CN120717410A - A closed-loop energy-saving ammonia-hydrogen-ammonia circulation system and control method - Google Patents
A closed-loop energy-saving ammonia-hydrogen-ammonia circulation system and control methodInfo
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- CN120717410A CN120717410A CN202510708508.5A CN202510708508A CN120717410A CN 120717410 A CN120717410 A CN 120717410A CN 202510708508 A CN202510708508 A CN 202510708508A CN 120717410 A CN120717410 A CN 120717410A
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Abstract
The invention discloses a closed-loop energy-saving ammonia-hydrogen-ammonia circulating system and a control method, the device comprises a liquid ammonia tank, an ammonia decomposition module, a decomposition gas cooling and purifying module, a power supply module, a fuel cell module, an electrolyzed water module, a synthetic ammonia module and a burner. The system realizes energy cascade utilization through the multistage heat exchanger, wherein the first heat exchanger exchanges heat between high-temperature gas in the ammonia decomposition and ammonia synthesis process and the fused salt heat storage module, and the heat stored by the fused salt can be used for turbine power generation. The decomposed gas is purified by a TSA and a PSA adsorption column and then is respectively supplied to a fuel cell and a synthetic ammonia module, electric power, water and tail gas generated by the fuel cell are respectively supplied to an electrolytic water module and a burner, and hydrogen generated by electrolytic water can supplement synthetic ammonia raw materials. The system innovatively combines ammonia decomposition hydrogen production with electrolytic water hydrogen production, realizes zero-carbon operation through heat energy recovery, power self-supply and material circulation, has the characteristics of energy conservation, environmental protection, high efficiency, stability and the like, is suitable for a dry environment with water shortage, and can realize the functions of grid connection, peak clipping and valley filling.
Description
Technical Field
The invention relates to the technical field of hydrogen energy equipment, in particular to a closed-loop energy-saving ammonia-hydrogen-ammonia circulating system integrating ammonia decomposition, ammonia synthesis, electrolysis water and a fuel cell and a control method.
Background
As global energy structures are transformed to low carbonization, hydrogen energy is attracting attention as a clean energy carrier. However, hydrogen has technical bottlenecks such as poor safety in storage and transportation, high cost and the like. Ammonia (NH 3) is considered an ideal hydrogen energy carrier due to its high hydrogen content, ease of liquefaction, and mature storage and transportation infrastructure. In recent years, an Ammonia-Hydrogen fusion energy system (A2H) becomes a research hot spot, but the prior art still has the key problems that 1) the energy conversion efficiency is low, the traditional Ammonia decomposition Hydrogen production needs high temperature above 600 ℃, the reaction heat is not fully recycled, the energy efficiency is less than 60%, 2) the carbon footprint problem is that the industrial synthesis Ammonia depends on fossil energy Hydrogen production (such as natural gas reforming), the emission of about 1.8 tons of CO 2 per ton of Ammonia is difficult to meet the carbon neutralization requirement, 3) the system fragmentation is that the prior art mainly develops Ammonia decomposition, fuel cells or electrolytic water units in isolation, the lack of 'Ammonia-Hydrogen-electricity-Hydrogen-Ammonia' closed loop coupling design leads to low material and energy utilization rate, 4) the dynamic response is insufficient, when renewable energy power supply fluctuates, the traditional system cannot flexibly adjust the Ammonia decomposition and synthesis rate, the power load requirement is difficult to be matched, and aiming at the defects, a novel closed-loop Ammonia-Hydrogen circulation system is required, the full-Hydrogen generation energy recycling technology is realized by deep integration of Ammonia decomposition, the renewable energy electrolysis water, low carbon electrolysis fuel cells and the low carbon synthesis energy, and the energy synthesis Hydrogen production and the energy generation system is difficult to realize near zero emission.
Chinese patent CN113594526A discloses a polygeneration system based on ammonia energy storage and a working method thereof, which combine renewable energy power generation, electrolyzed water hydrogen production, ammonia fuel energy storage, ammonia decomposition hydrogen production and fuel cells, realize polygeneration of oxygen, hydrogen and electric power and are suitable for long-distance transportation, however, the polygeneration system is independently carried out in each working procedure in the operation process, coordination and energy effective distribution of each working procedure are difficult to realize in the operation process, and the whole energy consumption is high and the operation efficiency is low.
