a port b of the SOFC stack (9), an inlet of the impurity filter (17) is communicated with water, a water outlet of the impurity filter (17) is respectively communicated with a water inlet of the ion filter (19) and a water inlet of the fourth valve (28), a water outlet of the ion filter (19) is communicated with a port c of the water vapor generator (22) after sequentially passing through the third valve (20) and the metering water pump (21), an outlet of the fourth valve (28) is communicated with a port a of the hot water tank (25), the port c port of the catalytic reformer (5) is communicated with the port b of the water vapor generator (22), and the port c port of the catalytic reformer (5) is communicated with a port b of the water vapor generator (22) through a pipe of the steam generator (22), and a pipe of the second heat exchanger (7) is communicated with a mixing chamber of the second heat exchanger (15 a), and a mixing chamber of the second heat exchanger (23 a) is communicated with a heat exchanger (23 b) communicated with a water outlet of the water generator (23 b) of the steam generator (22 a heat exchanger (23 b), the port c of the second heat exchanger (23) is communicated with the port d of the water vapor generator (22), the port d of the second heat exchanger (23) is communicated with the water outlet of the circulating water pump (24), the port b of the second heat exchanger (23) is communicated with the port c of the hot water tank (25), the port b of the hot water tank (25) is communicated with the water inlet of the circulating water pump (24), and the port a of the second heat exchanger (23) is communicated with the outside atmosphere.
2. Solid oxide fuel cell cogeneration device according to claim 1, characterized in that the d port of the hot water tank is communicated with the inlet of the fifth valve (26), and the outlet of the fifth valve (26) is communicated with the outside.
3. Solid oxide fuel cell cogeneration unit according to claim 1, characterized in that an electric heater (27) is provided in the hot water tank (25).
4. Solid oxide fuel cell cogeneration unit according to claim 1, characterized by further comprising a control board (8); the control plate (8) is electrically connected with the SOFC electric stack (9).
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| CN202211360474.8A CN115799561A (en) | 2022-11-02 | 2022-11-02 | Solid oxide fuel cell cogeneration device |
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| CN202211360474.8A CN115799561A (en) | 2022-11-02 | 2022-11-02 | Solid oxide fuel cell cogeneration device |
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