CN113540511A - Organic liquid integrated energy system capable of efficiently recovering heat - Google Patents
Organic liquid integrated energy system capable of efficiently recovering heat Download PDFInfo
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- CN113540511A CN113540511A CN202110804947.8A CN202110804947A CN113540511A CN 113540511 A CN113540511 A CN 113540511A CN 202110804947 A CN202110804947 A CN 202110804947A CN 113540511 A CN113540511 A CN 113540511A
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- 239000007788 liquid Substances 0.000 title claims abstract description 113
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 83
- 239000001257 hydrogen Substances 0.000 claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 47
- 238000010248 power generation Methods 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 238000007906 compression Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000006835 compression Effects 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002918 waste heat Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical group [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 5
- 238000005485 electric heating Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 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
- 238000005086 pumping Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010438 heat treatment 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 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
Images
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 for efficient heat recovery, and belongs to the technical field of organic liquid hydrogen storage. 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 generates endothermic dehydrogenation reaction, the heat required by 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 enough 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 a hydrogen discharge process, improves the overall energy efficiency, and has obvious efficiency improvement compared with the modes of electric heating or hydrogen catalytic combustion and the like.
Description
Technical Field
The invention belongs to the technical field of organic liquid hydrogen storage, 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 the existing energy storage technology such as a lithium ion battery is replaced by the advantages of high energy density, cleanness, no pollution and the like.
The large-scale utilization of hydrogen energy presents more challenges, and the current major hydrogen storage methods have various disadvantages. The high-pressure gaseous hydrogen storage is widely applied and has low cost, but hydrogen charging and discharging need a high-pressure environment and potential safety hazards exist; the metal hydride has safe and stable hydrogen storage and lower pressure, but the metal hydride has large mass, and the hydrogen charging and discharging process is limited by the heat and mass transfer capacity, so the metal hydride is not suitable for being applied in the field of mobile traffic; the low-temperature liquid hydrogen storage has higher energy density and is a hot technology in the field of aerospace, but the technology 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 the key point of hydrogen energy development in the future. The organic liquid hydrogen storage material represented by ethyl carbazole needs a system to provide considerable heat in the hydrogen discharge process, and for many application scenarios, the selection of a heat source is the key to the application of the organic hydrogen storage technology. At present, the common technology adopts electric heating for heat supply, the electric energy of a 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, electricity is converted into heat, and 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 burning to the dehydrogenation reactor heat supply, and efficiency improves to some extent than the electric heating scheme, but has wasted partly heat quality among 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 for efficient heat recovery, which mainly solves the problem that equipment lacking an external heat source is difficult to store and supply energy by applying an organic liquid hydrogen storage technology.
In order to solve the technical problems, the technical defects to be overcome by the invention are as follows: how to select a heat source for the organic hydrogen storage material in the hydrogen discharging 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;
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 generates endothermic dehydrogenation reaction, and the heat required by the dehydrogenation reaction is provided by the heat pump unit;
reaction products in the dehydrogenation reaction unit enter the gas-liquid separation unit, the gas-liquid separation unit separates the reaction products into hydrogen and organic liquid poor in hydrogen, and the organic liquid poor in hydrogen is sequentially introduced into the heat exchange unit and the organic liquid poor in hydrogen storage tank in the storage unit; said hydrogen is pumped into said power generation unit;
the power generation unit mainly comprises a proton exchange membrane fuel cell, 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 beneficial technical effects directly brought by the technical scheme are as follows:
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 additionally heating the dehydrogenation reaction unit.
In 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 the absorption heat pump unit and the vapor compression heat pump unit convert waste heat generated by the power generation unit into a heat source with sufficient heat and supply the heat source to the dehydrogenation reaction unit.
As another preferable aspect of the present invention, the storage unit includes 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 with heat load of 23.55 MJ/h.
Preferably, the dehydrogenation reaction unit is a porous medium fixed bed reactor, works at the temperature of 160-170 ℃, and adopts Pd/Al2O3Porous medium catalyst filled with inert substance Al2O3The space velocity of the reactor is 1.1h-1The flow rate of organic liquid in the dehydrogenation process is 750mol/h, and the flow rate of hydrogen is 100Nm3/h。
Further preferably, the generating efficiency of the generating unit is 50%, the electric energy is output at 532MJ/h, and the waste heat is generated at 320 MJ/h.