Disclosure of Invention
Aiming at the defects that an ammonia-hydrogen fusion energy system in the prior art has low energy conversion efficiency, independent operation and fragmentation, incapability of realizing coordinated and orderly operation and effective output of each working procedure, high overall energy consumption, low operation efficiency and the like, the closed-loop energy-saving ammonia-hydrogen-ammonia circulation system capable of efficiently operating and integrating ammonia decomposition, water electrolysis hydrogen production, synthetic ammonia and fuel cells with low energy consumption and the control method are provided.
The invention solves the technical problems by adopting the technical scheme that the closed-loop energy-saving ammonia-hydrogen-ammonia circulating system comprises a liquid ammonia tank, an ammonia decomposition module, a decomposition gas cooling and purifying module, a power supply module, a fuel cell module, an electrolyzed water module, an ammonia synthesis module and a combustor, wherein the liquid ammonia tank is used for providing ammonia for the ammonia hydrogen production module, the combustor is used for providing heated gas for the ammonia hydrogen production module, a first heat exchanger is arranged between the ammonia decomposition module and the decomposition gas cooling and purifying module, the first heat exchanger is further connected with a fused salt heat storage module and the ammonia synthesis module, the first heat exchanger can exchange heat between gas discharged from the ammonia decomposition module and ammonia discharged from the ammonia synthesis module and fused salt discharged from the fused salt heat storage module, the first heat exchanger is communicated with the liquid ammonia tank, the decomposition gas cooling and purifying module comprises a TSA adsorption column, a PSA adsorption column and a first buffer tank which are connected in series, the TSA adsorption column is further connected with the fuel cell module, the PSA adsorption column is further connected with the ammonia synthesis module, the first buffer tank is used for storing gas which is sequentially subjected to TSA adsorption column and PSA adsorption purification, the first buffer column is further connected with the fuel cell module, the first buffer tank is further connected with the fuel cell module and the fuel cell module through the power supply module and the fuel cell module, and the fuel cell cooling and the fuel cell module is further connected with the power supply module through the power supply module and the fuel cell module.
The ammonia decomposing module comprises an evaporator, a second buffer tank, a second heat exchanger, an ammonia hydrogen production reactor, a hydrogen cylinder and a blower, wherein the liquid ammonia tank is sequentially connected with the evaporator, the second buffer tank and the second heat exchanger in series, the ammonia hydrogen production reactor is of a sleeve type structure, a nickel-based catalyst or a ruthenium-based catalyst is filled in a tube side of the ammonia hydrogen production reactor, the blower and the hydrogen cylinder are simultaneously connected with a burner, and the burner is connected with a shell side of the ammonia hydrogen production reactor.
Further, a tube side outlet and a shell side outlet of the ammonia hydrogen production reactor are both connected with a first heat exchanger, the molten salt heat storage module comprises a first molten salt storage tank, a molten salt pump and a second molten salt storage tank which are separately and independently arranged, the first molten salt storage tank is connected with the molten salt pump, the molten salt pump is connected with the first heat exchanger, and the first heat exchanger is connected with the second molten salt tank.
Further, the fuel cell module comprises a pile, a steam-water separator, a deionizing device, a first water tank and a condensation drying separator, wherein an outlet of the pile is sequentially connected with the steam-water separator, the deionizing device and the first water tank, the steam-water separator is connected with the condensation drying separator, and the condensation drying separator is connected with the burner.
The power supply module comprises a solar power generation unit, a steam turbine power generation unit and a power storage unit, wherein the solar power generation unit and the steam turbine power generation unit are respectively and electrically communicated with the power storage unit, the electric pile is also electrically communicated with the power storage unit, the power storage unit is further electrically communicated with the electrolyzed water module, the first water tank is connected with the electrolyzed water module, the steam turbine power generation unit is connected with the second water tank and the fifth heat exchanger, the second water tank is connected with the water pump, and the fifth heat exchanger is respectively connected with the second molten salt storage tank and the first molten salt storage tank.
Further, the water electrolysis module comprises an electrolytic tank, a sixth buffer tank, a first pressure reducing valve, a seventh buffer tank and a second pressure reducing valve, one end of the electrolytic tank is connected with the sixth buffer tank and the first pressure reducing valve, the other end of the electrolytic tank is connected with the seventh buffer tank and the second pressure reducing valve, and the first pressure reducing valve and the second pressure reducing valve are connected with the fuel cell module.
