High-temperature proton exchange membrane fuel cell cooling, heating and power dehumidification combined supply system based on utilization of waste heat of dehydrogenation reaction of organic hydrogen storage liquid

Abstract

The invention discloses a high-temperature proton exchange membrane fuel cell cooling, heating and power dehumidification combined supply system based on organic hydrogen storage liquid dehydrogenation reaction waste heat utilization, which comprises a high-temperature proton exchange membrane fuel cell comprising a cathode and an anode. The system further comprises a fuel supply system, an air supply system, a high-temperature proton exchange membrane fuel cell stack condensation system, an organic Rankine cycle power generation system, an ammonia vapor compression type refrigeration cycle and hot water supply system, an air dehumidification circulation system, a lithium bromide absorption type refrigeration circulation system and an organic hydrogen storage liquid recovery system which are communicated through pipelines. According to the system, the function of distributed electricity with the organic hydrogen storage liquid as fuel can be achieved, no greenhouse gas and pollution gas are generated in the utilization process and can be recycled, high practical and popularization value is achieved, low-grade waste heat is fully utilized, the comprehensive energy utilization efficiency of the system is improved, and the resource utilization effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of organic hydrogen storage liquid utilization, and in particular to a high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on utilization of waste heat from dehydrogenation reaction of organic hydrogen storage liquid. Background Art

[0002] Organic liquid hydrogen storage materials (LOHCs) are a type of hydrogen storage material with a fully reversible hydrogenation-dehydrogenation cycle. In recent years, they have become the focus of hydrogen research due to their reversibility and zero CO2 emissions. LOHCs are based on reversible catalytic hydrogenation and dehydrogenation reactions of unsaturated bonds in compounds to achieve safe and efficient storage and release of hydrogen. In addition, hydrogen-rich LOHCs compounds (Hn-LOHCs) can store hydrogen for a long time under normal pressure without causing energy loss. Since Hn-LOHCs compounds have similar properties to crude oil derivatives (such as diesel and gasoline), they can be transported over long distances using existing liquid fuel transportation logistics (such as pipelines, ships, and trucks). Therefore, in the context of the transition to a "hydrogen economy", the comprehensive utilization of organic hydrogen storage liquids on existing infrastructure is of great significance. Organic liquid hydrogen storage technology consumes a lot of heat during the dehydrogenation process, and the dehydrogenation temperature is generally between 140℃ and 300℃. This high temperature environment is one of the key factors to ensure reaction efficiency and quality. The high-temperature proton exchange membrane fuel cell is an efficient energy conversion device that can directly convert the chemical energy in the fuel into electrical energy. It has the characteristics of high efficiency, low emissions, high power density and simple stacking design. In distributed power generation technology, the high-temperature proton exchange membrane battery can achieve integrated output of cold, heat and electricity. Combined with hydrogen energy technology, how to improve the dehydrogenation efficiency and use the hydrogen generated by the dehydrogenation system to generate electricity through the high-temperature proton exchange membrane fuel cell, and better utilize the waste heat generated by the high-temperature proton exchange membrane fuel cell power generation so that it can effectively save energy and reduce environmental pollution and other resource utilization goals is a work worthy of continuous research.

[0003] In this regard, the inventor has conducted useful explorations and attempts and found a solution to the above-mentioned problem. The solution to be introduced below is produced under this background. Summary of the invention

[0004] The technical problem to be solved by the present invention is to address the energy and waste heat waste caused by the use of organic hydrogen storage liquid and high-temperature proton exchange membrane fuel cells alone, and propose a high-temperature proton exchange membrane fuel cell heat, cooling, electricity and dehumidification combined supply system based on the waste heat of the dehydrogenation reaction of the organic hydrogen storage liquid. The heat generated during the reaction of the fuel cell stack and the low-grade waste heat generated by the cooling of the exhaust gas and the cooling oil are used as the driving force to drive the subsystem to perform power generation, cooling, heating and dehumidification functions. In addition, for complex energy conversion systems, heat sources are used through appropriate coupling methods to meet the heat load of other parts of the system. The waste heat of the exhaust gas at the cathode outlet of the fuel cell stack is used to preheat the inlet air, and the heat generated by the combustion of the exhaust gas at the anode outlet of the fuel cell stack mixed with air is used to preheat the organic hydrogen storage liquid fuel. The waste heat generated during the operation of the fuel cell is fully utilized, greatly improving the comprehensive energy utilization efficiency.

[0005] The technical problem solved by the present invention can be achieved by adopting the following technical solutions:

[0006] A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid, comprising a high-temperature proton exchange membrane fuel cell having a cathode and an anode, characterized in that it also comprises a fuel supply system, an air supply system, a high-temperature proton exchange membrane fuel cell stack condensation system, an organic Rankine cycle power generation system, an ammonia vapor compression refrigeration cycle and hot water supply system, an air dehumidification cycle system, a lithium bromide absorption refrigeration cycle system, and an organic hydrogen storage liquid recovery system connected through pipelines;

[0007] The fuel supply system includes a dehydrogenation reaction device, a gas-liquid separator, a humidifier, and a hydrogen compressor connected by pipelines. After the organic hydrogen storage liquid is preheated by the preheater, it enters the dehydrogenation reaction device to undergo a dehydrogenation reaction. After gas-liquid separation by the gas-liquid separator, humidification by the humidifier, and compression by the hydrogen compressor, the anode of the high-temperature proton exchange membrane fuel cell receives the hydrogen processed by the hydrogen compressor.

