CN115259079B - Organic liquid hydrogen storage system of high-efficiency coupling heat storage system and use method - Google Patents
Organic liquid hydrogen storage system of high-efficiency coupling heat storage system and use method Download PDFInfo
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- CN115259079B CN115259079B CN202211048715.5A CN202211048715A CN115259079B CN 115259079 B CN115259079 B CN 115259079B CN 202211048715 A CN202211048715 A CN 202211048715A CN 115259079 B CN115259079 B CN 115259079B
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- 238000005338 heat storage Methods 0.000 title claims abstract description 124
- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000007788 liquid Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000008878 coupling Effects 0.000 title claims abstract description 21
- 238000010168 coupling process Methods 0.000 title claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000005485 electric heating Methods 0.000 claims abstract description 16
- 230000001932 seasonal effect Effects 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 238000003795 desorption Methods 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000011232 storage material Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical group 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
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- General Engineering & Computer Science (AREA)
- Sorption Type Refrigeration Machines (AREA)
Abstract
The invention discloses an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system and a use method thereof, belonging to the technical field of organic liquid hydrogen storage equipment. The hydrogenation reaction device comprises a storage unit, a hydrogenation reaction unit, a chemical heat storage unit and an electric heating unit which are sequentially connected from front to back; the storage unit is used for storing hydrogen, hydrogen-lean organic liquid and hydrogen-rich organic liquid, wherein the hydrogen-lean organic liquid and the hydrogen are introduced into the hydrogenation reaction unit; the hydrogen-rich organic liquid generated by the reaction in the hydrogenation reaction unit is led into the storage unit, and the heat generated by the reaction is led out through the heat conduction oil and is conveyed into the chemical heat storage unit connected with the heat conduction oil; heat is transported to the hydrogenation reaction unit while the equipment is preheated or seasonally temperature compensated. The chemical heat storage unit stores heat generated by the reaction, and supplies the heat to equipment for preheating and seasonal temperature compensation, so that the electric heating heat load is reduced, the demand on external energy is reduced, and compared with a pure electric heating system, the thermal efficiency is obviously improved.
Description
Technical Field
The invention belongs to the technical field of organic liquid hydrogen storage equipment, and particularly relates to an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system and a use method thereof.
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. Organic liquid hydrogen storage materials represented by ethylcarbazole need the system to provide considerable heat in the initial stage of the hydrogen release process and the hydrogen absorption process, and for many application scenes, the selection of a heat source is a key to the application of the organic hydrogen storage technology. It is worth noting that the stable operation of the hydrogen absorption reaction of the system is continuously exothermic, and part of heat is usually directly exhausted after being led out by the heat conducting oil, so that part of energy is wasted. The heat is stored selectively, and the heat is reserved for preheating the system or for seasonal temperature compensation, so that the demand of the system for external energy can be reduced, and the energy density can be improved.
Disclosure of Invention
The invention aims to provide an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system, which mainly solves the problem of energy storage of equipment lacking an external heat source in the application of an organic liquid hydrogen storage technology.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system comprises a storage unit, a hydrogenation reaction unit, a chemical heat storage unit and an electric heating unit which are sequentially connected from front to back;
the storage unit is used for storing hydrogen, hydrogen-lean organic liquid and hydrogen-rich organic liquid, wherein the hydrogen-lean organic liquid and the hydrogen are introduced into the hydrogenation reaction unit;
the hydrogen-rich organic liquid generated by the reaction in the hydrogenation reaction unit is led into the storage unit, and the heat generated by the reaction is led out through heat conduction oil and is conveyed into a chemical heat storage unit connected with the heat conduction oil;
the chemical heat storage unit comprises a heat storage reactor, a condenser, a water storage tank and an evaporator which are sequentially connected, wherein the evaporator is connected with the heat storage reactor, and the heat storage reactor, the condenser, the water storage tank and the evaporator form a closed system; when the chemical heat storage unit stores heat, heat generated by the reaction in the hydrogenation reaction unit is led out through heat conduction oil and is led into the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor enters the water storage tank for storage after being condensed by the condenser; when the chemical heat storage unit releases heat, water stored in the water storage tank is pumped into the evaporator, becomes water vapor under the action of the evaporator, enters the heat storage reactor, and undergoes exothermic adsorption reaction with the heat storage material in the heat storage reactor, and the heat released by the reaction enters the heat conduction oil pipeline through heat exchange and heats subsequent equipment;
the heat storage reactor comprises a reactor body, wherein the top of the reactor body is of an arc-shaped design, the wall surface in the reactor body is coated with a super-hydrophilic coating, heat storage reaction beds and heat conducting oil flow channels are arranged in the reactor body in a staggered manner, and the heat storage reaction beds and the heat conducting oil flow channels are separated by an arc-shaped plate; groove parts are arranged on two sides of the reactor body and used as condensate water flow passages.