The ammonia synthesis module comprises an air compressor, a nitrogen making unit, a third buffer tank, a fourth buffer tank, a first compressor, a second compressor, a fifth buffer tank, a third compressor, a third heat exchanger and an ammonia synthesis tower, wherein the air compressor is sequentially connected with the nitrogen making unit and the third buffer tank, the third buffer tank is connected with the first compressor, the fourth buffer tank is connected with the first buffer tank, the fourth buffer tank is connected with the second compressor, the first compressor and the second compressor are simultaneously connected with the fifth buffer tank, the fifth buffer tank is connected with the third compressor, the third compressor is connected with the third heat exchanger, the third heat exchanger is connected with the ammonia synthesis tower, the nitrogen making unit is further connected with the fuel cell module, the third buffer tank is further connected with the PSA adsorption column, and the ammonia synthesis tower is connected with the second heat exchanger.
The TSA adsorption column is connected with the first heat exchanger, the second heat exchanger is connected with the first heat exchanger, the first heat exchanger is also connected with the fourth heat exchanger, the liquid ammonia separator and the liquid ammonia pump in series in sequence, the fourth heat exchanger is connected with the refrigerator, the TSA adsorption column is also connected with the fourth heat exchanger, and the liquid ammonia separator is connected with the third compressor.
A control method of a closed-loop energy-saving ammonia-hydrogen-ammonia circulating system; firstly, gasifying liquid ammonia in a liquid ammonia tank into ammonia gas, and then introducing the ammonia gas into an ammonia decomposition module; the method comprises the steps of respectively introducing air and hydrogen into a combustor for combustion, introducing the combusted gas into an ammonia decomposition module, decomposing ammonia into hydrogen-nitrogen mixed gas by the ammonia decomposition module, discharging the decomposed hydrogen-nitrogen mixed gas and the combusted gas from the ammonia decomposition module and introducing the decomposed hydrogen-nitrogen mixed gas into a first heat exchanger, introducing molten salt in a molten salt heat storage module into the first heat exchanger for heat exchange with the hydrogen-nitrogen mixed gas, introducing the heat exchanged hydrogen-nitrogen mixed gas into a TSA adsorption column for purification, introducing part of the hydrogen-nitrogen mixed gas purified by the TSA adsorption column into a fuel cell module, introducing air into a fuel cell module, introducing the fuel cell module for converting chemical energy of the gas into electric energy, introducing the rest hydrogen-nitrogen mixed gas into a PSA adsorption column for separation of hydrogen and nitrogen, introducing part of the hydrogen separated from the PSA column into the fuel cell module for substitution of the hydrogen-nitrogen mixed gas introduced from the TSA adsorption column as fuel of the fuel cell module, introducing part of the hydrogen separated from the adsorption column into the ammonia synthesis gas, introducing part of the hydrogen gas into the fuel cell module for purification, introducing part of the hydrogen gas purified from the PSA column into the fuel cell module for purification, introducing part of the hydrogen gas into the fuel cell module for electrolysis of the fuel cell module, introducing the hydrogen into the fuel cell module for water, introducing the hydrogen into the fuel cell module for water-gas after purifying the hydrogen and introducing the hydrogen into the fuel cell module for water, introducing the hydrogen into the fuel cell module for water, and generating hydrogen and producing hydrogen from the water The method comprises the steps of separating nitrogen, introducing the separated nitrogen into a synthetic ammonia module, increasing the volume of hydrogen entering the synthetic ammonia module from a PSA adsorption column, cooling ammonia in the synthetic ammonia module to form liquid ammonia, and introducing the cooled liquid ammonia into a liquid ammonia tank.
The method comprises the steps of first, introducing ammonia gas into a first heat exchanger for heat exchange, introducing the ammonia gas into a liquid ammonia tank for cooling, introducing gas discharged from an outlet of a fuel cell module into a combustor for combustion, introducing hydrogen generated by electrolysis of a part of an electrolysis water module into the synthesis ammonia module for synthesizing the ammonia gas, and introducing the separated gas into the synthesis ammonia module for synthesizing the ammonia gas in a cooling process of the ammonia gas.
