CN115995575B - Fuel cell system based on carbon trapping and heat storage sharing and thermoelectric decoupling method - Google Patents
Fuel cell system based on carbon trapping and heat storage sharing and thermoelectric decoupling method Download PDFInfo
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Abstract
The invention provides a fuel cell system based on carbon trapping and heat storage sharing and a thermoelectric decoupling method, wherein the solid oxide fuel cell driven by hydrocarbon fuel can trap CO by adopting an adsorption method 2 ，CO 2 Adsorption and adsorbent regeneration are exothermic and endothermic processes, respectively, the adsorbent volume energy density is equivalent to that of the heat storage material, and carbon traps CO 2 The adsorption/regeneration process can have a heat storage effect at the same time, and the thermal decoupling of the system is realized by the operation decoupling of adsorption (heat release)/regeneration (heat storage) time. According to the thermoelectric load change, the adsorption and regeneration processes are not performed simultaneously: when the heat generated by the system is larger than the heat load, the waste heat can be used for driving the regeneration process; on the contrary, the heat absorption and the heat release in the regeneration process meet the heat load gap. According to the invention, two functions of carbon capture and heat storage are realized through one set of carbon adsorption/regeneration equipment, the requirement on special equipment for heat storage is reduced, and flexible decoupling regulation and control of heat supply and power supply of the system are realized.
Description
Technical Field
The invention belongs to the technical field of energy utilization, and particularly relates to a fuel cell system based on carbon trapping and heat storage sharing and a thermoelectric decoupling method.
Background
The fuel cell can directly convert fuel chemical energy into electric energy through electrochemical reaction, generates heat without being limited by Carnot cycle, has the advantages of high energy conversion efficiency, low carbon, no pollution and the like, and is widely considered as one of key energy technologies for supporting an energy system to realize zero carbon emission. The solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC) is a fuel cell technology currently undergoing technical transformation and industrialization in China, the working temperature is 700-1000 ℃, the waste heat utilization value is high, the solid oxide fuel cell can be used for cogeneration, and the energy utilization efficiency is improved to more than 90%. The solid oxide fuel cell can be combined with hydrocarbon fuel reforming hydrogen production of diesel, methanol, methane and the like to construct a fuel cell system directly utilizing on-site reforming hydrogen production, has wide and flexible fuel source and can powerfully ensure continuous operation of the system. The solid oxide fuel cell can be used as a distributed cogeneration system for supplying power and heat for various civil and industrial buildings, island frontier defense, emergency rescue and other scenes, and has good development prospect and application value.
The heat and electricity load changes of the application scene are asynchronous, and the heat and electricity cogeneration system of the solid oxide fuel cell is required to have the capability of independently regulating and controlling heat production and electricity production, namely the capability of regulating and controlling thermal decoupling, so that the application requirements can be met. However, in the electrochemical reaction process of the solid oxide fuel cell, electric energy is accompanied by heat energy, and the thermoelectric coupling property is strong. Therefore, how to improve the thermal decoupling regulation capability of the system is a problem to be solved in technical application and popularization.
The co-production system needs to explore and establish the thermal-decoupling regulation and control capability to meet the application requirements, but the additional energy storage equipment is added to improve the thermal-decoupling regulation and control capability of the system, so that the equipment investment is increased, and the equipment installation space requirement is increased.
Disclosure of Invention
The invention aims to provide a fuel cell system and a thermoelectric decoupling method based on carbon trapping and heat storage sharing, which can reduce the requirement on special equipment for heat storage and realize flexible decoupling regulation and control of heat supply and power supply of a system.