[0008] The air supply system includes a preheater, an air compressor, and an air delivery pipeline connected to the cathode of the high-temperature proton exchange membrane fuel cell through a pipeline; the air enters the air compressor for compression after being preheated, and then flows into the cathode of the high-temperature proton exchange membrane fuel cell;

[0009] When the system is running, the anode of the high-temperature proton exchange membrane fuel cell receives the hydrogen processed by the hydrogen compressor and then reacts chemically with the air supplied by the air supply system to generate electricity and heat energy; the gas coming out of the anode of the high-temperature proton exchange membrane fuel cell enters the hydrogen burner, mixes with the air entering from the outside and burns to preheat the fuel; the gas coming out of the cathode of the high-temperature proton exchange membrane fuel cell enters the air preheater to preheat the air;

[0010] In addition, the cooling oil enters the high-temperature proton exchange membrane fuel cell stack for heat exchange cooling, and is connected to the first waste heat exchanger, the first condenser, and the hot water heater through pipelines, and circulates in sequence;

[0011] The organic Rankine cycle power generation system includes a first waste heat exchanger, a turbine, and a second condenser connected to a high-temperature proton exchange membrane fuel cell stack through a pipeline; wherein the cooling medium is cooled from the high-temperature proton exchange membrane fuel cell stack to form low-grade waste heat, and is heated by the first waste heat exchanger to drive the turbine to generate electricity; the cooling medium flowing through the turbine flows back to the first waste heat exchanger through the second condenser to circulate and drive the organic Rankine cycle power generation system to operate continuously;

[0012] The ammonia vapor compression refrigeration cycle and hot water supply system includes an ammonia compressor, a first condenser, a third condenser, a first throttle valve, and a first evaporator connected by pipelines. On the one hand, the ammonia gas is compressed into a high-temperature gas by the ammonia compressor and then enters the first condenser, the third condenser, the first throttle valve and the first evaporator in sequence, and finally flows back to the ammonia compressor to complete the refrigeration cycle; the heat released by the condensation of the third condenser can heat the normal temperature water, and then connected to the hot water heater through a pipeline to heat the hot water to the required hot water temperature; on the other hand, the heat released by the condensation of the first condenser can heat the cooling medium from the first waste heat exchanger, and the heated cooling medium temperature is increased as a heat source for the hot water heater, and after heating the water, it enters the high-temperature proton exchange membrane fuel cell stack.

[0013] The air dehumidification cycle system includes a second waste heat exchanger, a regenerator, a first heat exchanger, a fourth condenser, and a dehumidifier connected to the gas-liquid separator through a pipeline. The dehumidifier is provided with a dehumidifying medium. On the one hand, the dehumidifying medium absorbs moisture in the air in the dehumidifier and performs a temperature reduction treatment, and then flows through the first heat exchanger, the second waste heat exchanger, and the regenerator, wherein the dehumidifying medium absorbs low-grade waste heat carried by the organic hydrogen storage liquid flowing out from the bottom of the gas-liquid separator in the second waste heat exchanger, and regenerates the dehumidifying medium in the regenerator; on the other hand, the dehumidifying medium flowing out of the regenerator flows through the first heat exchanger and the fourth condenser, and finally flows back to the dehumidifier to complete the air dehumidification cycle, wherein the cooling capacity required by the fourth condenser is drawn from the second evaporator;

[0014] The lithium bromide absorption refrigeration cycle system includes a generator connected to a second waste heat exchanger through a pipeline and filled with a dilute lithium bromide solution. On the one hand, the dilute lithium bromide solution is heated and concentrated in the generator to generate water vapor, and the water vapor flows through the fifth condenser and the second throttle valve in sequence through the pipeline, and finally enters the second evaporator to absorb heat and provide cold capacity to the fourth condenser. The water vapor generated in the second evaporator enters the absorber through the pipeline; on the other hand, the lithium bromide concentrated solution flowing out of the generator is connected to the second regenerator and the third throttle valve in sequence through the pipeline and finally enters the absorber. At this time, the lithium bromide concentrated solution and the water vapor flowing out of the second evaporator form a dilute lithium bromide solution in the absorber and flow to the second regenerator and the generator to complete the lithium bromide absorption refrigeration cycle system;

[0015] The organic hydrogen storage liquid recovery system includes a third waste heat exchanger equipped with a lithium bromide dilute solution generator and an organic hydrogen storage liquid recovery device connected by a pipeline. The organic hydrogen storage liquid heats the normal temperature water in the third waste heat exchanger and then flows to the organic hydrogen storage liquid recovery device for recovery.

[0016] In a preferred embodiment of the present invention, the reaction occurring in the burner is an adiabatic reaction.

[0017] In a preferred embodiment of the present invention, the pipeline model involved in the system is a steel pipe or a silicone pipe.

[0018] In a preferred embodiment of the present invention, the system also includes a first delivery pump, a second delivery pump, a third delivery pump, a fourth delivery pump, and a fifth delivery pump; the first delivery pump is installed between the pipeline connecting the high-temperature proton exchange membrane fuel cell stack and the first waste heat exchanger, the second delivery pump is installed between the pipeline connecting the second condenser and the first waste heat exchanger, the third delivery pump is installed between the pipeline connecting the first regenerator and the second waste heat exchanger, the fourth delivery pump is installed between the pipeline connecting the first regenerator and the first regenerator, and the fifth delivery pump is installed between the pipeline connecting the absorber and the second regenerator.

[0019] In a preferred embodiment of the present invention, the component of the organic hydrogen storage liquid is perhydro-N-propylcarbazole.

[0020] In a preferred embodiment of the present invention, the operating temperature of the high temperature proton exchange membrane fuel cell stack is 175°C-190°C.

