CN113540511B - Organic liquid integrated energy system with high-efficiency heat recovery - Google Patents
Organic liquid integrated energy system with high-efficiency heat recovery Download PDFInfo
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- CN113540511B CN113540511B CN202110804947.8A CN202110804947A CN113540511B CN 113540511 B CN113540511 B CN 113540511B CN 202110804947 A CN202110804947 A CN 202110804947A CN 113540511 B CN113540511 B CN 113540511B
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- 239000007788 liquid Substances 0.000 title claims abstract description 109
- 238000011084 recovery Methods 0.000 title abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 47
- 238000010248 power generation Methods 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 238000007906 compression Methods 0.000 claims abstract description 14
- 230000006835 compression Effects 0.000 claims abstract description 13
- 239000002918 waste heat Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000004146 energy storage Methods 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical group [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 5
- 238000005485 electric heating Methods 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/02—Heat pumps of the compression type
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/04—Heat pumps of the sorption type
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/06—Heat pumps characterised by the source of low potential heat
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an organic liquid integrated energy system with high-efficiency heat recovery, and belongs to the technical field of organic liquid hydrogen storage. The device comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a power generation unit and a heat pump unit which are sequentially connected from the storage unit to the heat exchange unit, wherein hydrogen-rich organic liquid provided by the storage unit enters the dehydrogenation reaction unit after being preheated in the heat exchange unit; the hydrogen-rich liquid in the dehydrogenation reaction unit undergoes endothermic dehydrogenation reaction, the heat required for the dehydrogenation reaction is provided by the heat pump unit, and the waste heat generated by the power generation unit is converted into a heat source with sufficient heat through the absorption heat pump unit and the vapor compression heat pump unit and is supplied to the dehydrogenation reaction unit. The invention utilizes the waste heat generated in the fuel cell through the two-stage heat pump unit, does not need an external heat source to supply and discharge hydrogen, improves the overall energy efficiency, and has obvious efficiency improvement relative to modes such as electric heating or hydrogen catalytic combustion.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage of organic liquid, and particularly relates to an organic liquid integrated energy system.
Background
The hydrogen energy is used as a new energy mode with bright prospect, and has the opportunity to replace the existing energy storage technologies such as lithium ion batteries and the like by virtue of the advantages of high energy density, cleanness, no pollution and the like.
The large-scale utilization of hydrogen energy faces more challenges, and the main hydrogen storage modes at present have various disadvantages. The high-pressure gas hydrogen storage has wide application and low cost, but the hydrogen charging and discharging needs a high-pressure environment and has potential safety hazards; the metal hydride is safe and stable in hydrogen storage and low in pressure, but the mass of the metal hydride is large, and the hydrogen charging and discharging process is limited by heat transfer capacity, so that the metal hydride is not suitable for being applied to the field of mobile traffic; the low-temperature liquid hydrogen storage has higher energy density, is a hot spot technology in the aerospace field, but has high cost and complex technology, and is difficult to store hydrogen for a long time.
The organic liquid hydrogen storage technology has high energy density, is safe and stable, is convenient for large-scale long-distance transportation, and is an important point for the development of hydrogen energy in the future. The organic liquid hydrogen storage material represented by ethyl carbazole needs the system to provide considerable heat in the hydrogen release process, and for many application scenes, the selection of a heat source is key to the application of the organic hydrogen storage technology. At present, the common technology adopts electric heating to supply heat, the electric energy of the heater is obtained from a fuel cell, but the power generation efficiency of the fuel cell is only 40% -55%, a large amount of waste heat is wasted, and the electricity is converted into heat, so that the energy efficiency of the system is further reduced. Application number 201910537030.9 discloses a dehydrogenation device based on hydrogen catalytic combustion heating, adopts the mode of hydrogen combustion to supply heat to the dehydrogenation reactor, and efficiency improves to some extent than the electrical heating scheme, but has wasted a part of heat quality in the combustion process, and the system efficiency has certain promotion space.
Disclosure of Invention
The invention aims to provide an organic liquid integrated energy system with high-efficiency heat recovery, which mainly solves the problems of equipment lacking an external heat source in energy storage and power supply by using an organic liquid hydrogen storage technology.
