CN114725432A - Zero-carbon power generation system and power generation process of solid oxide fuel cell - Google Patents
Zero-carbon power generation system and power generation process of solid oxide fuel cell Download PDFInfo
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Abstract
The invention combines the hydrogen production process by cracking natural gas with the power generation process by high-temperature solid oxide fuel cells, directly uses natural gas for desulfurization and purification, adopts molten metal to carry out molten metal cracking and decarburization on the natural gas to obtain a carbon product, simultaneously utilizes a separator to cool, separate and purify, reduce pressure and raise temperature the hydrogen in the mixed gas cracked by the molten metal, and uses high-temperature pure hydrogen as the power generation raw material of the high-temperature solid oxide fuel cell stack to generate power. Therefore, on one hand, the energy consumption of the hydrogen production process by cracking molten metal is reduced, on the other hand, the power generation process by directly utilizing the high-temperature hydrogen generated by cracking the molten metal in the high-temperature solid oxide fuel cell realizes the hydrogen production by decarbonizing the natural gas molten metal and the zero carbon emission power generation process of the high-temperature solidified oxide fuel cell by taking hydrogen as fuel.
Description
Technical Field
The invention relates to the technical field of high-temperature solid oxide fuel cell power generation, in particular to a high-temperature solid oxide fuel cell zero-carbon power generation system and a power generation process.
Background
In the high-temperature solid oxide fuel cell power generation technology for producing hydrogen by reforming natural gas, because decarburization treatment is not carried out, carbon in the natural gas is discharged in the form of carbon dioxide, and the problem of carbon discharge of the natural gas for power generation of the high-temperature solid oxide fuel cell cannot be thoroughly solved; in addition, the reformed natural gas is used as a power generation raw material of the high-temperature solid oxide fuel cell, which causes the problem of carbon deposition pollution of the fuel cell, influences the power generation efficiency of the fuel cell, degrades the catalyst performance of the fuel cell, and finally reduces the power generation efficiency and the service life of the fuel cell. Patent CN109372636A discloses a zero-carbon-emission three-cycle integrated coal gasification fuel cell power generation system and method, which realizes the cascade utilization of energy by providing a three-cycle power generation method, but the technical device has a complicated structure, and needs to generate power by using coal as a raw material, thereby consuming energy. In the prior art, hydrogen and carbon products are produced by cracking natural gas by using molten metal, hydrogen is produced by adopting a separation and purification technology, and the hydrogen is compressed and stored. The natural gas molten metal cracking needs to consume heat, meanwhile, various heat exchange devices exist in the system, and the hydrogen production cost is high at present.
Disclosure of Invention
In view of the above, the invention provides a high-temperature solid oxide fuel cell zero-carbon power generation system and a power generation process, which combine a process of producing hydrogen by cracking natural gas with molten metal and a high-temperature solid oxide fuel cell power generation system process to solve the problems in the prior art.
The invention directly uses natural gas for desulfurization and purification, carries out molten metal cracking and decarbonization on the natural gas under the support of a catalyst to obtain a carbon product, and simultaneously uses a separator to separate, purify and heat hydrogen in the molten metal cracking mixed gas, and high-temperature pure hydrogen is directly used as a power generation raw material of a high-temperature solid oxide fuel cell to generate power. Therefore, on one hand, the energy consumption of the purification process is reduced, on the other hand, the power generation process of the high-temperature solidified oxide fuel cell which uses the natural gas for decarbonization to prepare hydrogen and uses hydrogen as fuel and has zero carbon emission is realized by directly using the high-temperature hydrogen generated by the pyrolysis of the molten metal in the high-temperature solid oxide fuel cell. Meanwhile, the high-temperature unreacted tail gas and the purified hydrogen of the high-temperature fuel cell are used as fuels and are combusted in a combustor to provide heat energy for the air, natural gas, hydrogen, a molten metal cracking reactor and the fuel cell of the whole process, so that the comprehensive utilization of energy is realized, and the zero carbon emission of the whole natural gas decarburization, hydrogen production and high-temperature solid oxide fuel cell power generation process is realized.