The closed-loop energy-saving ammonia-hydrogen-ammonia circulating system fully utilizes gas energy in the operation process of the synthetic ammonia, ammonia decomposition, electrolytic water and fuel cell modules by adopting a plurality of heat exchangers, reduces the energy consumption of the system, simultaneously realizes the cooperative operation of each module, ensures the cooperative operation of each module, also realizes the rapid power generation and starting of the fuel cell modules by the cooperative action of the ammonia decomposition and the electrolytic water, effectively improves the operation efficiency of the system, finally realizes the stable circulating function of an ammonia-hydrogen-ammonia supply chain, and also ensures that the reaction gas hydrogen of ammonia synthesis is from the electrolytic water hydrogen production system and the ammonia decomposition hydrogen production system, the two sets of systems do not relate to carbon-containing fuel, ensures the zero carbon circulation of the device, realizes the green and environment-friendly functions, the power supply of the electrolytic water hydrogen production system and the power supply of other equipment of the device are from the system, realizes the self-sufficiency of electricity consumption and peak clipping and valley filling functions, stores heat after the high-temperature gas generated by the ammonia decomposition system and the ammonia synthesis system is subjected to heat exchange by using molten salt, and carries out steam power generation by combining, thereby realizing the comprehensive energy generation by combining the steam, the energy-saving and the energy-saving hydrogen and the water-saving hydrogen production system and the full-saving hydrogen production system and the energy-saving and the water-saving system can be supplied to the environment-saving system in a certain place, and the environment-friendly system, and the water-saving system can realize the full-saving and the water-saving system.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are required for the embodiments will be briefly described, and it will be apparent that the drawings in the following description are some embodiments of the present invention and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a closed-loop energy-saving ammonia-hydrogen-ammonia circulation system according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in FIG. 1, the closed-loop energy-saving ammonia-hydrogen-ammonia circulation system comprises a liquid ammonia tank A, an ammonia decomposition module B, a decomposed gas cooling and purifying module C, a power supply module D, a fuel cell module E, an electrolyzed water module F, a synthetic ammonia module G and a combustor 17, wherein the liquid ammonia tank A is used for providing ammonia for the ammonia hydrogen production module B, and the combustor 17 is used for providing heated gas for the ammonia hydrogen production module B;
A first heat exchanger 21 is arranged between the ammonia decomposition module B and the decomposed gas cooling and purifying module C, the first heat exchanger 21 is also connected with a fused salt heat storage module H and the synthetic ammonia module G, the first heat exchanger 21 can exchange heat between gas discharged from the ammonia decomposition module B and ammonia gas discharged from the synthetic ammonia module G and fused salt discharged from the fused salt heat storage module H, and the first heat exchanger 21 is communicated with the liquid ammonia tank A;
The decomposed gas cooling and purifying module C comprises a TSA adsorption column 22, a PSA adsorption column 23 and a first buffer tank 24 which are connected in series, wherein the TSA adsorption column 22 is also connected with the fuel cell module E, the PSA adsorption column 23 is also connected with the synthesis ammonia module G, the first buffer tank 24 is used for storing gas purified by the TSA adsorption column 22 and the PSA adsorption column 23 in sequence, and the first buffer tank 24 is also respectively connected with the synthesis ammonia module G and the fuel cell module E;
The outlet of the fuel cell module E is respectively connected with the electrolyzed water module F and the burner 17, the fuel cell module E is electrically communicated with the power supply module D, the power supply module D is electrically communicated with the fuel cell module E, and the electrolyzed water module F is communicated with the inlet of the fuel cell module E.
As shown in fig. 1, the ammonia decomposition module B includes an evaporator 12, a second buffer tank 13, a second heat exchanger 14, an ammonia hydrogen production reactor 15, a hydrogen cylinder (not shown), and a blower 16; the liquid ammonia tank A is sequentially connected with the evaporator 12, the second buffer tank 13 and the second heat exchanger 14 in series, liquid ammonia discharged from the liquid ammonia tank A is heated and evaporated by the evaporator 12 to generate ammonia, the generated ammonia firstly enters the evaporator 12 for heating and evaporation, the evaporated ammonia enters the second buffer tank 13 and then enters the first heat exchanger 14 for further heat exchange with a heat source, the temperature of the ammonia entering the ammonia hydrogen production reactor 15 is increased to be beneficial to the decomposition of the ammonia, the heating time of gas and ammonia is saved, the temperature gradient of a gas and ammonia inlet of the reactor is reduced, the temperature is heated from 30 ℃ to 70 ℃ to 300 ℃ to 450 ℃, the ammonia after the temperature rise enters the ammonia hydrogen production reactor 15 for carrying out ammonia decomposition reaction, the ammonia hydrogen production reactor 15 is mainly used for producing green hydrogen, the ammonia hydrogen production reactor 15 is of a sleeve structure, a nickel-based catalyst or a ruthenium-based catalyst is filled in a tube side of the ammonia hydrogen production reactor 15, or a combination of the two catalysts is carried out, the ammonia hydrogen production reactor is simultaneously connected with the blower 17 and the combustion sleeve-type hydrogen production reactor 17 according to the specific working conditions, the air blower 16 introduces air into the combustor 17, the hydrogen cylinder is used for introducing hydrogen into the combustor 17, the combustor 17 mixes and combusts the introduced air and the hydrogen to generate high-temperature gas, the combustor 17 is connected with the shell side of the ammonia hydrogen production reactor 15, the high-temperature gas combusted by the combustor 17 enters the shell side of the ammonia hydrogen production reactor 15 and provides heat for ammonia decomposition in the tube side, the ammonia in the tube side is decomposed into high-temperature hydrogen-nitrogen mixed gas through heat absorption under the action of a catalyst, and the high-temperature hydrogen-nitrogen mixed gas enters the first heat exchanger 21 for cooling.