[0021] In a preferred embodiment of the present invention, the dehydrogenation reaction device comprises a dehydrogenation reaction tank, a liquid heater disposed in the dehydrogenation reaction tank, a heat conduction plate disposed below the liquid heater, and a hydrogen liquid stirring device;

[0022] The upper part of the dehydrogenation reaction tank is connected to a hydrogen liquid inlet pipe, and the lower part of the dehydrogenation reaction tank is connected to a hydrogen liquid outlet pipe; a hot hydrogen outlet;

[0023] The liquid-passing heater comprises a cylindrical shell, a liquid-passing plate arranged in the cylindrical shell, a heating tube arranged below the liquid-passing plate, and a liquid-passing hole and a driving rod hole are provided on the surface of the liquid-passing plate;

[0024] An electric heating tube is arranged below the heat conduction plate; the hydrogen liquid stirring device comprises a driving motor, a driving rod and a stirring blade, the driving motor is arranged on the top of the dehydrogenation reaction tank, one end of the driving rod is connected to the driving motor, and the other end passes through the rod hole of the driving rod and extends to above the heat conduction plate and is connected to the stirring blade.

[0025] In a preferred embodiment of the present invention, it also includes a dehydrogenation reaction heat exchanger and a waste heat utilization pipe, wherein the waste heat utilization pipe is arranged in the dehydrogenation reaction tank, and the dehydrogenation reaction heat exchanger is installed on the outer surface of the dehydrogenation reaction tank, including an air inlet, a cold hydrogen outlet, a hot air outlet, and a hot hydrogen inlet located at the lower end of the dehydrogenation reaction heat exchanger; wherein the hot hydrogen inlet is connected to the hot hydrogen outlet of the dehydrogenation reaction tank through a connecting pipe; the hot air outlet is connected to the waste heat utilization pipe through a connecting pipe, and the gas outlet end of the waste heat utilization pipe is connected to an external environment or a gas-liquid separator.

[0026] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0027] (1) The present invention discloses a high-temperature proton exchange membrane fuel cell combined heat, cooling and electricity dehumidification system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid. The system can realize the function of distributed electricity using the organic hydrogen storage liquid as fuel. During the utilization process, no greenhouse gas or pollutant gas is generated and the system can be recycled and reused, which has high practical and promotion value.

[0028] (2) The present invention discloses a high-temperature proton exchange membrane fuel cell combined cooling, heating, and electricity dehumidification system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid. The system makes full use of the low-grade waste heat from the dehydrogenation of the organic hydrogen storage liquid, draws heat from the waste heat through a coupling subsystem to drive a dehumidification system to dehumidify the air, and a lithium bromide absorption refrigeration system to generate cold energy and finally recover the organic hydrogen storage liquid after providing domestic hot water through the waste heat, thereby improving the waste heat utilization rate of the system.

[0029] (3) The present invention discloses a high-temperature proton exchange membrane fuel cell combined cooling, heating, electricity and dehumidification system based on the waste heat of the dehydrogenation reaction of an organic hydrogen storage liquid. The waste heat generated during the operation of the high-temperature proton exchange membrane fuel cell is fully utilized, and the heat is taken away from the fuel cell stack through the coupling subsystem to drive the organic Rankine cycle power generation system to generate electricity, the ammonia vapor compression refrigeration system to generate cold energy, and finally the waste heat is used to shut down domestic hot water, thereby improving the comprehensive energy utilization efficiency of the system.

[0030] (4) The present invention provides a high-temperature proton exchange membrane fuel cell combined heat, cooling and dehumidification system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid. The cathode outlet gas is directly used to preheat the cathode feed in the high-temperature proton exchange membrane fuel cell, and the anode outlet gas is further burned to provide the heat required for fuel preheating, thereby further reducing the waste of hydrogen and the energy consumption of providing additional heat.

[0031] (5) The dehydrogenation reaction device in the high-temperature proton exchange membrane fuel cell heat and power dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid of the present invention has an excellent structural design. Part of the heat generated by the combustion of hydrogen in the hydrogen burner is used for preheating the organic hydrogen storage liquid preheater, and part is directly used for more uniform heating of the organic hydrogen storage liquid in the dehydrogenation reaction device. The two processes are carried out simultaneously to improve the dehydrogenation efficiency. In addition, a dehydrogenation waste heat utilization device is provided to further improve the utilization rate of energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0033] Figure 1 It is a schematic diagram of a high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid according to the present invention.

[0034] Figure 2 This is another schematic diagram of a high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid according to the present invention.

[0035] Figure 3 For the present invention Figure 2 Schematic diagram of the structure of the dehydrogenation reaction unit.

[0036] Figure 4 For the present invention Figure 2 A schematic diagram of the structure of a dehydrogenation reaction tank in a dehydrogenation reaction device with a portion of the tank wall removed.

[0037] Figure 5 For the present invention Figure 2 Schematic diagram of the separation structure of the cover and body of the dehydrogenation reaction tank in the dehydrogenation reaction device.

[0038] Figure 6 For the present invention Figure 3 Schematic diagram of the structure of the supernatant heater in the dehydrogenation reaction unit.

[0039] Figure 7 The superheater in the dehydrogenation reaction device of the present invention is different from Figure 6 Schematic diagram of the structure of the perspective. DETAILED DESCRIPTION

[0040] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] In the description of the present invention, it should be noted that the terms "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0042] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "connected", "connected" and "connected" should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection; for example, "connected" can be a direct "connected" or an indirect "connected" through an intermediate medium. For ordinary technicians in this field, the specific meanings of the above terms in the present invention should be understood according to specific circumstances.