Meanwhile, the high-temperature tail gas of the high-temperature solid oxide fuel cell and the hydrogen separated by the cracking of the molten metal are used as fuels, and are combusted in a combustor to generate heat, so that heat energy is provided for an air, natural gas, hydrogen and molten metal cracking reactor of the whole process, and the zero carbon emission of the whole natural gas decarburization, hydrogen production and high-temperature solid oxide fuel cell power generation process is realized while the comprehensive utilization of energy is achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high temperature solid oxide fuel cell zero carbon power generation system comprising: the device comprises an air processing unit, a natural gas processing unit, a molten metal cracking mixed gas processing unit and a molten metal cracking reaction furnace;
the air unit, the natural gas processing unit and the molten metal cracking mixed gas unit are all connected with the molten metal cracking reaction furnace;
wherein the air handling unit comprises: the system comprises an air and air primary preheater, a starting electric heater I, an air secondary preheater, a cold air bypass valve, a high-temperature solid oxide fuel cell stack and a combustor; the air is sequentially connected with the air primary preheater, the starting electric heater I, the air secondary preheater, the cold air bypass valve, the high-temperature solid oxide fuel cell stack and the combustor; the burner is connected with the molten metal cracking reaction furnace;
the natural gas processing unit comprises: the system comprises natural gas, a desulfurization unit, a compressor and a natural gas preheater; the natural gas is sequentially connected with the desulfurization unit, the compressor and the natural gas preheater; the natural gas preheater is connected with the molten metal cracking reaction furnace;
the molten metal cracking mixed gas treatment unit comprises: the system comprises a separator, a pressure reducing valve, a hydrogen preheater and a cold hydrogen bypass valve; the separator is sequentially connected with the pressure reducing valve, the hydrogen preheater and the cold hydrogen bypass valve; the separator is connected with the molten metal cracking reaction furnace through the air primary preheater; the separator is also connected with the combustor and the compressor respectively; the natural gas preheater is connected with the air secondary preheater through the hydrogen preheater; the cold hydrogen bypass valve is connected with the high-temperature solid oxide fuel cell stack;
and a second starting electric heater is arranged in the molten metal cracking reaction furnace.
Preferably, the system further comprises: a hydrothermal heat exchanger; the water heat exchanger is connected with the molten metal cracking reaction furnace.
Preferably, the system further comprises: a tail gas emission unit; and the tail gas emission unit is connected with the air secondary preheater.
Preferably, a first branch is arranged between the air and the primary air preheater, and the air is directly connected with the cold air bypass valve through the first branch.
Preferably, a second branch is arranged between the pressure reducing valve and the hydrogen preheater, and the pressure reducing valve is directly connected with the cold hydrogen bypass valve through the second branch.