The ammonia hydrogen production reactor 15 is characterized in that a tube side outlet and a shell side outlet are connected with the first heat exchanger 21, generated hydrogen-nitrogen mixed gas discharged from the tube side of the ammonia hydrogen production reactor 15 and heated high-temperature gas discharged from the shell side enter the first heat exchanger 21 to be cooled, the molten salt heat storage module H comprises a first molten salt storage tank 81, a molten salt pump 82 and a second molten salt storage tank 83 which are separately and independently arranged, the first molten salt storage tank 81 is connected with the molten salt pump 82, the molten salt pump 82 is connected with the first heat exchanger 21 again, the first heat exchanger 21 is connected with the second molten salt tank 83, molten salt discharged from the first molten salt tank 81 enters the first heat exchanger 21 under the pushing action of the molten salt pump 82 to exchange heat with the heated high-temperature gas discharged from the ammonia hydrogen production reactor 15, the temperature of the mixed gas is increased and the heated high-temperature gas discharged from the first molten salt tank 81, the temperature of the mixed gas is lowered, the molten salt and the high-temperature gas discharged from the first molten salt tank 81 is cooled, the mixed gas discharged from the first molten salt pump 82 is cooled, and the high-temperature gas discharged from the second molten salt tank is cooled, and the mixed gas discharged from the first heat exchanger is cooled, and the mixed gas discharged from the first molten salt tank is cooled, and the mixed gas is discharged from the first heat exchanger 21 is cooled.
The first heat exchanger 21 is directly connected with the TSA adsorption column 22, and the cooled hydrogen-nitrogen mixed gas subjected to heat exchange in the first heat exchanger 21 enters the TSA adsorption column 22 for adsorption and cooling; by adjusting the temperature in the TSA adsorption column 22, the unreacted ammonia gas remaining in the hydrogen-nitrogen mixture is adsorbed; the method comprises the steps of improving the purity of hydrogen-nitrogen mixed gas, leading the hydrogen-nitrogen mixed gas after adsorption into a galvanic pile 51 and a PSA adsorption column 23 in a fuel cell module E correspondingly, respectively using the galvanic pile 51 and the PSA adsorption column 23 for generating electricity of the galvanic pile 51 and separating hydrogen and nitrogen in the PSA adsorption column 23, wherein an anode inlet of the galvanic pile 51 is connected with a TSA adsorption column 22, a cathode inlet of the galvanic pile 51 is used for introducing air, leading the air into the galvanic pile 51 synchronously after the hydrogen-nitrogen mixed gas after adsorption in the TSA adsorption column 22 enters the galvanic pile 51, the galvanic pile 51 can convert chemical energy of the hydrogen-nitrogen mixed gas and the air into electric energy, initially generate water and electricity, completing the initial starting of the galvanic pile 51, leading the rest hydrogen-nitrogen mixed gas into the PSA adsorption column 23, separating hydrogen and nitrogen by adjusting the gas pressure in the PSA adsorption column, connecting the PSA adsorption column 23 with a synthetic ammonia module G and a first buffer tank 24, leading the ammonia from the TSA adsorption column 23 out of the galvanic pile 22 into the synthetic ammonia module G and the first buffer tank 24, leading the hydrogen from the galvanic pile 51 out of the first buffer tank 24, using the hydrogen-nitrogen mixed gas after the hydrogen is separated from the galvanic pile 51, leading the hydrogen-nitrogen mixed gas into the PSA adsorption column 23 out of the first buffer tank 24, the valves are respectively arranged between the PSA adsorption column 23 and the electric pile 51, the opening of the corresponding valve is adjusted to control the gas flow entering the electric pile 51 from the TSA adsorption column 22 or from the PSA adsorption column 23, the generation of electricity and liquid water of the electric pile 51 are better controlled, more specifically, when the PSA adsorption column 23 finishes the separation of hydrogen and nitrogen, the separated hydrogen with high purity is led into the electric pile 51, and the valves between the TSA adsorption column 22 and the electric pile 51 are closed at the same time, so that the electricity generation efficiency of the electric pile 51 and the generation of liquid water are improved, and the nitrogen in the PSA adsorption column 23 is produced to provide sufficient nitrogen for the synthetic ammonia module G, thereby realizing the cooperative operation of the synthetic ammonia and the electricity generation of the fuel cell module.