Preferably, the heat pump unit mainly controls the working range through the electric energy provided by the power generation unit; under the rated working condition, the heat pump unit needs 64MJ/h of electricity, 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 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 heat load is 177MJ/h, the working temperatures of an evaporator and a generator are 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 230MJ/h heat load 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 750 mol/h.
The invention also aims to provide application of the 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 waste heat generated in the fuel cell through the two-stage heat pump unit, does not need an external heat source to supply a hydrogen discharge process, improves the overall energy efficiency, has obvious efficiency improvement compared with the modes of electric heating or hydrogen catalytic combustion and the like, improves the power generation effect by more than 15 to 23 percent compared with the hydrogen catalytic combustion scheme, and is a novel technical scheme with wide application range and higher energy storage efficiency.
The system disclosed by the invention does not need external heat supply, is high in energy storage density, safe and environment-friendly, and is suitable for energy storage power stations and other application scenes pursuing energy efficiency.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic structural diagram of an efficient heat recovery organic liquid integrated energy system according to the present invention;
FIG. 2 is a working condition cycle pressure-enthalpy diagram of the compression heat pump according to 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 type heat pump unit, 8, an absorption type heat pump unit, 9, a hydrogen-rich organic liquid storage tank, 10 and a hydrogen-poor organic liquid storage tank.
a-b is a compression process
b-c are condensation processes
c-d is a throttling process
d-a is the evaporation process.
Detailed Description
The invention provides an organic liquid integrated energy system for efficient heat recovery, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is described in detail with reference to specific embodiments.
As shown in fig. 1, the invention provides an organic liquid integrated energy system for efficient 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 2.
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, the specific structure of the plate-fin heat exchanger refers to the prior art, and detailed description is omitted here.
Pumping the hydrogen-rich organic liquid out of the hydrogen-rich organic liquid storage tank 9, preheating the hydrogen-rich organic liquid by the heat exchange unit 2, entering the dehydrogenation reaction unit 3, entering a gas-liquid mixture obtained by the dehydrogenation reaction unit 3 into the gas-liquid separation unit 4, separating the hydrogen-rich organic liquid by the gas-liquid separation unit 4, cooling the obtained hydrogen-poor organic liquid by the heat exchange unit 2, entering the hydrogen-poor organic liquid storage tank 10 for storage, and waiting for later-stage circulation treatment; the hydrogen obtained after separation by the gas-liquid separation unit 4 enters a power generation unit.
The general structure of the dehydrogenation reaction unit 3 is as follows: the device comprises a dehydrogenation reactor, a heat exchanger, a corresponding pump valve and an electric control device, wherein the specific structure of each device refers to the prior art, the hydrogen-rich organic liquid in the dehydrogenation reaction unit 3 is subjected to endothermic dehydrogenation reaction, the heat required by heat absorption is obtained from the heat pump unit 6, the obtained heat is supplied to the dehydrogenation process, and the reaction product reaches the gas-liquid separation unit 4;
reaction products in the gas-liquid separation unit 4 are 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 an electric control device, air and hydrogen react in the power generation unit 5 to generate electricity, a part of generated electric energy is input into the heat pump unit 6 to support the normal work of the vapor compression type heat pump 7, and most of the electric energy is output to the outside to supply other electric appliances for work; the heat pump unit 6 mainly comprises 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 high-quality and sufficient-heat source through two stages of heat pumps in sequence and finally supplied to the dehydrogenation reaction unit 3.
According to the organic liquid integrated energy system for efficient heat recovery, the organic liquid is N-ethylcarbazole organic hydrogen storage liquid, the hydrogen-rich liquid is dodecahydroethylcarbazole, and the flow rate of the hydrogen-rich organic liquid is 750 mol/h.
In the organic liquid integrated energy system for efficient heat recovery, the dehydrogenation reaction unit 3 is a porous medium fixed bed reactor, works at the temperature of 160-170 ℃, and adopts Pd/Al2O3Porous medium catalyst filled with inert substance Al2O3The space velocity of the reactor is 1.1h-1The flow rate of organic liquid in the dehydrogenation process is 750mol/h, and the flow rate of hydrogen is 100Nm3/h。
In the organic liquid integrated energy system for efficient heat recovery, the heat exchange unit 2 adopts a shell-and-tube heat exchanger with heat load 23.55 MJ/h.
According to the organic liquid integrated energy system for efficient heat recovery, the power generation unit 5 adopts a proton exchange membrane hydrogen fuel cell, the power generation efficiency is 50%, the electric energy is output at 532MJ/h, and the waste heat is generated at 320 MJ/h.