[0043] See also Figure 1 As shown, the present invention is a high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid. The system includes a high-temperature proton exchange membrane fuel cell comprising a cathode and an anode, a fuel supply system connected by pipelines, an air supply system, a high-temperature proton exchange membrane fuel cell stack condensation system, an organic Rankine cycle power generation system, an ammonia vapor compression refrigeration cycle and hot water supply system, an air dehumidification cycle system, a lithium bromide absorption refrigeration cycle system, and an organic hydrogen storage liquid recovery system.

[0044] The structure or device involved in the system includes a fuel preheater 10; a dehydrogenation reaction device 400; a gas-liquid separator 30; a humidifier 40; a hydrogen compressor 50; a high-temperature proton exchange membrane fuel cell stack 60; a hydrogen burner 70; an air preheater 80; an air compressor 90; a second waste heat exchanger 100; a regenerator 110; a fourth delivery pump 120; a first regenerator 130; a fourth condenser 140; a dehumidifier 150; a third delivery pump 160; a generator 170; a fifth condenser 180; a second Throttle valve 190; second evaporator 200; absorber 210; fifth delivery pump 220; second regenerator 230; third throttle valve 240; third waste heat exchanger 250; organic hydrogen storage liquid recovery device 260; first delivery pump 270; first waste heat exchanger 280; turbine 290; second condenser 300; second delivery pump 310; first condenser 320; hot water heater 330; third condenser 340; first throttle valve 350; first evaporator 360; ammonia compressor 370 and several pipelines. It should be noted that for those skilled in the art, these devices are all devices in the prior art, and this embodiment mainly describes the connection method, operation principle, etc. of the system. It should also be noted that the specific way of connecting or connecting the pipelines and devices can be clearly known from the attached drawings, so the specific structure of the device and the connection of certain pipeline devices will not be described in detail. First, the component of the organic hydrogen storage liquid in the system is perhydro-N-propylcarbazole, which is preheated in the fuel preheater 10. The fuel supply system includes a dehydrogenation reaction device 400, a gas-liquid separator 30, a hydrogen humidifier 40, and a hydrogen compressor 50 connected by pipelines. After the organic hydrogen storage liquid is preheated by the preheater 10, it enters the dehydrogenation reaction device 400 for dehydrogenation reaction. After the hydrogen is separated and humidified by the gas-liquid separator 30 and compressed by the hydrogen compressor 50, the high-temperature proton exchange membrane fuel cell anode stack 60 receives the hydrogen processed by the hydrogen compressor 50; the operating temperature of the high-temperature proton exchange membrane fuel cell stack 60 in the system is 175-190°C, and the high-temperature proton exchange membrane fuel cell stack 60 is 175-190°C. The membrane exchange fuel cell stack 60 includes: a high-temperature proton exchange membrane fuel cell anode inlet 61, a high-temperature proton exchange membrane fuel cell anode outlet 62, a high-temperature proton exchange membrane fuel cell cathode inlet 63, and a high-temperature proton exchange membrane fuel cell cathode outlet 64. When the system is running to generate electricity and heat energy, the gas coming out of the high-temperature proton exchange membrane fuel cell anode outlet 62 enters the hydrogen combustion reactor 70 to burn with the air, and then provides heat to the fuel preheater 10 to improve energy utilization. The reaction occurring in the hydrogen burner 70 is an adiabatic reaction. In the embodiment of the present invention, it is necessary to ensure air tightness and high-temperature resistance and service life requirements. The pipeline model is preferably a steel pipe or a silicone pipe.

[0045] It should be noted that the pipeline for the reaction of the high-temperature fuel cell stack 60 in the system is divided into two routes, which involves not only the above-mentioned fuel supply system but also the air supply system. The air supply system includes an air preheater 80, an air compressor 90, and a high-temperature proton exchange membrane fuel cell cathode inlet 63 which are sequentially connected through pipelines. After being preheated by the air preheater 80, the air flows sequentially through the air compressor 90 and the high-temperature proton exchange membrane fuel cell cathode inlet 63; the air preheater 80 includes: an air preheater cold flow inlet 81, an air preheater hot flow inlet 83, an air preheater cold flow outlet 82, and an air preheater hot flow outlet 84. The air enters from the air preheater cold flow inlet 81 and flows from the air preheater cold flow outlet 82 to the air compressor 90 after heat exchange.

[0046] In the present system, the high temperature proton exchange membrane fuel cell stack 60 further includes a cooling medium inlet 66 and a cooling medium outlet 65. The cooling medium is cooled by heat exchange from the high temperature proton exchange membrane fuel cell stack 60. Specifically, the cooling medium enters from the cooling medium inlet 66 and flows from the cooling medium outlet 65 to the first waste heat exchanger 280 through heat exchange, and then flows through the first inlet 321 of the first condenser, the first outlet 322 of the first condenser, the first inlet 331 of the hot water heater, and the first outlet 332 of the hot water heater, and circulates in sequence. In order to enhance the circulation driving power, the present system is provided with a first delivery pump 270, which is installed between the pipelines connecting the high temperature proton exchange membrane fuel cell stack 60 and the first waste heat exchanger 280.