In order to achieve the above object, the present invention provides a fuel cell system based on the common use of carbon capture and heat storage, comprising a solid oxide fuel cell, a reformer, an evaporator, an air preheater, a condenser, an adsorber, a regenerator, a first confluence device, a second confluence device, a first flow divider, a second flow divider, a first compressor, a second compressor and a pump;
the outlet of the pump is connected with the low-temperature fluid inlet of the evaporator, the low-temperature fluid outlet of the evaporator is connected with the first inlet of the first confluence device, and the outlet of the first confluence device is connected with the reactant inlet of the reformer;
the product outlet of the reformer is connected with the first inlet of the second flow combiner, the outlet of the second flow combiner is connected with the anode inlet of the solid oxide fuel cell, the anode outlet of the solid oxide fuel cell is connected with the inlet of the second gas compressor, the outlet of the second gas compressor is connected with the inlet of the first flow divider, the first outlet of the first flow divider is connected with the second inlet of the first flow combiner, and the second outlet of the first flow divider is connected with the inlet of the second flow divider;
the first outlet of the second flow divider is connected with the high-temperature fluid inlet of the condenser, the second outlet of the second flow divider is connected with the heating fluid inlet of the regenerator, the heating fluid outlet of the regenerator is connected with the high-temperature fluid inlet of the condenser, the high-temperature fluid outlet of the condenser is connected with the gas inlet of the absorber, and the outlet of the absorber gas is connected with the second inlet of the second flow combiner;
the outlet of the first compressor is connected with the low-temperature fluid inlet of the air preheater, the low-temperature fluid outlet of the air preheater is connected with the cathode inlet of the solid oxide fuel cell, and the cathode outlet of the solid oxide fuel cell is connected with the high-temperature fluid inlet of the air preheater;
the adsorbent outlet of the adsorber is connected with the adsorbent inlet of the regenerator, and the adsorbent outlet of the regenerator is connected with the adsorbent inlet of the adsorber.
Further, the first flow divider can adjust the flow dividing ratio, so that the flow ratio of the tail gas which flows back to drive the reformer and the tail gas which enters the dehydration and decarbonization processes is adjusted, and the external heat generation amount is further adjusted.
Further, the adsorber may regulate CO of the outlet fluid 2 Concentration and regulation of CO 2 The adsorption process, and then the heat generation amount is adjusted.
Further, the adsorber is a low temperature solid adsorber.
Further, the regenerator can adjust the regeneration reaction process of the adsorbent, thereby adjusting the heat absorption capacity.
In order to achieve the above object, the present invention further provides a thermoelectric decoupling method of the above fuel cell system, including the following procedures:
air flow path treatment: the air enters the air preheater after passing through the first air compressor and is preheated by the tail gas of the cathode of the battery, and is converted into hot air, and the hot air enters the cathode of the solid oxide fuel battery to participate in electrochemical reaction;
hydrocarbon fuel and water flow path treatment: the mixture of hydrocarbon fuel and water enters the evaporator through the pump, and is heated and evaporated through the evaporator to be converted into a water-gas mixture of hydrocarbon fuel and water, the water-gas mixture of hydrocarbon fuel and water enters the first confluence device to be converged with the first branch anode tail gas to be mixed gas, the mixed gas enters the reformer to be subjected to hydrocarbon fuel reforming reaction to be converted into reformed gas, the reformed gas enters the second confluence device to be converged with the anode tail gas to be anode fuel gas, and the anode fuel gas enters the anode of the solid oxide fuel cell to participate in electrochemical reaction;
anode tail gas flow path treatment: the anode tail gas enters the first flow divider through the second compressor and is divided into a first branch anode tail gas and a second branch anode tail gas, and the first branch anode tail gas flows back to the first flow divider; the second branch anode tail gas is divided into third branch anode tail gas and fourth branch anode tail gas through the second flow divider; the third branch anode tail gas passes through the regenerator, is heated by the regenerator and then enters the condenser together with the fourth branch anode tail gas to be fedHot water from a heat user is heated, flows out of the condenser and enters the adsorber to react with the adsorbent to remove CO 2 And then back flowing into the second confluence device.
Hot water flow path treatment: hot water from a heat user enters a cold fluid inlet of the absorber after being heated by the condenser, and enters the solid oxide fuel cell for heat exchange and further heating after the reaction heat in the adsorption process is absorbed and heated, and finally the hot water is sent to the heat user.