In the organic liquid integrated energy system for efficient heat recovery, the heat pump unit 6 mainly controls the working range through the electric energy provided by the power generation unit 5; under a rated working condition, the heat pump unit 6 needs 64MJ/h of electricity, 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 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 the absorber is about 130 ℃, the heat load is 177MJ/h, the working ranges of the evaporator and the generator are about 80 ℃, the working range of the condenser is about 25 ℃, and the COP is 0.56; a vapor compression heat pump 7 in a 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 230MJ/h heat load is provided, and the temperature-enthalpy diagram of the system is shown in figure 2;
according to the organic liquid integrated energy system for efficient heat recovery, the chemical energy of the product hydrogen obtained by dehydrogenation is 1079MJ/h, the integral power generation power of a power supply system is 470MJ/h, 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 above system of the present invention is explained below.
The method specifically comprises the following steps:
firstly, pumping out hydrogen-rich organic liquid from a hydrogen-rich organic liquid storage tank, pretreating the hydrogen-rich organic liquid 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, the separated hydrogen-poor liquid is cooled by a heat exchange unit and enters a hydrogen-poor organic liquid storage tank for storage, and the later cycle treatment is waited;
pumping the hydrogen obtained by the gas-liquid separation unit into a power generation unit, reacting air and the hydrogen in the power generation unit to generate power, inputting a part of generated electric energy into a heat pump unit to support the operation of a vapor compression heat pump, and outputting most of the generated electric energy to the outside to supply other electric appliances for operation; waste heat obtained from the power generation unit is converted into a high-quality and sufficient-heat source through two stages of heat pumps in sequence and is finally supplied to the dehydrogenation reaction unit.
Parts which are 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 reaction unit 3, the gas-liquid separation unit 4, etc. are used more frequently herein, the possibility of using other terms is not excluded, and these terms are used only for the purpose of more conveniently describing and explaining the essence of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
It is further understood that the specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. An organic liquid integrated energy system, characterized in that: the heat pump dehydrogenation 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;
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 generates endothermic dehydrogenation reaction, and the heat required by the dehydrogenation reaction is provided by the heat pump unit;
reaction products in the dehydrogenation reaction unit enter the gas-liquid separation unit, the gas-liquid separation unit separates the reaction products into hydrogen and organic liquid poor in hydrogen, and the organic liquid poor in hydrogen is sequentially introduced into the heat exchange unit and the organic liquid poor in hydrogen storage tank in the storage unit; said hydrogen is pumped into said power generation unit;
the power generation unit mainly comprises a proton exchange membrane fuel cell, 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 to support the normal work of the heat pump unit, and the other part of the generated electric energy is output to the outside.
2. The organic liquid integrated energy system according to claim 1, wherein: 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 enough heat through the absorption heat pump unit and the vapor compression heat pump unit and is supplied to the dehydrogenation reaction unit.
3. The organic liquid integrated energy system according to 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 with heat load of 23.55 MJ/h.
4. The organic liquid integrated energy system according to claim 1, wherein: the dehydrogenation reaction unit is a porous medium fixed bed reactor, works at 160-170 ℃, and adopts Pd/Al2O3Porous medium catalyst filled with inert substance Al2O3The space velocity of the reactor is 1.1h-1The flow rate of organic liquid in the dehydrogenation process is 750mol/h, and the flow rate of hydrogen is 100Nm3/h。
5. The organic liquid integrated energy system according to claim 1, wherein: the generating efficiency of the generating unit is 50%, 532MJ/h of electric energy is output, and 320MJ/h of waste heat is generated.
6. The organic liquid integrated energy system according to claim 1, wherein: the heat pump unit mainly controls the working range through the electric energy provided by the power generation unit; under the rated working condition, the heat pump unit needs 64MJ/h of electricity, 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 heat load of 230MJ/h at about 180 ℃.
7. The organic liquid integrated energy system according to claim 2, wherein: 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 heat load is 177MJ/h, the working temperatures of an evaporator and a generator are 70-90 ℃, the working temperature of a condenser is 160-190 ℃, and the COP is 1.2-1.4.
8. The organic liquid integrated energy system according to 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 230MJ/h heat load is provided.
9. The organic liquid integrated energy system according to 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 750 mol/h.
10. Use of an organic liquid integrated energy system according to any one of claims 1 to 9 in an energy storage power station.
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