Further, the electric heating unit is used for heating heat conduction oil.
Further, the hydrogenation reaction unit comprises a hydrogenation reactor, wherein the hydrogenation reactor is a fixed bed reactor, and the periphery of the fixed bed reactor is wrapped with a heat conducting oil jacket.
Further, the storage unit comprises a hydrogen storage tank for storing hydrogen, a hydrogen-lean organic liquid storage tank for storing a hydrogen-lean organic liquid, and a hydrogen-rich organic liquid storage tank for storing a hydrogen-rich organic liquid.
Further, a pump is provided on a pipe connected between the thermal storage reactor and the condenser.
Preferably, the heat storage material in the heat storage reaction bed layer is MgCl 2 Composites with graphite, zeolites, or CaCl 2 And graphite and zeolite.
Preferably, the super-hydrophilic coating is SiO 2 A base super hydrophilic coating.
Another object of the present invention is to provide a method for using an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system, comprising the following steps in order:
a. introducing hydrogen and a hydrogen-deficient organic liquid into the hydrogenation reaction unit through the storage unit;
b. the hydrogen-rich liquid generated by the reaction of the hydrogenation reaction unit returns to the storage unit, and the heat generated by the reaction is exported through the heat conduction oil and is conveyed to the heat storage unit;
c. when the system needs heat to preheat the reactor or balance the seasonal temperature difference, the heat storage reactor generates adsorption exothermic reaction and works as a system heat source, and the specific working method comprises the following steps:
firstly, high-temperature heat conduction oil flows through the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor is condensed by the condenser and enters the water storage tank for storage;
d. when the hydrogenation reaction unit in the system stably works to release heat, the heat storage reactor generates desorption endothermic reaction and works as a system cold source, and the specific working method is as follows:
the water in the water storage tank is pumped into the evaporator, becomes water vapor in the evaporator, then enters the heat storage reactor to perform exothermic adsorption reaction with the heat storage material, and the released heat enters the heat conduction oil to heat subsequent equipment through heat exchange.
Compared with the prior art, the invention has the following beneficial technical effects:
the organic liquid hydrogen storage system of the high-efficiency coupling heat storage system comprises a storage unit, a hydrogenation reaction unit, a chemical heat storage unit and an electric heating unit which are sequentially connected, wherein the chemical heat storage unit can be used as a system heat source or a system cold source, and the chemical heat storage unit is arranged, so that the hydrogenation system can recover heat emitted in the hydrogenation reaction process, the waste of the system heat is reduced, the heat load of the electric heating unit is further reduced, and the dependence on external energy is reduced.
Specifically, the chemical heat storage unit comprises a heat storage reactor, a condenser, a water storage tank and an evaporator which are sequentially connected, wherein the evaporator is connected with the heat storage reactor, and the four are formed into a closed system; when the chemical heat storage unit releases heat, water in the water storage tank is pumped into the evaporator, becomes water vapor in the evaporator, and then enters the heat storage reactor to perform exothermic adsorption reaction with the heat storage material, and the released heat enters the heat conduction oil to heat subsequent equipment through heat exchange.
In addition, through improving the concrete structure of heat storage reactor, for example utilize the arcuate plate to with heat storage reaction bed and conduction oil runner staggered arrangement, can improve heat exchange efficiency. The arc design at the top of the reactor avoids the condensed liquid drops on the wall surface of the reactor from dripping back into the reaction bed layer, and improves the efficiency of the water desorption of the reactor; the super-hydrophilic coating on the wall surface of the reactor reduces the contact angle of liquid, can cause membranous condensation to occur at the wall surface, reduces the heat transfer coefficient, inhibits the further condensation of water vapor, can better maintain the temperature of the reactor, and improves the moisture desorption efficiency; the design of the grooves on the wall surface is the same, the condensed water is discharged as soon as possible, the condensed water is prevented from contacting the bed layer, and the interference of the external low temperature to the high temperature desorption process in the reactor is reduced.