[0047] The organic Rankine cycle power generation system of the present system includes a first waste heat exchanger 280 connected to a high-temperature proton exchange membrane fuel cell stack 60 through a pipeline, a turbine 290, a generator (not shown in the figure), and a second condenser 300; wherein the cooling medium is cooled by heat exchange from the high-temperature proton exchange membrane fuel cell stack 60 to form low-grade waste heat, and the cooling medium is heated by the first waste heat exchanger 280 to drive the turbine 290 to operate and connect to the generator (not shown in the figure) to generate electricity; specifically, the first waste heat exchanger 280 has a first waste heat exchanger heat inflow The first waste heat exchanger hot flow outlet 281, the first waste heat exchanger cold flow outlet 282, the first waste heat exchanger cold flow inlet 283, the first waste heat exchanger cold flow outlet 284, the second condenser 300 has the second condenser normal temperature water inlet 303, the second condenser hot water outlet 304, the second condenser hot flow inlet 301, the second condenser cold flow outlet 302, the organic Rankine cycle power generation system cooling medium enters from the first waste heat exchanger cold flow inlet 283, flows from the first waste heat exchanger cold flow outlet 284 to the turbine 290 to drive the generator (not shown) to generate electricity. The cooling medium after power generation passes through the second condenser hot flow inlet 301, the second condenser cold flow outlet 302, and the normal temperature water flows through the second condenser normal temperature water inlet 303, the second condenser hot water outlet 304 to exchange heat to form hot water supply. The system is provided with a second delivery pump 310 between the first waste heat exchanger cold flow inlet 283 and the second condenser cold flow outlet 302 to circulate and drive the organic Rankine cycle power generation system to operate continuously. In addition, in the embodiment of the present invention, the cooling medium mainly refers to the refrigerant R123.

[0048] The ammonia vapor compression refrigeration cycle and hot water supply system includes an ammonia compressor 370, a first condenser 320, a third condenser 340, a first throttle valve 350, and a first evaporator 360 connected by pipelines. On the one hand, the ammonia gas is compressed into a high-temperature gas by the ammonia compressor 370 and then enters the second inlet 323 of the first condenser, the second outlet 324 of the first condenser, the first inlet 341 of the third condenser, the first outlet 342 of the third condenser, the first throttle valve 350, and the first evaporator 360 in sequence, and finally flows back to the ammonia compressor 370 to complete the refrigeration cycle. , wherein the heat released by the condensation of the third condenser 340 can heat the normal temperature water entering from the second inlet 343 of the third condenser, flow out through the second outlet 344 of the third condenser, and then connect to the second inlet 333 of the hot water heater through a pipeline to heat the required hot water temperature; on the other hand, the heat released by the condensation of the first condenser 320 can heat the cooling medium from the first waste heat exchanger 280, and the heated cooling medium temperature rises as the heat source of the hot water heater 330 to heat the water and then enter the high-temperature proton exchange membrane fuel cell stack. In some embodiments, the normal temperature water inlet temperature, i.e., the temperature of the second inlet 343 of the third condenser, is 25°C, and the temperature of the hot water outlet 334 of the hot water heater is 60°C, which meets the standard of domestic hot water. Among them, the ammonia gas in the ammonia vapor compression refrigeration system is compressed into high-temperature gas by the ammonia compressor 370, and then enters the first condenser 320, the third condenser 340, the first throttle valve 350 and the first evaporator 360 in sequence, and finally returns to the ammonia compressor 370 to complete the refrigeration cycle. In some embodiments, the condensing temperature of the third condenser 340 is 30° C., and the evaporating temperature of the first evaporator 360 is −17° C., which can provide cooling capacity.

[0049] The air dehumidification circulation system of the present system includes a second waste heat exchanger 100, a regenerator 110, a first heat exchanger 130, a fourth condenser 140, and a dehumidifier 150 connected to the gas-liquid separator 30 through a pipeline. On the one hand, the dehumidifying medium absorbs moisture in the air in the dehumidifier 150 and performs a temperature reduction treatment, and then flows through the second inlet 133 of the first heat exchanger, the second outlet 134 of the first heat exchanger, the cold flow inlet 103 of the second waste heat exchanger, the cold flow outlet 104 of the second waste heat exchanger, and the regenerator 110, wherein the dehumidifying medium is received by the second waste heat exchanger 100 through the low-grade waste heat carried by the organic hydrogen storage liquid flowing out from the bottom of the gas-liquid separator 30. The dehumidifying medium is heated, and the dehumidifying medium is regenerated by passing air into the regenerator 110 to remove the moisture in the dehumidifying medium; on the other hand, the dehumidifying medium flowing out of the regenerator 110 flows through the fourth delivery pump 120, the first inlet 131 of the first regenerator, the first outlet 132 of the first regenerator, and the fourth condenser 140, and finally flows back to the dehumidifier 150 to complete the air dehumidification cycle, wherein the third delivery pump 160 is installed on the connecting pipeline between the second outlet 134 of the first regenerator and the cold flow inlet 103 of the second waste heat exchanger, and the cold capacity required by the fourth condenser 140 is drawn from the second evaporator 200 in the lithium bromide absorption refrigeration cycle system described later. In some embodiments, the air temperature after dehumidification and condensation can reach 26°C and the dehumidification efficiency can reach 94%. In the embodiment of the present invention, the dehumidifying medium mainly refers to a lithium chloride LiCL concentrated solution (41% LiCL, 59% water).

[0050] The lithium bromide absorption refrigeration cycle system of the present system includes a second waste heat exchanger 100 and a generator 170 filled with a dilute lithium bromide solution connected through a pipeline. On the one hand, the dilute lithium bromide solution is heated and concentrated in the generator 170 to generate water vapor, and the water vapor flows through the fifth condenser 180 and the second throttle valve 190 in sequence through the pipeline, and finally enters the second evaporator 200 to absorb heat and provide cooling capacity to the fourth condenser 140. The water vapor generated in the second evaporator 200 enters the absorber 210 through the pipeline; on the other hand, the lithium bromide concentrated solution flowing out of the generator 170 is connected to the second regenerator 230 and the third throttle valve 240 in sequence through the pipeline, and finally enters the absorber 210. At this time, the lithium bromide concentrated solution and the water vapor flowing out of the second evaporator 200 form a dilute lithium bromide solution in the absorber 210 and flow to the second regenerator 230 and the generator 170 to complete the lithium bromide absorption refrigeration cycle system.