In order to solve the technical problems, the invention has the following technical defects: how the organic hydrogen storage material chooses a heat source during the hydrogen desorption process.
The invention adopts the following technical scheme:
an organic liquid integrated energy system comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a power generation unit and a heat pump unit which are sequentially connected from front to back;
the storage unit is used for storing hydrogen-rich organic liquid and hydrogen-poor organic liquid;
the hydrogen-rich organic liquid provided by the storage unit enters the dehydrogenation reaction unit after being preheated in the heat exchange unit;
the hydrogen-rich liquid in the dehydrogenation reaction unit undergoes endothermic dehydrogenation reaction, and the heat required by the dehydrogenation reaction is provided by the heat pump unit;
the reaction product in the dehydrogenation reaction unit enters the gas-liquid separation unit, the gas-liquid separation unit separates the reaction product into hydrogen and hydrogen-poor organic liquid, and the hydrogen-poor organic liquid is sequentially introduced into the heat exchange unit and a hydrogen-poor organic liquid storage tank in the storage unit; the hydrogen is pumped into the power generation unit;
the power generation unit takes a proton exchange membrane fuel cell as a main part, air and hydrogen react in the power generation unit to generate power, one part of generated electric energy is input into the heat pump unit, and the other part of generated electric energy is output to the outside.
The technical scheme directly brings the following beneficial technical effects:
by arranging the heat pump unit, waste heat generated in the power generation unit is collected, and the collected heat can be used in dehydrogenation reaction of the dehydrogenation reaction unit without additional heating.
As a preferred embodiment of the present invention, the heat pump unit includes an absorption heat pump unit and a vapor compression heat pump unit, and waste heat generated by the power generation unit is converted into a heat source sufficient in heat by the absorption heat pump unit and the vapor compression heat pump unit and is supplied to the dehydrogenation reaction unit.
As another preferred aspect of the present invention, the storage unit includes a hydrogen-rich organic liquid storage tank and a hydrogen-lean organic liquid storage tank; the heat exchange unit adopts a shell-and-tube heat exchanger, and the heat load is 23.55MJ/h.
Further preferably, the dehydrogenation reaction unit is a porous medium fixed bed reactor, works at the temperature range of 160-170 ℃ and adopts Pd/Al 2 O 3 Porous medium catalyst filled with inert material Al 2 O 3 The space velocity of the reactor is 1.1h -1 Organic liquid flow rate in dehydrogenation process is 750mol/h, hydrogen flow rate is 100Nm 3 /h。
Further preferably, the generating efficiency of the generating unit is 50%, the output electric energy is 532MJ/h, and the waste heat is 320MJ/h.
Preferably, the heat pump unit controls the working range mainly through the electric energy provided by the power generation unit; under rated working conditions, the power required by the heat pump unit is 64MJ/h, and the power generation unit supplies 12% of electric energy to the heat pump unit, so that the heat pump unit provides a heat source with a heat load of 230MJ/h at about 180 ℃.
Preferably, the absorption heat pump unit is a lithium bromide/water second-class single-effect absorption heat pump, wherein the working temperature of an absorber is 120-150 ℃, the working temperature of an evaporator and a generator is 70-90 ℃, the working temperature of a condenser is 160-190 ℃, and the COP is 1.2-1.4.
Preferably, the vapor compression heat pump unit adopts a high-temperature refrigerant R11, wherein the working temperature of an evaporator is 110-130 ℃, the working temperature of a condenser is 170-190 ℃, the COP is 1.28, and a heat source with a heat load of 230MJ/h is provided.
The organic liquid is N-ethyl carbazole organic hydrogen storage liquid, the hydrogen-rich organic liquid is dodecahydro ethyl carbazole, and the flow rate of the hydrogen-rich organic liquid is 750mol/h.
Another object of the present invention is to provide an application of the above-mentioned organic liquid integrated energy system in an energy storage power station.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention utilizes the waste heat generated in the fuel cell through the two-stage heat pump unit, does not need an external heat source to supply and discharge hydrogen, improves the overall energy efficiency, has obvious efficiency improvement relative to modes such as electric heating or hydrogen catalytic combustion, and the like, improves the power generation effect by more than 15-23 percent relative to a hydrogen catalytic combustion scheme, and is a novel technical scheme with wide application range and higher energy storage efficiency.