Further, the operation modes of the thermocouple include:
enhanced heating mode: at the moment, the thermoelectric ratio is increased, the second flow divider is adjusted to reduce the flow of the anode tail gas B of the third branch, and the flow of the anode tail gas C of the fourth branch is increased, so that more heat is transferred to hot water; the operating state point of the solid oxide fuel cell stack moves towards reducing the generated power; in an extreme case, the flow of the third branch anode tail gas B is zero, the adsorber is decoupled from the regenerator, and the regenerator stops running;
enhanced power mode: at the moment, the thermoelectric ratio is reduced, the second flow divider is adjusted to increase the flow of the anode tail gas B of the third branch, and the flow of the anode tail gas C of the fourth branch is reduced, so that more heat is used for driving the regenerator; the operating state point of the solid oxide fuel cell stack moves towards increasing the generated power; in the extreme case, the flow of the anode tail gas C of the fourth branch is zero, the adsorber is decoupled from the regenerator, and the regenerator stops operating.
Further, the hydrocarbon fuel is diesel oil, methanol, formic acid or methane.
Further, the chemical reaction in the reformer includes:
hydrocarbon fuel steam reforming reaction:
；
dry reforming reaction of hydrocarbon fuel:
；
reverse water vapor reaction:
；
methanation reaction:
；
methanation reaction:
。
compared with the prior art, the invention has the beneficial effects that:
in order to reduce carbon emission, the solid oxide fuel cell driven by hydrocarbon fuel can capture CO by adopting an adsorption method 2 ，CO 2 Adsorption and regeneration of the adsorbent are exothermic and endothermic processes, respectively, the adsorbent has a volumetric energy density comparable to that of the heat storage material (e.g., calcium oxide itself is both a heat storage material and CO 2 Adsorbent material), carbon-captured CO 2 The adsorption/regeneration process can have a heat storage effect at the same time, and the thermal decoupling of the system is realized by the operation decoupling of adsorption (heat release)/regeneration (heat storage) time. According to the thermoelectric load change, the adsorption and regeneration processes are not performed simultaneously: when the heat generated by the system is larger than the heat load, the waste heat can be used for driving the regeneration process; on the contrary, the heat absorption and the heat release in the regeneration process meet the heat load gap.
According to the invention, two functions of carbon capture and heat storage are realized through one set of carbon adsorption/regeneration equipment, the requirement on special equipment for heat storage is reduced, and flexible decoupling regulation and control of heat supply and power supply of the system are realized.
Drawings
FIG. 1 is a block diagram of a fuel cell system based on carbon capture and thermal storage sharing provided by an embodiment of the present invention;
FIG. 2 is a block diagram of a fuel cell system according to an embodiment of the present invention in a heat-enhanced mode of operation;
fig. 3 is a block diagram of a fuel cell system according to an embodiment of the present invention in an enhanced power mode of operation.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "front", "rear", "vertical", "horizontal", "inner", "outer", etc., are based on those shown in the drawings, are merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or elements referred to must have a specific direction, be configured and operated in the specific direction, and thus should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be directly connected or indirectly connected through an intermediate medium, and can be the communication between the two parts. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Referring to fig. 1, a fuel cell system based on carbon capture and heat storage sharing provided in this embodiment includes a solid oxide fuel cell, a reformer, an evaporator, an air preheater, a condenser, an adsorber, a regenerator, a first combiner, a second combiner, a first splitter, a second splitter, a first compressor, a second compressor, and a pump.
The outlet of the pump is connected with the low-temperature fluid inlet of the evaporator, the low-temperature fluid outlet of the evaporator is connected with the first inlet of the first confluence device, and the outlet of the first confluence device is connected with the reactant inlet of the reformer.
The product outlet of the reformer is connected with the first inlet of the second confluence device, the outlet of the second confluence device is connected with the anode inlet of the solid oxide fuel cell, the anode outlet of the solid oxide fuel cell is connected with the inlet of the second air compressor, the outlet of the second air compressor is connected with the inlet of the first flow divider, the first outlet of the first flow divider is connected with the second inlet of the first confluence device, and the second outlet of the first flow divider is connected with the inlet of the second flow divider.