A zero-carbon power generation process of a solid oxide fuel cell utilizes the zero-carbon power generation system of the solid oxide fuel cell to generate power; the method specifically comprises the following steps:
(1) air treatment: the filtered air is divided into two paths, wherein one path enters a cold air bypass valve and is used for air temperature regulation of the high-temperature solid oxide fuel cell stack; the other path of the hot air enters an air primary preheater to absorb heat energy, the heated hot air enters a starting electric heater I (used for heating air during cold starting and not used after normal operation), the air which passes through the starting electric heater I enters an air secondary preheater to absorb heat energy, the reheated hot air is mixed with cold air entering from a cold air bypass valve to realize temperature regulation, the temperature of the hot air is controlled to be the temperature required by a high-temperature solid oxide fuel cell stack and enters the high-temperature solid oxide fuel cell stack for reaction, the electric energy generated by the high-temperature solid oxide fuel cell stack is output for users to use, the hot air tail gas of the anode after the fuel cell reaction enters a combustor to participate in combustion, and the heat energy and the residual oxygen are further utilized; in addition, the starting electric heater I is used for preheating the whole power generation system, and does not work after the power generation system works normally;
(2) natural gas treatment: after the natural gas is desulfurized by a desulfurization unit, the pressure of the natural gas is increased by a compressor to form high-pressure natural gas, the high-pressure natural gas is absorbed by a natural gas preheater and provides heat energy from a hydrogen combustor to form high-pressure high-temperature natural gas, the high-pressure high-temperature natural gas enters a molten metal cracking reaction furnace, the high-pressure high-temperature natural gas is decarburized and subjected to molten metal cracking in a catalyst which is heated by a heater of the molten metal cracking reaction furnace (the heat energy is provided by a starting electric heater II during cold starting and the heat energy is provided by the combustion hydrogen of the combustor after normal operation), a carbon product separated from the natural gas enters a water heat exchanger and is changed into a normal-temperature carbon product to be discharged, and hot water discharged from the water heat exchanger can be used for production and life;
(3) and (3) treating the molten metal cracking mixed gas: the mixed gas of the cracking of the molten metal enters the first-level preheater of air, give the air with the heat energy exchange, the mixed gas of the cracking of the molten metal after the cooling enters the separator and decomposes out methane and hydrogen, the methane of separating out and natural gas after the desulfurization enter into the cracking reaction furnace of the molten metal in the lump and melt the metal cracking again, the hydrogen of separating out is divided into two routes: one path of hydrogen is sent into a combustor to be combusted as fuel to provide heat energy for the whole system, the product after the hydrogen combustion is water, no carbon is discharged in tail gas, the other path of hydrogen is decompressed by a decompression valve to obtain low-pressure hydrogen, the low-pressure hydrogen enters a hydrogen preheater to absorb heat, the formed low-pressure high-temperature hydrogen is mixed with low-pressure cold hydrogen from a cold hydrogen bypass valve to obtain low-pressure high-temperature hydrogen with the temperature suitable for the power generation of a high-temperature solid oxide fuel cell stack, the low-pressure high-temperature hydrogen enters the high-temperature solid oxide fuel cell stack to generate power, the generated power can be output for a user, the residual hydrogen after the power generation is sent into the combustor to be combusted as the fuel to provide heat energy for the whole system, no carbon is discharged in the high-temperature tail gas of the combustor, and the residual hydrogen is discharged after being cooled by each stage of heat exchanger.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the high-temperature waste heat of the high-temperature solid oxide fuel cell power generation system can be used as the condition of natural gas molten metal cracking decarburization reaction, and the hydrogen which is not completely reacted in the high-temperature tail gas of the fuel cell enters a burner to be burned so as to realize the comprehensive utilization of the energy of the whole system, thereby improving the energy utilization efficiency of the whole process.
(2) After natural gas molten metal is cracked, the generated high-purity hydrogen directly enters a solid oxide fuel cell to generate electricity, and zero emission of carbon of a power generation system is realized.
(3) The hot water generated by the natural gas decarbonization product through the water heat exchanger can be used for production and life, and the methane separated from the mixed gas of the molten metal cracking can be directly returned to the molten metal cracking reaction furnace for remelting metal cracking.
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 embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a process diagram of zero-carbon power generation of a high-temperature solid oxide fuel cell according to the invention.