In summary, the organic liquid hydrogen storage system of the high-efficiency coupling heat storage system provided by the invention is taken as a whole, so that the demand of the system on external energy can be reduced, and the energy density can be improved.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of an organic liquid hydrogen storage system of the present invention with high efficiency coupled heat storage system;
FIG. 2 is a schematic diagram of a heat storage unit according to the present invention;
FIGS. 3 and 4 are side views of the thermal storage reactor of the present invention;
in the figure:
1. the device comprises a storage unit, 2, a hydrogenation reaction unit, 3, a chemical heat storage unit, 4, an electric heating unit, 5, a hydrogen storage tank, 6, a hydrogen-poor organic liquid storage tank, 7, a hydrogen-rich organic liquid storage tank, 8, a hydrogenation reactor, 9, a jacket, 10, a heat storage reactor, 11, a condenser, 12, a water storage tank, 13, an evaporator, 14, a pump, a, an arc, b, a condensate water flow channel, c, a heat storage reaction bed layer, d and a heat conducting oil flow channel.
Detailed Description
The invention provides an organic liquid hydrogen storage system of a high-efficiency coupling heat storage system and a use method thereof, and in order to make the advantages and the technical scheme of the invention clearer and more definite, the invention is further described below by combining specific embodiments.
As shown in fig. 1, the organic liquid hydrogen storage system of the high-efficiency coupling heat storage system comprises a storage unit 1, a hydrogenation reaction unit 2, a chemical heat storage unit 3 and an electric heating unit 4 which are sequentially connected from front to back.
The storage unit 1 is used for storing hydrogen, a hydrogen-lean organic liquid and a hydrogen-rich organic liquid, which are respectively stored by a hydrogen storage tank 5, a hydrogen-lean organic liquid storage tank 6 and a hydrogen-rich organic liquid storage tank 7. Wherein the hydrogen-depleted organic liquid and hydrogen are passed to a hydrogenation reaction unit. The hydrogen-rich organic liquid and hydrogen provided by the storage unit 1 enter the hydrogenation reaction unit 2; the hydrogenation reaction unit 2 reacts to generate hydrogen-rich organic liquid, the hydrogen-rich organic liquid returns to a hydrogen-rich organic liquid storage tank of the storage unit 1, and heat released by the reaction is absorbed by the heat conduction oil and stored in the chemical heat storage unit 3; the chemical heat storage unit 3 and the electric heating unit 4 work cooperatively to transport heat into the hydrogenation reaction unit when the apparatus is preheated or seasonal temperature compensation is performed.
The hydrogenation reaction unit 2 mainly comprises a hydrogenation reactor 8, preferably a fixed bed reactor, and the outer layer of the fixed bed reactor is wrapped by a heat conducting oil jacket 9.
The electric heating unit 4 mainly comprises equipment for heating heat conduction oil, and is a core component for performing system heat management. The chemical heat storage unit 3 is reasonably complemented with the electric heating unit 4, so that the heat load of the electric heating unit 4 can be reduced.
As a main innovation point of the present invention, the chemical heat storage unit 3 can store heat released from the hydrogenation reaction unit and supply the equipment with preheating and seasonal temperature compensation, thereby reducing the thermal load of electric heating and reducing the demand of external energy. And for chemical heat storage units it is specifically designed for the special case of the reaction of the invention. As shown in fig. 2.
When the chemical heat storage unit 3 needs heat to preheat the hydrogenation reactor or balance the seasonal temperature difference, the heat storage reactor 10 generates adsorption exothermic reaction and works as a system heat source; when the hydrogenation reaction unit 2 in the system stably works to release heat, the heat storage reactor 10 generates desorption endothermic reaction and works as a system cold source.
As shown in fig. 3 and 4, the chemical heat storage unit includes a heat storage reactor 10, a condenser 11, a water storage tank 12 and an evaporator 13 connected in sequence, a pump 14 is provided on a pipe connected between the heat storage reactor 10 and the condenser, the evaporator is connected with the heat storage reactor, and the four form a closed system; when the chemical heat storage unit stores heat, heat generated by the reaction in the hydrogenation reaction unit is led out through heat conduction oil and is led into the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor enters the water storage tank for storage after being condensed by the condenser; when the chemical heat storage unit releases heat, water stored in the water storage tank is pumped into the evaporator, becomes water vapor under the action of the evaporator, enters the heat storage reactor, and undergoes exothermic adsorption reaction with the heat storage material in the heat storage reactor, and the heat released by the reaction enters the heat conduction oil pipeline through heat exchange and heats subsequent equipment;
the invention further improves the structure of the heat storage reactor, the heat storage reactor comprises a reactor body, the top of the reactor body is designed into an arc shape a, and the aim of the design is that: the method has the advantages that the phenomenon that condensed liquid drops on the wall surface of the reactor drop into a reaction bed layer is avoided, the water desorption efficiency of the reactor is improved, the super-hydrophilic coating is coated on the wall surface in the reactor body, the contact angle of liquid is reduced, membranous condensation can be generated on the wall surface, the heat transfer coefficient is reduced, the further condensation of water vapor is inhibited, the temperature of the reactor can be better kept, and the water desorption efficiency is improved; a heat storage reaction bed layer and a heat conducting oil flow channel are arranged in the reactor body in a staggered manner, and the heat storage reaction bed layer c and the heat conducting oil flow channel d are separated by a cambered plate; the two sides of the reactor body are provided with groove parts serving as condensate water flow passages b, and the purpose of the design of the grooves is as follows: and the condensed water is discharged as soon as possible, so that the condensed water is prevented from contacting the bed layer, and the interference of the external low temperature to the high-temperature desorption process in the reactor is reduced.