The first outlet of the second flow divider is connected with the high-temperature fluid inlet of the condenser, the second outlet of the second flow divider is connected with the heating fluid inlet of the regenerator, the heating fluid outlet of the regenerator is connected with the high-temperature fluid inlet of the condenser, the high-temperature fluid outlet of the condenser is connected with the gas inlet of the absorber, and the gas outlet of the absorber is connected with the second inlet of the second flow combiner.
The outlet of the first air compressor is connected with the low-temperature fluid inlet of the air preheater, the low-temperature fluid outlet of the air preheater is connected with the cathode inlet of the solid oxide fuel cell, and the cathode outlet of the solid oxide fuel cell is connected with the high-temperature fluid inlet of the air preheater.
The adsorbent outlet of the absorber is connected with the adsorbent inlet of the regenerator, and the adsorbent outlet of the regenerator is connected with the adsorbent inlet of the absorber.
Specifically, the first flow divider can adjust the flow dividing ratio, so as to adjust the flow ratio of the tail gas of the reflux driving reformer and the tail gas entering the dehydration and decarbonization process, and further adjust the external heat generation amount.
Adsorber adjustable outlet fluid CO 2 Concentration and regulation of CO 2 The adsorption process is used for further adjusting the heat generation amount; the adsorber is a low temperature solid adsorber, such as a solid amine adsorber.
The regenerator can adjust the regeneration reaction process of the adsorbent, thereby adjusting the heat absorption capacity.
The embodiment also provides a thermoelectric decoupling method of the fuel cell system, which comprises the following steps:
air flow path treatment: the air 1 enters an air preheater after passing through a first air compressor, is preheated by the tail gas of the cathode of the battery and is converted into hot air 2, and the hot air 2 enters the cathode of the solid oxide fuel battery to participate in electrochemical reaction;
hydrocarbon fuel and water flow path treatment: the mixture 3 of hydrocarbon fuel and water enters an evaporator through a pump, the mixture is heated and evaporated by the evaporator and then is converted into a water-gas mixture 4 of hydrocarbon fuel and water, the water-gas mixture 4 of hydrocarbon fuel and water enters a first converging device and is converged with the first branch anode tail gas 5 to form mixed gas 6, the mixed gas 6 enters a reformer to generate hydrocarbon fuel reforming reaction and is converted into reformed gas 7, the reformed gas 7 enters a second converging device and is converged with the anode tail gas 8 to form anode fuel gas 9, and the anode fuel gas 9 enters an anode of the solid oxide fuel cell to participate in electrochemical reaction;
anode tail gas flow path treatment: the anode tail gas 10 enters a first flow divider through a second compressor and is divided into a first branch anode tail gas 5 and a second branch anode tail gas 11, and the first branch anode tail gas 5 flows back to a first flow combiner; the second branch anode tail gas 11 is divided into a third branch anode tail gas 12 and a fourth branch anode tail gas 13 through a second flow divider; the third branch anode tail gas 12 passes through a regenerator, is heated by the regenerator, then enters a condenser together with the fourth branch anode tail gas 13 to heat hot water 14 from a heat user, flows out of the condenser, enters an adsorber to react with an adsorbent, and removes CO 2 And then flows back to the second confluence device.
Hot water flow path treatment: hot water 14 from a heat user is heated by a condenser and then enters a cold fluid inlet of an absorber, reaction heat in the adsorption process is absorbed and then enters a solid oxide fuel cell for heat exchange and further heating, and finally the hot water is sent to the heat user.
