CN113548643B - Organic liquid hydrogen supply system integrated with high-temperature heat pump - Google Patents
Organic liquid hydrogen supply system integrated with high-temperature heat pump Download PDFInfo
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- CN113548643B CN113548643B CN202110804941.0A CN202110804941A CN113548643B CN 113548643 B CN113548643 B CN 113548643B CN 202110804941 A CN202110804941 A CN 202110804941A CN 113548643 B CN113548643 B CN 113548643B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 143
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 143
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000007788 liquid Substances 0.000 title claims abstract description 93
- 239000007789 gas Substances 0.000 claims abstract description 54
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 47
- 230000006835 compression Effects 0.000 claims abstract description 41
- 238000007906 compression Methods 0.000 claims abstract description 41
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims description 12
- 239000002918 waste heat Substances 0.000 claims description 9
- 238000004146 energy storage Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 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
- 239000003507 refrigerant Substances 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67D—DISPENSING, DELIVERING OR TRANSFERRING LIQUIDS, NOT OTHERWISE PROVIDED FOR
- B67D7/00—Apparatus or devices for transferring liquids from bulk storage containers or reservoirs into vehicles or into portable containers, e.g. for retail sale purposes
- B67D7/06—Details or accessories
- B67D7/76—Arrangements of devices for purifying liquids to be transferred, e.g. of filters, of air or water separators
-
- 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
- Y02E60/32—Hydrogen storage
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
Abstract
The invention discloses an organic liquid hydrogen supply system integrated with a high-temperature heat pump, and belongs to the technical field of organic liquid hydrogen storage. The hydrogen gas heat pump device comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a hydrogen gas distribution unit and a compression type gas heat pump unit which are sequentially connected from front to back, wherein the hydrogen gas distribution unit is supplied with sufficient hydrogen gas; the hydrogen distribution unit continuously supplies hydrogen to the outside and the compression type gas heat pump unit at the same time, and the hydrogen generated by the hydrogen distribution unit burns and works in the compression type gas heat pump unit to drive the internal compression type heat pump to continuously release heat and serve as a reliable heat source suitable for endothermic reaction in the dehydrogenation unit. The high energy utilization efficiency of the gas heat pump is utilized, the fire loss in the traditional hydrogen catalytic combustion and heat transfer process is reduced, a proper heat source is found for the dehydrogenation unit, external heat supply is not needed, the hydrogen supply efficiency is improved, and the system is widely applicable to various mobile devices.
Description
Technical Field
The invention belongs to the technical field of organic liquid hydrogen storage, and particularly relates to an organic liquid hydrogen supply system integrated with a high-temperature heat pump.
Background
The hydrogen energy is used as a new energy source mode with bright prospect, and the existing energy storage technologies such as lithium ion batteries and the like can be replaced 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. Such as: 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 great 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 a dehydrogenation reactor, and efficiency is improved than the electric heating scheme. However, a part of heat quality is wasted in the combustion process, and if the system is coupled with the fuel cell to externally supply power, the waste heat of the fuel cell is difficult to utilize, the energy efficiency of the system is not competitive, and the further application of the organic liquid hydrogen storage technology is limited.
Disclosure of Invention
The invention aims to provide an organic liquid hydrogen supply system integrated with a high-temperature heat pump, which mainly solves the problems of energy storage and hydrogen supply by applying an organic liquid hydrogen storage technology in equipment lacking an external heat source.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic liquid hydrogen supply system of an integrated high-temperature heat pump comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a hydrogen distribution unit and a compression type gas 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 compression type gas 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 hydrogen distribution unit;
and part of hydrogen generated by the hydrogen distribution unit is input into the compressed gas heat pump unit so as to support the normal operation of the compressed gas heat pump unit, and the other part of hydrogen is output to the outside.
The technical scheme directly brings the following beneficial technical effects:
by arranging the compression type gas heat pump unit, waste heat generated by hydrogen combustion is converted into a heat source with proper quality and sufficient heat through the heat pump, and finally the heat source is supplied to the dehydrogenation reaction unit without additional heating.
As a preferred embodiment 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 plate-fin heat exchanger.
As another preferable scheme of the invention, the dehydrogenation reaction unit comprises a porous medium fixed bed dehydrogenation reactor, a shell-and-tube heat exchanger, a corresponding pump valve and electric control equipment, and the working temperature of the dehydrogenation reaction unit is 160-180 ℃.
Further preferably, the compression type gas heat pump unit mainly comprises a gas engine and a vapor compression type heat pump, the gas engine transmits the obtained work to the vapor compression type heat pump so as to support the work of a refrigerant compressor, and the waste heat generated by hydrogen combustion is converted into a heat source with proper quality and sufficient heat through the compression type gas heat pump unit and finally supplied to the dehydrogenation reaction unit.