Preferably, mgCl is used in the thermal storage reactor 10 2 Or CaCl 2 And the heat storage material is compounded with porous medium materials such as graphite, zeolite and the like and is filled in a reactor bed.
The organic liquid adopted by the system is N-ethyl carbazole organic hydrogen storage liquid, and the hydrogen-rich liquid is dodecahydro ethyl carbazole.
The main equipment of the hydrogenation reaction unit 2 is a fixed bed reactor, and 750mol/h hydrogen-deficient organic liquid and 100Nm are treated under the design working condition of the reactor 3 And/h hydrogen, wherein the exothermic power of the reactor is 230MJ/h, the outer layer of the reactor is wrapped by a heat conducting oil jacket 9, and the heat exchange efficiency is 95%.
The following describes a method for using the organic liquid hydrogen storage system of the high-efficiency coupling heat storage system.
The method comprises the following steps:
a. opening valves among the hydrogen storage tank, the hydrogen-lean organic liquid storage tank and the hydrogenation reactor, and introducing hydrogen and the hydrogen-lean organic liquid into the hydrogenation reactor;
b. the hydrogen-rich liquid generated by the reaction of the hydrogenation reaction unit returns to the hydrogen-rich organic liquid storage tank, and the heat generated by the reaction is exported through the heat conduction oil and is conveyed to the heat storage unit;
c. when the system needs heat to preheat the reactor or balance the seasonal temperature difference, the heat storage reactor generates adsorption exothermic reaction and works as a system heat source, and the specific working method comprises the following steps:
firstly, high-temperature heat conduction oil flows through the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor is condensed by the condenser and enters the water storage tank for storage;
d. when the hydrogenation reaction unit in the system stably works to release heat, the heat storage reactor generates desorption endothermic reaction and works as a system cold source, and the specific working method is as follows:
the water in the water storage tank is pumped into the evaporator, becomes water vapor in the evaporator, then enters the heat storage reactor to perform exothermic adsorption reaction with the heat storage material, and the released heat enters the heat conduction oil to heat subsequent equipment through heat exchange.
The desorption temperature of the hydrogenation reactor is 140-160 ℃, the adsorption temperature is 50-70 ℃, and MgCl is used for preparing the catalyst 2 The heat storage material was filled with 200kg and had a heat storage capacity of 197MJ. The chemical heat storage unit 3 is added, so that the energy efficiency of the system is improved, and the electricity consumption is reduced by 14.8%.
In summary, according to the organic liquid hydrogen storage system and the application method of the efficient coupling heat storage system, through recovering waste heat, the demand level of external energy sources is reduced, and the difficult problem of equipment lacking an external heat source in energy storage by applying an organic liquid hydrogen storage technology is solved.
The parts not described in the invention can be realized by referring to the prior art.
It is noted that any equivalent or obvious modification made by those skilled in the art under the teachings of this specification shall fall within the scope of this invention.