The operation modes of the thermoelectric decoupling of the present embodiment include:
enhanced heating mode: referring to fig. 2, the heat-electricity ratio is increased, the second current divider is adjusted to reduce the flow of the anode tail gas 12 of the third branch, and increase the flow of the anode tail gas 13 of the fourth branch, so that more heat is transferred to the hot water; the operating state point of the solid oxide fuel cell stack moves towards reducing the generated power; in extreme cases, the flow of the third branch anode tail gas 12 is zero, the adsorber and the regenerator are decoupled to operate, and the regenerator stops operating;
enhanced power mode: referring to fig. 3, at this point the heat-to-electricity ratio is reduced, the second current divider is adjusted to increase the flow of the third branch anode off-gas 12 and decrease the flow of the fourth branch anode off-gas 13 so that more heat is used to drive the regenerator; the operating state point of the solid oxide fuel cell stack moves towards increasing the generated power; in the extreme case, the flow of the anode tail gas 1 of the fourth branch is zero, the adsorber and the regenerator are decoupled to operate, and the regenerator stops operating.
In particular, the hydrocarbon fuel may be diesel, methanol, formic acid or methane.
The chemical reaction in the reformer includes:
hydrocarbon fuel steam reforming reaction:
；
dry reforming reaction of hydrocarbon fuel:
；
reverse water vapor reaction:
；
methanation reaction:
；
methanation reaction:
。
in order to reduce carbon emissions, the fuel cell system provided in this embodiment uses an adsorption method to capture CO in a solid oxide fuel cell driven by hydrocarbon fuel 2 ，CO 2 Adsorption and regeneration of the adsorbent are exothermic and endothermic processes, respectively, the adsorbent has a volumetric energy density comparable to that of the heat storage material (e.g., calcium oxide itself is both a heat storage material and CO 2 Adsorbent material), carbon-captured CO 2 The adsorption/regeneration process can have a heat storage effect at the same time, and the thermal decoupling of the system is realized by the operation decoupling of adsorption (heat release)/regeneration (heat storage) time. According to thermoelectric load variationAdsorption and regeneration processes are not performed simultaneously: when the heat generated by the system is larger than the heat load, the waste heat can be used for driving the regeneration process; on the contrary, the heat absorption and the heat release in the regeneration process meet the heat load gap.
Therefore, the carbon capturing and heat storage functions are realized through the carbon adsorption/regeneration equipment, the requirement on special equipment for heat storage is reduced, and flexible decoupling regulation and control of heat supply and power supply of the system are realized.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The fuel cell system based on the common use of carbon capture and heat storage is characterized by comprising a solid oxide fuel cell, a reformer, an evaporator, an air preheater, a condenser, an adsorber, a regenerator, a first confluence device, a second confluence device, a first flow divider, a second flow divider, a first compressor, a second compressor and a pump;
the outlet of the pump is connected with the low-temperature fluid inlet of the evaporator, the low-temperature fluid outlet of the evaporator is connected with the first inlet of the first confluence device, and the outlet of the first confluence device is connected with the reactant inlet of the reformer;
the product outlet of the reformer is connected with the first inlet of the second flow combiner, the outlet of the second flow combiner is connected with the anode inlet of the solid oxide fuel cell, the anode outlet of the solid oxide fuel cell is connected with the inlet of the second gas compressor, the outlet of the second gas compressor is connected with the inlet of the first flow divider, the first outlet of the first flow divider is connected with the second inlet of the first flow combiner, and the second outlet of the first flow divider is connected with the inlet of the second flow divider;
the first outlet of the second flow divider is connected with the high-temperature fluid inlet of the condenser, the second outlet of the second flow divider is connected with the heating fluid inlet of the regenerator, the heating fluid outlet of the regenerator is connected with the high-temperature fluid inlet of the condenser, the high-temperature fluid outlet of the condenser is connected with the gas inlet of the absorber, and the outlet of the absorber gas is connected with the second inlet of the second flow combiner;
the outlet of the first compressor is connected with the low-temperature fluid inlet of the air preheater, the low-temperature fluid outlet of the air preheater is connected with the cathode inlet of the solid oxide fuel cell, and the cathode outlet of the solid oxide fuel cell is connected with the high-temperature fluid inlet of the air preheater;
the adsorbent outlet of the adsorber is connected with the adsorbent inlet of the regenerator, and the adsorbent outlet of the regenerator is connected with the adsorbent inlet of the adsorber.