Wherein, in the figure:
1-air; 2-air primary preheater; 3-starting the electric heating I; 4-air secondary preheater; 5-a cold air bypass valve; 6-high temperature solid oxide fuel cell stack; 7-a burner; 8-a molten metal cracking reaction furnace; 81-starting the second electric heater; 82-a reactor heater; 9-natural gas; 10-a desulfurization unit; 11-a compressor; 12-natural gas preheater; 13-a separator; 14-a pressure relief valve; 15-a hydrogen preheater; 16-a cold hydrogen bypass valve; 17-hydrothermal reactor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A solid oxide fuel cell zero carbon power generation system comprising: an air processing unit, a natural gas processing unit, a molten metal cracking mixed gas processing unit and a molten metal cracking reaction furnace 8;
the air unit, the natural gas processing unit and the molten metal cracking mixed gas unit are all connected with the molten metal cracking reaction furnace;
wherein the air handling unit comprises: the system comprises an air 1, an air primary preheater 2, a starting electric heater I3, an air secondary preheater 4, a cold air bypass valve 5, a high-temperature solid oxide fuel cell stack 6 and a combustor 7; the air 1 is sequentially connected with the air primary preheater 2, the starting electric heater I3, the air secondary preheater 4, the cold air bypass valve 5, the high-temperature solid oxide fuel cell stack 6 and the combustor 7; the burner 7 is connected with the molten metal cracking reaction furnace 8;
the natural gas processing unit comprises: natural gas 9, a desulfurization unit 10, a compressor 11 and a natural gas preheater 12; the natural gas 9 is sequentially connected with a desulfurization unit 10, a compressor 11 and a natural gas preheater 12; the natural gas preheater 12 is connected with the molten metal cracking reaction furnace 8;
the molten metal cracking mixed gas treatment unit comprises: a separator 13, a pressure reducing valve 14, a hydrogen preheater 15 and a cold hydrogen bypass valve 16; the separator 13 is connected with the pressure reducing valve 14, the hydrogen preheater 15 and the cold hydrogen bypass valve 16 in sequence; the separator 13 is connected with the molten metal cracking reaction furnace 8 through the air primary preheater 2; the separator 13 is also connected to the combustor 7 and the compressor 11, respectively; the natural gas preheater 12 is connected with the air secondary preheater 4 through the hydrogen preheater 15; the cold hydrogen bypass valve 16 is connected to the high temperature solid oxide fuel cell stack 6.
In order to further optimize the above technical solution, the power generation system further includes: a hydrothermal heat exchanger 17; the water heat exchanger 17 is connected to the molten metal cracking reactor 8.
In order to further optimize the technical scheme, a first branch is arranged between the air 1 and the primary air preheater 2, and the air 1 is directly connected with the cold air bypass valve 5 through the first branch.
In order to further optimize the technical scheme, a second branch is arranged between the pressure reducing valve 14 and the hydrogen preheater 15, and the pressure reducing valve 14 is directly connected with the cold hydrogen bypass valve 15 through the second branch;
in order to further optimize the technical scheme, a second pneumatic electric heater 81 and a heater 82 of the reaction furnace are arranged in the molten metal cracking reaction furnace 8.
Example 2
A zero-carbon power generation process of a solid oxide fuel cell specifically comprises the following steps:
(1) air treatment: the filtered air 1 is divided into two paths, one path enters a cold air bypass valve 5 and is used for air temperature regulation of a high-temperature solid oxide fuel cell stack 6; the other path of the hot air enters an air primary preheater 2 to absorb heat energy, the heated hot air enters a starting electric heater I3 (used for heating air during cold starting and not used after normal operation), the air passing through the starting electric heater I3 enters an air secondary preheater 4 to absorb heat energy, the reheated hot air is mixed with cold air entering from a cold air bypass valve 5 to realize temperature regulation, the temperature of the hot air is controlled to be the temperature required by a high-temperature solid oxide fuel cell stack 6 and enters a reaction, the generated electric energy is output for a user to use, the tail gas of the reacted hot air enters a combustor 7 to participate in combustion, the heat energy is sent into a molten metal cracking reaction furnace 8 to be used, and the heat energy and the residual oxygen are further utilized;
(2) natural gas treatment: after being desulfurized by a desulfurization unit 10, natural gas 9 is pressurized by a compressor 11 to become high-pressure natural gas, the high-pressure natural gas is absorbed by a natural gas preheater 12 and comes from a combustor 7 (heat energy firstly enters a molten metal cracking reaction furnace 8 and then enters a natural gas preheater 12) to provide heat energy to become high-pressure high-temperature natural gas, the high-pressure high-temperature natural gas enters the molten metal cracking reaction furnace 8, the high-temperature natural gas is decarburized and subjected to molten metal cracking in a catalyst heated by a molten metal cracking reaction furnace heater 82 (heat energy is provided by a starting electric heater II during cold start, and heat energy is provided by combustion hydrogen of the combustor 7 after normal operation), a high-temperature carbon product obtained by natural gas separation enters a water heat exchanger 17 and is changed into a normal-temperature carbon product to be discharged, and hot water discharged from the water heat exchanger 17 can be used for production and life;