The fuel cell module E comprises a pile 51, a vapor-water separator 52, a deionized device 53, a first water tank 54 and a condensation drying separator 75, wherein an outlet of the pile 51 is sequentially connected with the vapor-water separator 52, the deionized device 53 and the first water tank 54, the vapor-water separator 52 is connected with the condensation drying separator 75, during the power generation process of the pile 51, produced liquid water and residual hydrogen are discharged from the outlet of the pile 51 and then enter the vapor-water separator 52 for vapor-water separation, the separated liquid water enters the deionized device 53 for purification, then enters the first water tank 54 for liquid water storage, the residual hydrogen separated from the vapor-water separator 52 enters the condensation drying separator 75 for condensation and drying, preferably, the condensation drying separator 75 is connected with the combustor 17, the hydrogen separated by the condensation drying separator 75 enters the combustor 17 as fuel of the combustor 17, the separated liquid water enters the hydrogen tank 53 for purification, the separated liquid water enters the deionizing device 53 for purification, the hydrogen is discharged from the hydrogen tank 53 and then enters the first water tank 54 for storage, the hydrogen is discharged from the hydrogen tank and the hydrogen tank is completely separated, and the hydrogen is completely discharged from the hydrogen tank 17, and the hydrogen is completely discharged from the hydrogen tank is completely discharged from the combustor 17, and the hydrogen tank is completely discharged from the system, and the hydrogen system is completely discharged, and the hydrogen is effectively used, and the hydrogen is completely discharged from the system is completely and the system is stored by the hydrogen is completely discharged.
The galvanic pile 51 is in electrical communication with the power supply module D; the power supply module D comprises a solar power generation unit 41, a steam turbine power generation unit 42 and a power storage unit 43, wherein the solar power generation unit 41 and the steam turbine power generation unit 42 are respectively and electrically communicated with the power storage unit 43; the solar power generation unit 41 converts solar energy into electric energy and supplies power to the electric storage unit 43, the steam turbine power generation unit 42 converts water vapor energy into electric energy and supplies power to the electric storage unit 43, the electric pile 51 is further electrically communicated with the electric storage unit 43, the electric pile 51 stores electric energy converted by converting chemical energy of gas into electric energy in the electric storage unit 43, the electric storage unit 43 is electrically communicated with the electrolysis tank 61 in the water electrolysis module E again and is used for supplying power for the electrolysis reaction of the electrolysis tank 61, the first water tank 54 is connected with the electrolysis tank 61, the liquid water stored in the first water tank 54 after separation and deionization enters the electrolysis tank 61 for electrolysis, the recycling of the liquid water after the electric pile 51 generates power and the hydrogen yield in a system is also improved, the electrolysis tank 61 generates oxygen from the liquid water in the first water tank 54 under the power supply of the electric storage unit 43, the same first water tank 54 is connected with the hydrogen gas from the second buffer tank 62 and the sixth buffer tank 62 is connected with the first buffer tank 62, the sixth buffer tank 62 is connected with the sixth buffer tank 61, the seventh buffer tank 63 is used for storing oxygen discharged from the electrolytic tank 61, reducing the demand of hydrogen production by ammonia decomposition and providing hydrogen for the electric pile 51 in order to better utilize the gas generated in the operation process of the system, balancing the power generation of the electric pile 51, preferably, the first pressure reducing valve 64 is connected with the anode inlet of the electric pile 51, the second pressure reducing valve 65 is connected with the cathode inlet of the electric pile 51, the hydrogen discharged from the first pressure reducing valve 64 and the oxygen discharged from the second pressure reducing valve 65 are correspondingly introduced into the electric pile 51, and further improving the power generation efficiency of the electric pile 51 and the energy utilization rate of the system.