[0051] The specific process flow of this system is as follows: the organic hydrogen storage liquid working fluid passing through the second waste heat exchanger 100 enters the generator 170 from the hot flow outlet port 102 of the second waste heat exchanger 100 to drive the lithium bromide absorption refrigeration system to operate, wherein the lithium bromide dilute solution is heated and concentrated in the generator 170, and the water vapor enters the fifth condenser 180 from the first outlet 171 of the generator 170 and is cooled and releases heat, enters the second throttle valve 190 to reduce pressure, and then enters the second evaporator 200 to absorb heat, and supplies the fourth condenser 1 40 provides cooling capacity; the concentrated lithium bromide solution flowing out of the second outlet 172 of the generator 170 is cooled by the second regenerator 230 and then enters the third throttle valve 240 for decompression, and enters the absorber 210 together with the water vapor coming out of the second evaporator 200 to become a dilute lithium bromide solution, and then passes through the fifth delivery pump 220 and the second regenerator 230 in sequence to heat the lithium bromide solution diverted from the generator 170, and then returns to the generator 170 through the generator reflux pipeline 173, completing a refrigeration cycle.

[0052] The organic hydrogen storage liquid recovery system of the present system includes a third waste heat exchanger 250 equipped with a lithium bromide dilute solution generator 170 and an organic hydrogen storage liquid recovery device 260 connected by a pipeline. The organic hydrogen storage liquid heats the normal temperature water in the third waste heat exchanger 250 and flows to the organic hydrogen storage liquid recovery device 260 for recovery. Specifically, the organic hydrogen storage liquid flows into the third waste heat exchanger from the hot flow inlet 251 of the third waste heat exchanger to provide heat to the normal temperature water flowing into from the cold flow inlet 253 of the third waste heat exchanger, and then flows out from the hot flow outlet 252 of the third waste heat exchanger to the organic hydrogen storage liquid recovery device 260 for recovery. In summary, the present invention can achieve a higher comprehensive utilization rate of waste heat. First, the waste heat of the post-combustion gas in the reaction process of the high-temperature proton exchange membrane fuel cell stack 60 is used to preheat the waste heat of the gas. The heat from the combustion of the residual hydrogen at the anode outlet is used to preheat the imported fuel, and then the low-grade waste heat brought out by the cooling oil from the high-temperature proton exchange membrane fuel cell stack is used as the driving force, so that the organic Rankine cycle power generation system provides electricity for the cycle, the ammonia vapor compression refrigeration system provides cold energy for food storage, and the heat released during the condensation process of the ammonia vapor compression refrigeration system and the waste heat in the cooling oil provide heat for the water heater. Finally, the waste heat brought by the organic hydrogen storage liquid is used as the driving force, so that the air dehumidification system dehumidifies and cools the air, and the lithium bromide absorption refrigeration system provides cold energy for the air dehumidification system and the household. This makes full use of the waste heat generated during the operation of the high-temperature proton exchange membrane fuel cell, greatly improving the overall energy utilization efficiency of the system.

[0053] Please refer to Figure 2-7The system also proposes a specific embodiment of a dehydrogenation reaction device that can improve hydrogen dehydrogenation efficiency and waste heat utilization rate. The dehydrogenation reaction device 400 includes a dehydrogenation reaction tank 410, a liquid heater 420 arranged in the dehydrogenation reaction tank 410, a heat conduction plate 430 arranged below the liquid heater 420, and a hydrogen liquid stirring device 440; the upper part of the dehydrogenation reaction tank 410 is connected to a hydrogen liquid inlet pipe 411, and the lower part of the dehydrogenation reaction tank 410 is connected to a hydrogen liquid outlet 412; a temperature detector (not shown in the figure) is installed inside the dehydrogenation reaction tank 410 to detect the temperature of the organic hydrogen storage liquid, wherein the electrical components or circuit control systems related to temperature control are the same as or not much different from the existing temperature control principle system, because they belong to the existing technology and are not the innovation point in the implementation of the present invention, they will not be repeated here. The liquid-passing heater 420 includes a cylindrical shell 421, a liquid-passing plate 422 disposed in the cylindrical shell 421, and a heat transfer pipe 423 disposed below the liquid-passing plate 422. Heat transfer oil flows in the heat transfer pipe 423, which is in a disc shape. The heat transfer pipe 423 has a heat transfer pipe inlet end 423a and a heat transfer pipe outlet end 423b. The heat transfer between the heat transfer pipe inlet end 423a and the hydrogen burner 70 is carried out through the pipeline 21, and the heat transfer between the heat transfer pipe outlet end 423b and the hydrogen burner 70 is carried out through the pipeline 22. The pipeline 21, the heat transfer pipe 423, the pipeline 22 and the pipeline in the hydrogen burner 70 form a closed loop, and the pipeline 21 and the pipeline 22 are covered with The heat is transferred to the dehydrogenation reaction tank 410 through the heat transfer oil. The surface of the liquid plate 422 is provided with a liquid hole 422a and a driving rod hole 422b. The liquid plate 422 is cone-shaped as a whole, and its lower part is fixed in the cylindrical shell 421. The organic hydrogen storage liquid is transported from the hydrogen liquid inlet pipe 411 and scattered on the surface of the cone-shaped liquid plate 422. After being dispersed through the liquid hole 422a, it flows to the heat transfer plate 430 at the bottom of the dehydrogenation reaction tank 410. The liquid heater 420 heats the scattered organic hydrogen storage liquid and the air inside the dehydrogenation reaction tank 410, thereby realizing a relatively uniform initial heating of the organic hydrogen storage liquid, which reduces the time required for the organic storage liquid to reach the dehydrogenation reaction to a certain extent, and improves the dehydrogenation efficiency.