Further preferably, the compressed gas heat pump unit controls the working range through the hydrogen flow rate provided by the hydrogen distribution unit, and the hydrogen distribution unit supplies 14% -20% of hydrogen to the compressed gas heat pump unit according to mass percent.
Further preferably, the working range of the vapor compression type heat pump condenser in the compression type gas heat pump unit is 160-190 ℃, and the COP is 1.5-1.7.
Further preferably, the organic liquid in the hydrogen-rich organic liquid storage tank and the hydrogen-poor organic liquid storage tank is carbazole or ethylcarbazole.
Another object of the present invention is to provide an application of an organic liquid hydrogen supply system integrated with a high temperature heat pump in an automotive hydrogen adding station, a hydrogen storage station or an energy storage station.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention supplies sufficient hydrogen to the hydrogen distribution unit; the hydrogen distribution unit continuously supplies hydrogen to the outside and the compression type gas heat pump unit at the same time, and the hydrogen generated by the hydrogen distribution unit burns and works in the compression type gas heat pump unit to drive the internal compression type heat pump to continuously release heat and serve as a reliable heat source suitable for endothermic reaction in the dehydrogenation unit. The high energy utilization efficiency of the gas heat pump is utilized, the fire loss in the traditional hydrogen catalytic combustion and heat transfer process is reduced, a proper heat source is found for the dehydrogenation unit, external heat supply is not needed, the hydrogen supply efficiency is improved, and the system is widely applicable to various mobile devices.
The invention utilizes the waste heat generated in the hydrogen internal combustion engine through the compression type gas heat pump, reduces energy loss, improves the hydrogen utilization efficiency, does not need an external heat source to supply and discharge hydrogen, improves the overall energy efficiency, has obvious efficiency improvement compared with modes of electric heating or direct catalytic combustion of hydrogen and the like, improves the hydrogen supply efficiency by 12-18 percent compared with a hydrogen catalytic combustion scheme with higher efficiency, and is a novel technical scheme with wide application range and higher energy storage efficiency.
The hydrogen supply system does not need external heat supply, has high energy storage density, is safe and environment-friendly, and is suitable for fixed equipment such as an automobile hydrogen adding station, a hydrogen storage station, an energy storage station and the like.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of an organic liquid hydrogen supply system integrated with a high temperature heat pump according to the present invention;
in the figure:
1. the device comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a hydrogen distribution unit, a compression type gas heat pump unit, a hydrogen-rich organic liquid storage tank and a hydrogen-poor organic liquid storage tank, wherein the storage unit, the heat exchange unit, the dehydrogenation reaction unit, the gas-liquid separation unit, the hydrogen distribution unit, the compression type gas heat pump unit, the hydrogen-rich organic liquid storage tank and the hydrogen-poor organic liquid storage tank are arranged in sequence.
Detailed Description
The invention provides an organic liquid hydrogen supply system integrated with a high-temperature heat pump, which is described in detail below with reference to specific embodiments in order to make the advantages and technical schemes of the invention clearer and more definite.
The invention discloses an organic liquid hydrogen supply system of an integrated high-temperature heat pump, which comprises a storage unit, a heat exchange unit 2, a dehydrogenation reaction unit 3, a gas-liquid separation unit 4, a hydrogen distribution unit 5 and a compression type gas heat pump unit 6 which are sequentially connected from front to back, wherein the storage unit 1 comprises a hydrogen-rich organic liquid storage tank 7 and a hydrogen-poor organic liquid storage tank 8, and respectively stores specific hydrogen-rich and hydrogen-poor organic hydrogen storage liquids; two tanks in the storage unit 1 are respectively connected with the heat exchange unit 2, the heat exchange unit 2 consists of a plate-fin heat exchanger and a corresponding pump valve, and hydrogen-rich liquid is pumped out from a hydrogen-rich organic liquid storage tank 7 and preheated by the heat exchange unit 2 to enter the dehydrogenation reaction unit 3; the hydrogen-lean liquid obtained by the gas-liquid separation unit (4) is cooled by the heat exchange unit 2 and enters the hydrogen-lean organic liquid storage tank 8 for storage, and the later circulation treatment is waited.
The dehydrogenation reaction unit 3 comprises a dehydrogenation reactor, a heat exchanger, a corresponding pump valve and an electric control device, wherein hydrogen-rich liquid in the dehydrogenation reaction unit 3 undergoes endothermic hydrogen release reaction, the unit obtains sufficient heat from the compressed gas heat pump unit 6 to supply the dehydrogenation process, and reaction products sequentially reach 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 8 through the heat exchange unit, and the hydrogen is pumped into the hydrogen distribution unit 5; the hydrogen distribution unit 5 comprises a control valve, a pipe fitting and an electric control device, and inputs a part of hydrogen generated by the dehydrogenation reaction unit 3 into the compression type gas heat pump unit 6 to support the work of a hydrogen internal combustion engine (i.e. a gas engine), and most of the hydrogen is output to the outside to supply other devices for work; the compression type gas heat pump unit 6 mainly comprises a gas engine and a vapor compression type heat pump, work obtained from the gas engine in the compression type gas heat pump unit 6 is directly transmitted to the compression type heat pump to support the work of a refrigerant compressor therein, and waste heat generated by hydrogen combustion is converted into a heat source with proper quality and sufficient heat through the heat pump and finally supplied to the dehydrogenation reaction unit 3.