The system does not need external heat supply, has high energy storage density, is safe and environment-friendly, and is suitable for application scenes of energy storage power stations and the like pursuing energy efficiency.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of an organic liquid integrated energy system for efficient heat recovery according to the present invention;
FIG. 2 is a diagram of the pressure enthalpy of a compression heat pump cycle in accordance with the present invention;
in the figure: 1. the device comprises a storage unit, 2, a heat exchange unit, 3, a dehydrogenation reaction unit, 4, a gas-liquid separation unit, 5, a power generation unit, 6, a heat pump unit, 7, a vapor compression heat pump unit, 8, an absorption heat pump unit, 9, a hydrogen-rich organic liquid storage tank, 10 and a hydrogen-poor organic liquid storage tank.
a-b is the compression process
b-c is the condensation process
c-d is the throttling process
d-a is the evaporation process.
Detailed Description
The invention provides an organic liquid integrated energy system with high-efficiency heat recovery, which is described in detail below with reference to specific embodiments in order to make the advantages and technical scheme of the invention clearer and more definite.
As shown in fig. 1, the invention provides an organic liquid integrated energy system with high-efficiency heat recovery, which comprises a storage unit 1, a heat exchange unit 2, a dehydrogenation unit 3, a gas-liquid separation unit 4, a power generation unit 5 and a heat pump unit 6 which are sequentially connected from the storage unit to the heat exchange unit.
Wherein the storage unit 1 comprises a hydrogen-rich organic liquid storage tank 9 and a hydrogen-poor organic liquid storage tank 10, wherein a specific hydrogen-rich organic hydrogen storage liquid is stored in the hydrogen-rich organic liquid storage tank 9, and a hydrogen-poor organic hydrogen storage liquid is stored in the hydrogen-poor organic liquid storage tank 10;
the hydrogen-rich organic liquid storage tank 9 and the hydrogen-poor organic liquid storage tank 10 are respectively connected with the heat exchange unit 2, specifically, the heat exchange unit 2 is composed of a plate-fin heat exchanger and a corresponding pump valve, and the specific structure of the plate-fin heat exchanger is just described with reference to the prior art, and detailed description is omitted here.
The hydrogen-rich organic liquid is pumped out from a hydrogen-rich organic liquid storage tank 9, preheated by a heat exchange unit 2 and enters a dehydrogenation reaction unit 3, a gas-liquid mixture obtained by the dehydrogenation reaction unit 3 enters a gas-liquid separation unit 4, and after being separated by the gas-liquid separation unit 4, the obtained hydrogen-poor liquid is cooled by the heat exchange unit 2 and enters a hydrogen-poor organic liquid storage tank 10 for storage, and is waited for later circulation treatment; the hydrogen gas obtained after separation by the gas-liquid separation unit 4 enters the power generation unit.
The general structure of the dehydrogenation unit 3 is as follows: the dehydrogenation reaction unit 3 is characterized by comprising a dehydrogenation reactor, a heat exchanger, a corresponding pump valve and an electric control device, wherein the specific structure of each device is as shown in the prior art, hydrogen-rich organic liquid in the dehydrogenation reaction unit 3 undergoes endothermic dehydrogenation reaction, heat required by the heat absorption is obtained from the heat pump unit 6, the obtained heat is supplied to the dehydrogenation process, and a reaction product reaches the gas-liquid separation unit 4;
the reaction product in the gas-liquid separation unit 4 is separated into hydrogen and hydrogen-poor organic liquid, the hydrogen-poor liquid returns to the hydrogen-poor organic liquid storage tank 10 through the heat exchange unit, and the hydrogen is pumped into the power generation unit 5;
the power generation unit 5 mainly comprises a proton exchange membrane fuel cell and comprises a corresponding heat exchanger, a pipe fitting and electric control equipment, air and hydrogen react in the power generation unit 5 to generate power, part of the generated electric energy is input into the heat pump unit 6 to support the normal operation of the vapor compression heat pump 7, and most of the generated electric energy is output to the outside to supply other electric appliances to work; the heat pump unit 6 mainly includes an absorption heat pump unit 8 and a vapor compression heat pump unit 7, and waste heat obtained from the power generation unit 6 is converted into a heat source of high quality and sufficient heat by two stages of heat pumps in order and finally supplied to the dehydrogenation reaction unit 3.