2. The fuel cell system of claim 1, wherein the first flow divider is operable to adjust a split ratio to adjust a flow ratio of exhaust gas flowing back to drive the reformer to exhaust gas entering the dehydration and decarbonization process to thereby adjust an amount of external heat generation.
3. The fuel cell system of claim 1, wherein the adsorber is operable to regulate CO of the outlet fluid 2 Concentration and regulation of CO 2 The adsorption process, and then the heat generation amount is adjusted.
4. The fuel cell system of claim 1, wherein the adsorber is a low temperature solid adsorber.
5. The fuel cell system of claim 1, wherein the regenerator is operable to adjust the adsorbent regeneration reaction process and thereby adjust the amount of heat absorbed.
6. A method of thermoelectric decoupling a fuel cell system as claimed in claim 1, comprising the steps of:
air flow path treatment: the air enters the air preheater after passing through the first air compressor and is preheated by the tail gas of the cathode of the battery, and is converted into hot air, and the hot air enters the cathode of the solid oxide fuel battery to participate in electrochemical reaction;
hydrocarbon fuel and water flow path treatment: the mixture of hydrocarbon fuel and water enters the evaporator through the pump, and is heated and evaporated through the evaporator to be converted into a water-gas mixture of hydrocarbon fuel and water, the water-gas mixture of hydrocarbon fuel and water enters the first confluence device to be converged with the first branch anode tail gas to be mixed gas, the mixed gas enters the reformer to be subjected to hydrocarbon fuel reforming reaction to be converted into reformed gas, the reformed gas enters the second confluence device to be converged with the anode tail gas to be anode fuel gas, and the anode fuel gas enters the anode of the solid oxide fuel cell to participate in electrochemical reaction;
anode tail gas flow path treatment: the anode tail gas enters the first flow divider through the second compressor and is divided into a first branch anode tail gas and a second branch anode tail gas, and the first branch anode tail gas flows back to the first flow divider; the second branch anode tail gas is divided into third branch anode tail gas and fourth branch anode tail gas through the second flow divider; the third branch anode tail gas passes through the regenerator, is heated by the regenerator and then enters the condenser together with the fourth branch anode tail gas to heat hot water from a heat user, flows out of the condenser and enters the adsorber to react with the adsorbent to remove CO 2 Then, the mixture flows back to the second confluence device;
hot water flow path treatment: hot water from a heat user enters a cold fluid inlet of the absorber after being heated by the condenser, and enters the solid oxide fuel cell for heat exchange and further heating after the reaction heat in the adsorption process is absorbed and heated, and finally the hot water is sent to the heat user.
7. The method of thermocouple as recited in claim 6 wherein the mode of operation of thermocouple comprises:
enhanced heating mode: at the moment, the thermoelectric ratio is increased, the second flow divider is adjusted to reduce the flow of the anode tail gas B of the third branch, and the flow of the anode tail gas C of the fourth branch is increased, so that more heat is transferred to hot water; the operating state point of the solid oxide fuel cell stack moves towards reducing the generated power; in an extreme case, the flow of the third branch anode tail gas B is zero, the adsorber is decoupled from the regenerator, and the regenerator stops running;
enhanced power mode: at the moment, the thermoelectric ratio is reduced, the second flow divider is adjusted to increase the flow of the anode tail gas B of the third branch, and the flow of the anode tail gas C of the fourth branch is reduced, so that more heat is used for driving the regenerator; the operating state point of the solid oxide fuel cell stack moves towards increasing the generated power; in the extreme case, the flow of the anode tail gas C of the fourth branch is zero, the adsorber is decoupled from the regenerator, and the regenerator stops operating.
8. The method of thermocouple as set forth in claim 6 wherein said hydrocarbon fuel is diesel, methanol, formic acid or methane.
9. The method of thermocouple as set forth in claim 6 wherein said chemical reaction in said reformer comprises:
hydrocarbon fuel steam reforming reaction:
；
dry reforming reaction of hydrocarbon fuel:
；
reverse water vapor reaction:
；
methanation reaction:
；
methanation reaction:
。/>
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