The steam turbine power generation unit 42 is connected with a second water tank 91 and a fifth heat exchanger 93, the second water tank 91 is connected with a water pump 92, the fifth heat exchanger 93 is respectively connected with the second molten salt storage tank 83 and the first molten salt storage tank 81, liquid water stored in the second water tank 91 enters the fifth heat exchanger 93 under the pushing action of the water pump 92, heat exchange is conducted between the fifth heat exchanger 93 and high-temperature molten salt introduced from the second molten salt storage tank 83, the temperature of the liquid water entering from the second water tank 91 is increased to be better suitable for power generation of the steam turbine power generation unit 42, the steam turbine power generation unit 42 generates power by utilizing the heat of the heated liquid water and stores the generated power in the power storage unit 43, and the molten salt subjected to heat exchange in the fifth heat exchanger 93 flows back to the first molten salt storage tank 81 to be stored and recycled.
The ammonia synthesis module E comprises an air compressor 30, a nitrogen making unit 31, a third buffer tank 32, a fourth buffer tank 33, a first compressor 34, a second compressor 35, a fifth buffer tank 36, a third compressor 37, The third heat exchanger 38 and the synthesis ammonia synthesis column 39, the air compressor 30 is connected to the nitrogen production unit 31 and the third buffer tank 32 in sequence, the third buffer tank 32 is connected to the first compressor 34, the fourth buffer tank 33 is connected to the first buffer tank 24, the fourth buffer tank 33 is connected to the second compressor 35, the first compressor 34 and the second compressor 35 are connected to the fifth buffer tank 36 at the same time, the fifth buffer tank 36 is connected to the third compressor 37, the third compressor 37 is connected to the third heat exchanger 38, the third heat exchanger 38 is connected to the synthesis ammonia synthesis column 39, compressed air introduced from the air compressor 30 is introduced into the nitrogen production unit 31 to separate nitrogen and oxygen in the air and produce nitrogen and oxygen respectively, preferably the nitrogen production unit 31 is connected to the cathode of the electric pile 51, the nitrogen production unit 31 is introduced into the third buffer tank 31 as the air compressor 37 to produce nitrogen, the third air is introduced into the third buffer tank 32 from the third buffer tank 32 to the third buffer tank 32, the air compressor 37 is introduced into the third buffer tank 23 to produce nitrogen and the PSA tank 32 as the air for the PSA tank 32, the hydrogen in the fourth buffer tank 33 is compressed and pressurized by the second compressor 35 and then enters the fifth buffer tank 36, the hydrogen and the nitrogen are mixed in the fifth buffer tank 36, the mixed hydrogen and nitrogen enter the synthesis ammonia synthesis tower 39 for ammonia synthesis after being further compressed and pressurized by the third compressor 37, the nitrogen producing unit 31 can be a molecular sieve air nitrogen producing device or a membrane air nitrogen producing device, the outlet of the synthesis ammonia synthesis tower 39 is also connected with the third heat exchanger 38, the ammonia discharged from the synthesis ammonia synthesis tower 39 and the mixed gas of the hydrogen and the nitrogen compressed by the third compressor 37 are subjected to heat exchange in the third heat exchanger 38, the energy utilization rate of the system and the synthesis ammonia efficiency are improved, meanwhile, the energy consumption of the system is saved, the synthesis ammonia reaction tower 39 is filled with an iron catalyst or an alkaline earth ruthenium ternary hydride catalyst, the ammonia synthesized by the synthesis ammonia reaction tower 39 enters the storage tank A after being cooled, the ammonia enters the synthesis ammonia tower, the ammonia is discharged from the second heat exchanger 14 and then enters the second heat exchanger 39 for the synthesis ammonia synthesis tower 14, the ammonia is discharged from the second heat exchanger 14 for the synthesis tower, the ammonia is recycled from the second heat exchanger 39, the ammonia is discharged from the second heat exchanger 14, the ammonia is cooled and the ammonia is discharged from the second heat exchanger, the second heat exchanger is cooled and the second heat exchanger is used for the synthesis tower 14, providing heat to the molten salt in the first molten salt storage tank 81 while further reducing the temperature of the ammonia gas itself.