(3) and (3) treating the molten metal cracking mixed gas: the mixed gas of the pyrolysis of the molten metal enters the first-level preheater 2 of air, give the air with the heat energy exchange, the mixed gas of the pyrolysis of the molten metal after the cooling enters the separator 13 and decomposes out methane and hydrogen, the methane of separating out and natural gas after the desulfurization enter the pyrolysis of the molten metal in the reaction furnace 8 of the pyrolysis of the molten metal together, the hydrogen of separating out is divided into two routes: one path of hydrogen is sent into a combustor 7 and is combusted as fuel to provide heat energy for the whole system, the product after the hydrogen combustion is water, no carbon is discharged in tail gas, the other path of hydrogen is decompressed by a decompression valve 14 to obtain low-pressure hydrogen, the low-pressure hydrogen enters a hydrogen preheater 15 to absorb heat, the formed low-pressure high-temperature hydrogen is mixed with low-pressure cold hydrogen from a cold hydrogen bypass valve 16 to obtain low-pressure high-temperature hydrogen with the temperature suitable for the power generation of a high-temperature solid oxide fuel cell stack 6, the low-pressure high-temperature hydrogen enters the high-temperature solid oxide fuel cell stack 6 to generate power, the generated power is output for a user, the rest hydrogen after the power generation is sent into the combustor 7 to be combusted as fuel to provide heat energy for the whole system, no carbon is discharged in the high-temperature tail gas of the combustor 7, and the rest hydrogen is discharged after being cooled by heat exchangers at all levels.
In the invention, natural gas is subjected to desulfurization and molten metal cracking processes, and the generated high-purity hydrogen enters the high-temperature solid oxide fuel cell to generate electricity, so that zero-carbon electricity generation of the natural gas is realized. The high-temperature waste heat of the high-temperature solid oxide fuel cell power generation system is used for natural gas molten metal cracking, and the fuel cell power generation tail gas enters the combustor to be combusted together with hydrogen, so that the waste heat of the hydrogen and air is recycled, and the comprehensive utilization efficiency of energy is improved. The invention can solve the high-temperature catalytic condition required by hydrogen production and decarburization by natural gas molten metal cracking, the generated high-temperature hydrogen can directly enter the solid oxide fuel cell for power generation fuel without compression storage and temperature reduction, and additional energy consumption is not required.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A high temperature solid oxide fuel cell zero carbon power generation system, comprising: the device comprises an air processing unit, a natural gas processing unit, a molten metal cracking mixed gas processing unit and a molten metal cracking reaction furnace;
the air unit, the natural gas processing unit and the molten metal cracking mixed gas unit are all connected with the molten metal cracking reaction furnace;
wherein the air handling unit comprises: the system comprises an air and air primary preheater, a starting electric heater I, an air secondary preheater, a cold air bypass valve, a high-temperature solid oxide fuel cell stack and a combustor; the air is sequentially connected with the air primary preheater, the starting electric heater I, the air secondary preheater, the cold air bypass valve, the high-temperature solid oxide fuel cell stack and the combustor; the combustor is connected with the molten metal cracking reaction furnace;
the natural gas processing unit comprises: the system comprises natural gas, a desulfurization unit, a compressor and a natural gas preheater; the natural gas is sequentially connected with the desulfurization unit, the compressor and the natural gas preheater; the natural gas preheater is connected with the molten metal cracking reaction furnace;
the molten metal cracking mixed gas treatment unit comprises: the system comprises a separator, a pressure reducing valve, a hydrogen preheater and a cold hydrogen bypass valve; the separator is sequentially connected with the pressure reducing valve, the hydrogen preheater and the cold hydrogen bypass valve; the separator is connected with the molten metal cracking reaction furnace through the air primary preheater; the separator is also connected with the combustor and the compressor respectively; the natural gas preheater is connected with the air secondary preheater through the hydrogen preheater; the cold hydrogen bypass valve is connected with the high-temperature solid oxide fuel cell stack;
and a second starting electric heater and a reactor heater are respectively arranged in the molten metal cracking reactor.