An organic liquid hydrogen supply system integrated with a high-temperature heat pump, wherein 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.
An organic liquid hydrogen supply system integrated with a high-temperature heat pump, wherein a dehydrogenation reaction unit 3 is a porous medium fixed bed reactor and works at a 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。
An organic liquid hydrogen supply system integrated with a high-temperature heat pump adopts a shell-and-tube heat exchanger as a heat exchange unit 2, and the heat load is 23.55MJ/h.
The compression type gas heat pump unit 6 of the organic liquid hydrogen supply system integrated with the high-temperature heat pump consists of a gas engine, namely a hydrogen internal combustion engine and a vapor compression type heat pump, wherein the heat pump compressor mainly works through mechanical work provided by the gas internal combustion engine; under rated working conditions, the mechanical work required by the compression type gas heat pump unit 6 is 60.8MJ/h, the hydrogen distribution unit 5 supplies 19% of hydrogen to the gas engine, and the gas engine supplies 61MJ/h of mechanical work output and 135MJ/h of waste heat to the compression type heat pump, so that the heat pump supplies a heat source with about 180 ℃ and a heat load of 230MJ/h to the dehydrogenation reactor;
organic liquid hydrogen supply system integrated with high-temperature heat pump and dehydrogenating to obtainThe hydrogen flow of the product obtained was 100Nm 3 And/h, the whole hydrogen supply system supplies 81Nm of hydrogen 3 And/h, the hydrogen supply efficiency is 81%, and the hydrogen supply efficiency is improved by 17% compared with 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 a hydrogen distribution unit, the hydrogen distribution unit 5 comprises a control valve, a pipe fitting and an electric control device, a part of the hydrogen generated by the dehydrogenation reaction unit 3 is input into the compressed gas heat pump unit 6 to support the work of a hydrogen internal combustion engine (i.e. a gas engine), and most of the hydrogen is output to the outside to supply other devices for work; the compression type gas heat pump unit 6 mainly comprises a gas engine and a vapor compression type heat pump, work obtained from the gas engine in the compression type gas heat pump unit 6 is directly transmitted to the compression type heat pump to support the work of a refrigerant compressor therein, and waste heat generated by hydrogen combustion is converted into a heat source with proper quality and sufficient heat through the heat pump 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 (5)
1. An organic liquid hydrogen supply system of integrated high temperature heat pump which characterized in that: the device comprises a storage unit, a heat exchange unit, a dehydrogenation reaction unit, a gas-liquid separation unit, a hydrogen distribution unit and a compression type gas 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 compression type gas 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 hydrogen distribution unit;
a part of hydrogen generated by the hydrogen distribution unit is input into the compressed gas heat pump unit so as to support the normal operation of the compressed gas heat pump unit, and the other part of hydrogen is output to the outside;
the compression type gas heat pump unit mainly comprises a gas engine and a vapor compression type heat pump, the gas engine transmits the obtained work to the vapor compression type heat pump so as to support the work of a refrigerant compressor, and waste heat generated by hydrogen combustion is converted into a heat source with proper quality and sufficient heat through the compression type gas heat pump unit and finally supplied to the dehydrogenation reaction unit; the compressed gas heat pump unit controls the working range through the hydrogen flow rate provided by the hydrogen distribution unit, and the hydrogen distribution unit supplies 14-20% of hydrogen to the compressed gas heat pump unit according to the mass percentage; the working range of the vapor compression type heat pump condenser in the compression type gas heat pump unit is 160-190 ℃, and the COP is 1.5-1.7.
2. An organic liquid hydrogen supply system of an integrated high temperature heat pump 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 plate-fin heat exchanger.
3. An organic liquid hydrogen supply system of an integrated high temperature heat pump as claimed in claim 1, wherein: the dehydrogenation reaction unit comprises a porous medium fixed bed dehydrogenation reactor, a shell-and-tube heat exchanger, a corresponding pump valve and electric control equipment, and the working temperature of the dehydrogenation reaction unit is 160-180 ℃.
4. An organic liquid hydrogen supply system of an integrated high temperature heat pump as claimed in claim 1, wherein: the organic liquid in the hydrogen-rich organic liquid storage tank is carbazole or ethylcarbazole.
5. Use of an organic liquid hydrogen supply system integrated with a high temperature heat pump according to any of claims 1-4 in a car hydrogen addition station, hydrogen storage station or energy storage station.
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