The organic liquid integrated energy system for efficiently recovering heat is characterized in that the organic liquid is N-ethyl carbazole organic hydrogen storage liquid, the hydrogen-rich liquid is dodecahydro ethyl carbazole, and the flow rate of the hydrogen-rich organic liquid is 750mol/h.
The organic liquid integrated energy system with high-efficiency heat recovery, wherein the dehydrogenation reaction unit 3 is a porous medium fixed bed reactor, works at the temperature of 160-170 ℃ and adopts Pd/Al 2 O 3 Porous medium catalyst filled with inert material Al 2 O 3 The space velocity of the reactor is 1.1h -1 Organic liquid flow rate in dehydrogenation process is 750mol/h, hydrogen flow rate is 100Nm 3 /h。
The organic liquid integrated energy system with high-efficiency heat recovery adopts a shell-and-tube heat exchanger as the heat exchange unit 2, and the heat load is 23.55MJ/h.
In the organic liquid integrated energy system with high-efficiency heat recovery, the power generation unit 5 adopts a proton exchange membrane hydrogen fuel cell, the power generation efficiency is 50%, the output electric energy is 532MJ/h, and the waste heat is 320MJ/h.
In the organic liquid integrated energy system for efficient heat recovery, the heat pump unit 6 controls the working range mainly through the electric energy provided by the power generation unit 5; under the rated working condition, the power required by the heat pump unit 6 is 64MJ/h, and the power generation unit supplies 12% of electric energy to the heat pump unit 6, so that the heat pump unit provides a heat source with a heat load of 230MJ/h at about 180 ℃;
in the organic liquid integrated energy system for efficient heat recovery, the absorption heat pump 8 in the heat pump unit 6 is a lithium bromide/water second-type single-effect absorption heat pump, wherein the working range of an absorber is about 130 ℃, the heat load is 177MJ/h, the working range of an evaporator and a generator is about 80 ℃, the working range of a condenser is about 25 ℃, and the COP is 0.56; the vapor compression heat pump 7 in the heat pump unit 6 adopts a high-temperature refrigerant R11, wherein the working range of an evaporator is about 120 ℃, the working range of a condenser is about 180 ℃, the COP is 1.28, a heat source with a heat load of 230MJ/h is provided, and the system Wen Hantu is shown in the attached figure 2;
according to the organic liquid integrated energy system with high-efficiency heat recovery, the hydrogen chemical energy 1079MJ/h of the product obtained by dehydrogenation is generated, the overall power generation power 470MJ/h of the power supply system is generated, the power generation efficiency is 44%, and the power generation efficiency is improved by 23% compared with that of a catalytic combustion system.
The operation of the system of the present invention will be described below.
The method specifically comprises the following steps:
pumping hydrogen-rich organic liquid from a hydrogen-rich organic liquid storage tank, pretreating by a heat exchange unit, then entering a dehydrogenation reaction unit, and carrying out dehydrogenation reaction under the action of a catalyst in the dehydrogenation reaction unit to obtain a gas-liquid mixture;
secondly, the obtained gas-liquid mixture enters a gas-liquid separation unit, the gas-liquid separation unit is used for separating, and the separated hydrogen-lean liquid is cooled by a heat exchange unit and enters a hydrogen-lean organic liquid storage tank for storage, and the later-stage cyclic treatment is waited;
third, the hydrogen obtained by the gas-liquid separation unit is pumped into the power generation unit, the air and the hydrogen react in the power generation unit to generate power, part of the generated electric energy is input into the heat pump unit to support the work of the vapor compression heat pump, and most of the electric energy is output to the outside to supply other electric appliances to work; waste heat obtained from the power generation unit is converted into a heat source with high quality and sufficient heat through the two-stage heat pump in sequence and finally supplied to the dehydrogenation reaction unit.