2. The high temperature solid oxide fuel cell zero carbon power generation system of claim 1, further comprising: a hydrothermal heat exchanger; the water heat exchanger is connected with the molten metal cracking reaction furnace.
3. The system according to claim 2, wherein a first branch is provided between the air and the primary air preheater, and the air is directly connected to the cold air bypass valve through the first branch.
4. The high temperature solid oxide fuel cell zero carbon power generation system of claim 3, wherein a second branch is provided between the pressure reducing valve and the hydrogen preheater, and the pressure reducing valve is directly connected to the cold hydrogen bypass valve through the second branch.
5. A zero-carbon power generation process of a solid oxide fuel cell, which is characterized in that the zero-carbon power generation system of the solid oxide fuel cell of claim 4 is used for generating power; the method specifically comprises the following steps:
(1) air treatment: the filtered air is divided into two paths, one path enters a cold air bypass valve, the other path enters an air primary preheater to absorb heat energy, the heated hot air enters a starting electric heater I and then enters an air secondary preheater, the reheated hot air is mixed with cold air entering from the cold air bypass valve to realize temperature regulation, the temperature of the hot air is controlled to be the temperature required by a high-temperature solid oxide fuel cell stack and enters the high-temperature solid oxide fuel cell stack for reaction, the tail gas of the hot air after the reaction enters a combustor to participate in combustion reaction, the heat energy is used for supplying heat to a molten metal cracking reaction furnace and heating hydrogen and air, in addition, the starting electric heater I is used for preheating the whole power generation system, and the starting electric heater I does not work after the power generation system works normally;
(2) natural gas treatment: after the natural gas is desulfurized by a desulfurization unit, the pressure of the natural gas is increased by a compressor to form high-pressure natural gas, the high-pressure natural gas absorbs heat energy provided by a combustor through a natural gas preheater to form high-pressure high-temperature natural gas, the high-pressure high-temperature natural gas enters a molten metal cracking reaction furnace, the high-pressure high-temperature natural gas is decarburized in a catalyst heated by a heater of the molten metal cracking reaction furnace, molten metal is cracked to form a high-temperature carbon product and molten metal cracking mixed gas, and the high-temperature carbon product enters a water heat exchanger to exchange heat and cool to obtain a normal-temperature carbon product;
(3) and (3) treating the molten metal cracking mixed gas: the molten metal schizolysis gas mixture that produces in the molten metal schizolysis reacting furnace gets into air one-level pre-heater, gives the air with heat energy exchange, and the molten metal schizolysis gas mixture after the cooling gets into the separator and separates out methane and hydrogen, and the natural gas after the methane of separating and the desulfurization gets into in the molten metal schizolysis reacting furnace in the lump and carries out the schizolysis reaction again, and the hydrogen of separating is divided into two the tunnel: one path of hydrogen is sent into a combustor, the other path of hydrogen is decompressed by a decompression valve and then enters a hydrogen preheater to absorb heat, formed low-pressure high-temperature hydrogen is mixed with low-pressure cold hydrogen from a cold hydrogen bypass valve and then enters a high-temperature solid oxide fuel cell stack, electricity generated by the high-temperature solid oxide fuel cell stack is output to be used by a user, the residual hydrogen after reaction is sent into the combustor, and the heat energy generated by the combustor enters a molten metal cracking reaction furnace.
6. The solid oxide fuel cell zero-carbon power generation process of claim 5, wherein in the step (2), the molten metal cracking reaction furnace is heated by starting the electric heater II to reach the cracking reaction temperature condition during cold start.
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