[0054] An electric heating pipe 470 is arranged below the heat conducting plate 430; it is fixed in the dehydrogenation reaction tank 410 through a support ring 431, and is electrically connected to a power supply through a connector 480, so as to maintain a preferred temperature for a stable dehydrogenation reaction; in the embodiment of the present invention, the preferred temperature is 170°C-200°C. The hydrogen liquid stirring device 440 includes a driving motor 441, a driving rod 442, and a stirring blade 443. The driving motor 441 is arranged at the top of the dehydrogenation reaction tank 410, one end of the driving rod 442 is connected to the driving motor 441, and the other end passes through the driving rod hole 422b to extend to the top of the heat conducting plate 430, and is connected to a stirring blade 443. In the embodiment of the present invention, the stirring blade 443 is divided into two groups, the upper and lower groups, and the stirring blade 443 stirs the organic hydrogen storage liquid to mix the dehydrogenating agent and the organic hydrogen storage liquid evenly, improve the hydrogen oil heating efficiency, and further improve the dehydrogenation efficiency of the organic hydrogen storage liquid.

[0055] This embodiment of the invention is also provided with a dehydrogenation reaction heat exchanger 450 and a waste heat utilization pipe 460 . The waste heat utilization pipe 460 is arranged in the dehydrogenation reaction tank in a ring shape; preferably, it is arranged between the upper and lower groups of stirring blades 443 . The dehydrogenation reaction heat exchanger 450 is installed on the outer surface of the dehydrogenation reaction tank, including an air inlet 451, a cold hydrogen outlet 452, a hot air outlet 453, and a hot hydrogen inlet 454 located at the lower end of the dehydrogenation reaction heat exchanger 450; wherein the hot hydrogen inlet 454 is connected to the hot hydrogen outlet 413 of the dehydrogenation reaction tank through a connecting pipe; the hot air outlet 453 is connected to the waste heat utilization pipe inlet port 461 through a connecting pipe, and the waste heat utilization pipe outlet port 462 is connected to the external environment, and air enters the dehydrogenation reaction heat exchanger 450 from the air inlet 451, and the hot hydrogen heats the air entering the dehydrogenation reaction heat exchanger 450. The heated air pipeline is connected to enter the waste heat utilization pipe 460, and the waste heat utilization pipe 460 heats the organic hydrogen storage liquid, thereby utilizing the waste heat of the hot hydrogen and reducing the energy consumption required for dehydrogenation of the organic hydrogen storage liquid. The dehydrogenated organic hydrogen storage liquid flows out from the hydrogen liquid outlet 412 to the gas-liquid separator 30 for further gas-liquid separation. This design not only makes full use of the waste heat of the hot hydrogen, but also takes away part of the heat to the external environment through the waste heat utilization pipe outlet port 462, reducing the cold energy required for gas-liquid separation in the gas-liquid separator in the next step, thereby achieving the effect of energy saving and improving the utilization rate of hydrogen output.

[0056] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid, comprising a high-temperature proton exchange membrane fuel cell having a cathode and an anode, characterized in that: It also includes a fuel supply system, an air supply system, a high-temperature proton exchange membrane fuel cell stack condensation system, an organic Rankine cycle power generation system, an ammonia vapor compression refrigeration cycle and hot water supply system, an air dehumidification cycle system, a lithium bromide absorption refrigeration cycle system, and an organic hydrogen storage liquid recovery system connected through pipelines; The fuel supply system includes a dehydrogenation reaction device, a gas-liquid separator, a humidifier, and a hydrogen compressor connected by pipelines. After the organic hydrogen storage liquid is preheated by the preheater, it enters the dehydrogenation reaction device to undergo a dehydrogenation reaction. After gas-liquid separation by the gas-liquid separator, humidification by the humidifier, and compression by the hydrogen compressor, the anode of the high-temperature proton exchange membrane fuel cell receives the hydrogen processed by the hydrogen compressor. The air supply system includes a preheater, an air compressor, and an air delivery pipeline connected to the cathode of the high-temperature proton exchange membrane fuel cell through a pipeline; the air enters the air compressor for compression after being preheated, and then flows into the cathode of the high-temperature proton exchange membrane fuel cell; When the system is running, the anode of the high-temperature proton exchange membrane fuel cell receives the hydrogen processed by the hydrogen compressor and then reacts chemically with the air supplied by the air supply system to generate electricity and heat energy; the gas coming out of the anode of the high-temperature proton exchange membrane fuel cell enters the hydrogen burner, mixes with the air entering from the outside and burns to preheat the fuel; the gas coming out of the cathode of the high-temperature proton exchange membrane fuel cell enters the air preheater to preheat the air; In addition, the cooling oil enters the high-temperature proton exchange membrane fuel cell stack for heat exchange cooling, and is connected to the first waste heat exchanger, the first condenser, and the hot water heater through pipelines, and circulates in sequence; The organic Rankine cycle power generation system includes a first waste heat exchanger, a turbine, and a second condenser connected to a high-temperature proton exchange membrane fuel cell stack through a pipeline; wherein the cooling medium is cooled from the high-temperature proton exchange membrane fuel cell stack to form low-grade waste heat, and is heated by the first waste heat exchanger to drive the turbine to generate electricity; the cooling medium flowing through the turbine flows back to the first waste heat exchanger through the second condenser to circulate and drive the organic Rankine cycle power generation system to operate continuously; The ammonia vapor compression refrigeration cycle and hot water supply system includes an ammonia compressor, a first condenser, a third condenser, a first throttle valve, and a first evaporator connected by pipelines. On the one hand, ammonia gas is compressed into high-temperature gas by the ammonia compressor and then enters the first condenser, the third condenser, the first throttle valve, and the first evaporator in sequence, and finally flows back to the ammonia compressor to complete the refrigeration cycle; wherein the heat released by condensation of the third condenser can heat the normal temperature water, and then connected to the hot water heater through a pipeline to heat the hot water to the required hot water temperature; on the other hand, the heat released by condensation of the first condenser can heat the cooling medium from the first waste heat exchanger, and the heated cooling medium temperature is increased as the heat source of the hot water heater, and enters the high-temperature proton exchange membrane fuel cell stack after heating the water; The air dehumidification cycle system includes a second waste heat exchanger, a regenerator, a first heat exchanger, a fourth condenser, and a dehumidifier connected to the gas-liquid separator through a pipeline. The dehumidifier is provided with a dehumidifying medium. On the one hand, the dehumidifying medium absorbs moisture in the air in the dehumidifier and performs a temperature reduction treatment, and then flows through the first heat exchanger, the second waste heat exchanger, and the regenerator, wherein the dehumidifying medium absorbs low-grade waste heat carried by the organic hydrogen storage liquid flowing out from the bottom of the gas-liquid separator in the second waste heat exchanger, and regenerates the dehumidifying medium in the regenerator; on the other hand, the dehumidifying medium flowing out of the regenerator flows through the first heat exchanger and the fourth condenser, and finally flows back to the dehumidifier to complete the air dehumidification cycle, wherein the cooling capacity required by the fourth condenser is drawn from the second evaporator; The lithium bromide absorption refrigeration cycle system includes a generator connected to a second waste heat exchanger through a pipeline and filled with a dilute lithium bromide solution. On the one hand, the dilute lithium bromide solution is heated and concentrated in the generator to generate water vapor, and the water vapor flows through the fifth condenser and the second throttle valve in sequence through the pipeline, and finally enters the second evaporator to absorb heat and provide cold capacity to the fourth condenser. The water vapor generated in the second evaporator enters the absorber through the pipeline; on the other hand, the lithium bromide concentrated solution flowing out of the generator is connected to the second regenerator and the third throttle valve in sequence through the pipeline and finally enters the absorber. At this time, the lithium bromide concentrated solution and the water vapor flowing out of the second evaporator form a dilute lithium bromide solution in the absorber and flow to the second regenerator and the generator to complete the lithium bromide absorption refrigeration cycle system; The organic hydrogen storage liquid recovery system includes a third waste heat exchanger equipped with a lithium bromide dilute solution generator and an organic hydrogen storage liquid recovery device connected by a pipeline. The organic hydrogen storage liquid heats the normal temperature water in the third waste heat exchanger and then flows to the organic hydrogen storage liquid recovery device for recovery.

2. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The reaction taking place in the burner is an adiabatic reaction.

3. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The pipe types involved in this system are steel pipes or silicone pipes.

4. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The system also includes a first delivery pump, a second delivery pump, a third delivery pump, a fourth delivery pump, and a fifth delivery pump; the first delivery pump is installed between the pipeline connecting the high-temperature proton exchange membrane fuel cell stack and the first waste heat exchanger, the second delivery pump is installed between the pipeline connecting the second condenser and the first waste heat exchanger, the third delivery pump is installed between the pipeline connecting the first regenerator and the second waste heat exchanger, the fourth delivery pump is installed between the pipeline connecting the first regenerator and the first regenerator, and the fifth delivery pump is installed between the pipeline connecting the absorber and the second regenerator.

5. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The component of the organic hydrogen storage liquid is perhydro-N-propylcarbazole.

6. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The operating temperature of the high-temperature proton exchange membrane fuel cell stack is 175℃-190℃.

7. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 1, characterized in that: The dehydrogenation reaction device comprises a dehydrogenation reaction tank, a liquid heater arranged in the dehydrogenation reaction tank, a heat conduction plate arranged below the liquid heater, and a hydrogen liquid stirring device; The upper part of the dehydrogenation reaction tank is connected to a hydrogen liquid inlet pipe, and the lower part of the dehydrogenation reaction tank is connected to a hydrogen liquid outlet pipe; a hot hydrogen outlet; The liquid-passing heater comprises a cylindrical shell, a liquid-passing plate arranged in the cylindrical shell, a heating tube arranged below the liquid-passing plate, and a liquid-passing hole and a driving rod hole are provided on the surface of the liquid-passing plate; An electric heating tube is arranged below the heat conducting plate; The hydrogen liquid stirring device includes a driving motor, a driving rod, and a stirring blade. The driving motor is arranged on the top of the dehydrogenation reaction tank. One end of the driving rod is connected to the driving motor, and the other end passes through the driving rod hole and extends to the top of the heat conduction plate and is connected to the stirring blade.

8. A high-temperature proton exchange membrane fuel cell cooling, heating, electricity and dehumidification combined supply system based on the utilization of waste heat from the dehydrogenation reaction of an organic hydrogen storage liquid as claimed in claim 7, characterized in that: It also includes a dehydrogenation reaction heat exchanger and a waste heat utilization pipe, wherein the waste heat utilization pipe is arranged in the dehydrogenation reaction tank, and the dehydrogenation reaction heat exchanger is installed on the outer surface of the dehydrogenation reaction tank, including an air inlet, a cold hydrogen outlet, a hot air outlet, and a hot hydrogen inlet located at the lower end of the dehydrogenation reaction heat exchanger; wherein the hot hydrogen inlet is connected to the hot hydrogen outlet of the dehydrogenation reaction tank through a connecting pipe; the hot air outlet is connected to the waste heat utilization pipe through a connecting pipe, and the air outlet end of the waste heat utilization pipe is connected to the external environment.

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