Claims (8)
1. An organic liquid hydrogen storage system of high-efficient coupling heat accumulation system, its characterized in that: the hydrogenation reaction device comprises a storage unit, a hydrogenation reaction unit, a chemical heat storage unit and an electric heating unit which are sequentially connected from front to back;
the storage unit is used for storing hydrogen, hydrogen-lean organic liquid and hydrogen-rich organic liquid, wherein the hydrogen-lean organic liquid and the hydrogen are introduced into the hydrogenation reaction unit;
the hydrogen-rich organic liquid generated by the reaction in the hydrogenation reaction unit is led into the storage unit, and the heat generated by the reaction is led out through heat conduction oil and is conveyed into a chemical heat storage unit connected with the heat conduction oil;
the chemical heat storage unit comprises a heat storage reactor, a condenser, a water storage tank and an evaporator which are sequentially connected, wherein the evaporator is connected with the heat storage reactor, and the heat storage reactor, the condenser, the water storage tank and the evaporator form a closed system; when the chemical heat storage unit stores heat, heat generated by the reaction in the hydrogenation reaction unit is led out through heat conduction oil and is led into the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor enters the water storage tank for storage after being condensed by the condenser; when the chemical heat storage unit releases heat, water stored in the water storage tank is pumped into the evaporator, becomes water vapor under the action of the evaporator, enters the heat storage reactor, and undergoes exothermic adsorption reaction with the heat storage material in the heat storage reactor, and the heat released by the reaction enters the heat conduction oil pipeline through heat exchange and heats subsequent equipment;
the heat storage reactor comprises a reactor body, wherein the top of the reactor body is of an arc-shaped design, the wall surface in the reactor body is coated with a super-hydrophilic coating, heat storage reaction beds and heat conducting oil flow channels are arranged in the reactor body in a staggered manner, and the heat storage reaction beds and the heat conducting oil flow channels are separated by an arc-shaped plate; groove parts are arranged on two sides of the reactor body and used as condensate water flow passages;
the heat storage material in the heat storage reaction bed layer is MgCl 2 Composites with graphite, zeolites, or CaCl 2 And graphite and zeolite.
2. The organic liquid hydrogen storage system of an efficient coupling heat storage system of claim 1 wherein: the electric heating unit is used for heating heat conduction oil.
3. The organic liquid hydrogen storage system of an efficient coupling heat storage system of claim 1 wherein: the hydrogenation reaction unit comprises a hydrogenation reactor, wherein the hydrogenation reactor is a fixed bed reactor, and the periphery of the fixed bed reactor is wrapped with a heat conducting oil jacket.
4. The organic liquid hydrogen storage system of an efficient coupling heat storage system of claim 1 wherein: the storage unit comprises a hydrogen storage tank for storing hydrogen, a hydrogen-lean organic liquid storage tank for storing hydrogen-lean organic liquid and a hydrogen-rich organic liquid storage tank for storing hydrogen-rich organic liquid.
5. The organic liquid hydrogen storage system of an efficient coupling heat storage system of claim 1 wherein: a pump is arranged on the pipe connected between the thermal storage reactor and the condenser.
6. The organic liquid hydrogen storage system of an efficient coupling heat storage system of claim 1 wherein: the super-hydrophilic coating is SiO 2 A base super hydrophilic coating.
7. The method of using an organic liquid hydrogen storage system of a high efficiency coupling heat storage system according to any one of claims 1 to 6, comprising the steps of, in order:
a. introducing hydrogen and a hydrogen-deficient organic liquid into the hydrogenation reaction unit through the storage unit;
b. the hydrogen-rich liquid generated by the reaction of the hydrogenation reaction unit returns to the storage unit, and the heat generated by the reaction is exported through the heat conduction oil and is conveyed to the heat storage unit;
c. when the system needs heat to preheat the reactor or balance the seasonal temperature difference, the heat storage reactor generates adsorption exothermic reaction and works as a system heat source, and the specific working method comprises the following steps:
firstly, high-temperature heat conduction oil flows through the heat storage reactor, the heat storage reactor generates endothermic desorption reaction to generate water vapor, and the water vapor is condensed by the condenser and enters the water storage tank for storage;
d. when the hydrogenation reaction unit in the system stably works to release heat, the heat storage reactor generates desorption endothermic reaction and works as a system cold source, and the specific working method is as follows:
the water in the water storage tank is pumped into the evaporator, becomes water vapor in the evaporator, then enters the heat storage reactor to perform exothermic adsorption reaction with the heat storage material, and the released heat enters the heat conduction oil to heat subsequent equipment through heat exchange.
8. The method for using the organic liquid hydrogen storage system of the high-efficiency coupling heat storage system according to claim 7, wherein the method comprises the following steps: the desorption temperature of the thermal storage reactor is 140-160 ℃ and the adsorption temperature is 50-70 ℃.
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| CN115259079B true CN115259079B (en) | 2024-04-12 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503408A (en) * | 2018-05-22 | 2018-09-07 | 机科发展科技股份有限公司 | A kind of condensation collection system in tunnel type fermentation warehouse |
| CN112886040A (en) * | 2021-01-18 | 2021-06-01 | 上海簇睿低碳能源技术有限公司 | Utilize organic liquid to store up hydrogen energy power generation system |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503408A (en) * | 2018-05-22 | 2018-09-07 | 机科发展科技股份有限公司 | A kind of condensation collection system in tunnel type fermentation warehouse |
| CN112886040A (en) * | 2021-01-18 | 2021-06-01 | 上海簇睿低碳能源技术有限公司 | Utilize organic liquid to store up hydrogen energy power generation system |
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