The first heat exchanger 21 is also connected with a fourth heat exchanger 72, a liquid ammonia separator 73 and a liquid ammonia pump 74, ammonia gas subjected to heat exchange and temperature reduction in the first heat exchanger 21 enters the fourth heat exchanger 72 for further cooling, wherein the fourth heat exchanger 72 is connected with a refrigerating machine 71, the refrigerating machine 7 is used for introducing cold air into the fourth heat exchanger 72 and realizing cooling of the ammonia gas in the fourth heat exchanger 72, initially forming liquid ammonia, the generated liquid ammonia enters the liquid ammonia separator 73 for liquid ammonia purification and separation, liquid ammonia and impurity gas such as nitrogen are separated according to boiling point difference, the cooled liquid ammonia is discharged from the liquid ammonia separator 73 and then flows back to a liquid ammonia tank A again under the pushing action of the liquid ammonia pump 74, ammonia is provided for the ammonia hydrogen-producing reactor 15 and recycling of system gas, cold air discharged from the fourth heat exchanger 72 enters the electric pile 51 in the condensation drying separator 75 for further heat exchange, the temperature of the tail gas discharged from the electric pile 51 is increased, the temperature of the electric pile 51 is discharged from the electric pile is increased and the electric pile is better used for the combustion gas is better, the heat exchanger is better recycled with the refrigerating machine 37, the whole is better recycled with the refrigerating machine is connected with the third heat exchanger 73, and the heat exchanger is better in recycling the system is better cooled, and the heat is better recycled with the heat exchanger is better cooled down, and the heat pump is better cooled down by the heat pump is better cooled down in the heat pump system, the system is better cooled down by the heat pump air and the heat system, the heat is cooled down in the air and the air is cooled down in the air and the air, the first heat exchanger 21 is connected with the second water tank 91, the desorbed ammonia discharged from the TSA adsorption column 22 enters the fourth heat exchanger 72 for cooling, the recovery of the ammonia in the system is improved, the risk of directly exhausting the ammonia is avoided, and meanwhile, the gas separated from the liquid ammonia separator 73 enters the third compressor 37 for compression, and is used as a nitrogen raw material in the ammonia synthesis process;
The high temperature gas, mainly liquid water, which is heat-exchanged and cooled in the first heat exchanger 21 enters the second water tank 91, and is used as fuel for the turbine power generation unit 42.
The application also discloses a control method of the closed-loop energy-saving ammonia-hydrogen-ammonia circulation system, which comprises the following steps:
The method comprises the steps of gasifying liquid ammonia in a liquid ammonia tank into ammonia gas, and then introducing the ammonia gas into an ammonia decomposition module;
Discharging the decomposed hydrogen-nitrogen mixed gas and the combusted gas from the ammonia decomposition module and guiding the decomposed hydrogen-nitrogen mixed gas and the combusted gas into a first heat exchanger, and guiding the molten salt in the molten salt heat storage module into the first heat exchanger to exchange heat with the hydrogen-nitrogen mixed gas;
Introducing part of the hydrogen-nitrogen mixed gas purified by the TSA adsorption column into a fuel cell module, introducing air into the fuel cell module, converting chemical energy of the gas into electric energy by the fuel cell module, and introducing the rest of the hydrogen-nitrogen mixed gas into the PSA adsorption column for separating hydrogen and nitrogen;
Introducing part of hydrogen separated from the PSA adsorption column into a fuel cell module to replace hydrogen-nitrogen mixed gas introduced from the TSA adsorption column as fuel of the fuel cell module, introducing part of hydrogen separated from the PSA adsorption column into a synthetic ammonia module, introducing nitrogen separated from the PSA adsorption column into the synthetic ammonia module, synthesizing hydrogen and nitrogen into ammonia by the synthetic ammonia module, introducing liquid water discharged from an outlet of the fuel cell module into an electrolytic water module, introducing electric energy generated by the fuel cell module into the electrolytic water module, and hydrolyzing the liquid water to generate hydrogen and oxygen;
introducing hydrogen and oxygen generated by electrolysis water into a fuel cell module for generating electricity, fully introducing hydrogen and nitrogen mixed gas purified by a TSA adsorption column into a PSA adsorption column for separating hydrogen and nitrogen, and introducing the separated nitrogen into a synthetic ammonia module;
and step six, cooling the ammonia in the ammonia synthesis module to form liquid ammonia, and introducing the cooled liquid ammonia into a liquid ammonia tank.
In the second step, a steam turbine power generation unit is further included; the method comprises the steps of generating electricity by a steam turbine power generation unit through water vapor formed after heat exchange in a first heat exchanger, introducing ammonia synthesized by an ammonia synthesis module into the first heat exchanger for heat exchange in the step four, cooling the ammonia after heat exchange and introducing the ammonia into a liquid ammonia tank, introducing gas discharged from an outlet of a fuel cell module into a combustor for combustion, introducing hydrogen generated by electrolysis of a part of electrolytic water module into the ammonia synthesis module for synthesizing the ammonia in the step five, and introducing the separated gas into the ammonia synthesis module for synthesizing the ammonia in the ammonia cooling process in the step six.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (10)
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