The parts not described in the invention can be realized by adopting or referring to the prior art.
Although terms such as the storage unit 1, the heat exchange unit 2, the dehydrogenation unit 3, the gas-liquid separation unit 4, etc. are more used herein, the possibility of using other terms is not excluded, and these terms are used only for the convenience of describing and explaining the essence of the present invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention.
It should be further understood that the specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (8)
1. An organic liquid integrated energy system, characterized in that: the device comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a power generation unit and a heat pump unit which are sequentially connected from front to back;
the storage unit is used for storing hydrogen-rich organic liquid and hydrogen-poor organic liquid;
the hydrogen-rich organic liquid provided by the storage unit enters the dehydrogenation reaction unit after being preheated in the heat exchange unit;
the hydrogen-rich liquid in the dehydrogenation reaction unit undergoes endothermic dehydrogenation reaction, and the heat required by the dehydrogenation reaction is provided by the heat pump unit;
the reaction product in the dehydrogenation reaction unit enters the gas-liquid separation unit, the gas-liquid separation unit separates the reaction product into hydrogen and hydrogen-poor organic liquid, and the hydrogen-poor organic liquid is sequentially introduced into the heat exchange unit and a hydrogen-poor organic liquid storage tank in the storage unit; the hydrogen is pumped into the power generation unit;
the power generation unit takes a proton exchange membrane fuel cell as a main part, air and hydrogen react in the power generation unit to generate power, part of generated electric energy is input into the heat pump unit to support the normal operation of the heat pump unit, and the other part of generated electric energy is output to the outside; the heat pump unit comprises an absorption heat pump unit and a vapor compression heat pump unit, and waste heat generated by the power generation unit is converted into a heat source with sufficient heat through the absorption heat pump unit and the vapor compression heat pump unit and is supplied to the dehydrogenation reaction unit; the heat pump unit controls the working range mainly through the electric energy provided by the power generation unit; under rated working conditions, the power required by the heat pump unit is 64MJ/h, and the power generation unit supplies 12% of electric energy to the heat pump unit, so that the heat pump unit provides a heat source with a heat load of 230MJ/h at 180 ℃.
2. An organic liquid integrated energy system as claimed in claim 1, wherein: the storage unit comprises a hydrogen-rich organic liquid storage tank and a hydrogen-poor organic liquid storage tank; the heat exchange unit adopts a shell-and-tube heat exchanger, and the heat load is 23.55MJ/h.
3. An organic liquid integrated energy system as claimed in claim 1, wherein: the dehydrogenation reaction unit is a porous medium fixed bed reactor and works at 160-170 ℃ and adopts Pd/Al 2 O 3 Porous medium catalyst filled with inert material Al 2 O 3 The space velocity of the reactor is 1.1h -1 Organic liquid flow rate in dehydrogenation process is 750mol/h, hydrogen flow rate is 100Nm 3 /h。
4. An organic liquid integrated energy system as claimed in claim 1, wherein: the power generation efficiency of the power generation unit is 50%, the output electric energy is 532MJ/h, and the waste heat is 320MJ/h.
5. An organic liquid integrated energy system as claimed in claim 2, wherein: the absorption heat pump unit is a lithium bromide/water second-type single-effect absorption heat pump, wherein the working temperature of an absorber is 120-150 ℃, the working temperature of an evaporator and a generator is 70-90 ℃, the working temperature of a condenser is 160-190 ℃, and the COP is 1.2-1.4.
6. An organic liquid integrated energy system as claimed in claim 2, wherein: the vapor compression type heat pump unit adopts a high-temperature refrigerant R11, wherein the working temperature of an evaporator is 110-130 ℃, the working temperature of a condenser is 170-190 ℃, the COP is 1.28, and a heat source with a heat load of 230MJ/h is provided.
7. An organic liquid integrated energy system as claimed in claim 2, wherein: the organic liquid is N-ethyl carbazole organic hydrogen storage liquid, the hydrogen-rich organic liquid is dodecahydro ethyl carbazole, and the flow rate of the hydrogen-rich organic liquid is 750mol/h.
8. Use of an organic liquid integrated energy system according to any one of claims 1 to 7 in an energy storage power station.
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