CN109595961B - Thermochemical energy storage device - Google Patents
Thermochemical energy storage device Download PDFInfo
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- CN109595961B CN109595961B CN201710919539.0A CN201710919539A CN109595961B CN 109595961 B CN109595961 B CN 109595961B CN 201710919539 A CN201710919539 A CN 201710919539A CN 109595961 B CN109595961 B CN 109595961B
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 86
- 230000003647 oxidation Effects 0.000 claims abstract description 80
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 69
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- 238000005338 heat storage Methods 0.000 claims abstract description 66
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 58
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
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- 229910052751 metal Inorganic materials 0.000 claims description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 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
- Y02E60/14—Thermal energy storage
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Sorption Type Refrigeration Machines (AREA)
Abstract
The invention discloses a thermochemical energy storage device which comprises a particle transportation device, a thermal decomposition reactor, a carbothermic reduction reactor, an oxidation reactor and an oxidation heat exchanger. The high-valence metal oxide absorbs solar heat energy in a thermal decomposition reactor and a carbothermic reduction reactor, two reduction reactions are continuously carried out, the reduced metal oxide enters an oxidation reactor and an oxidation heat exchanger, two oxidation reactions are continuously carried out, and solar energy is stored in the form of combustible gas and chemical energy of the reduced metal oxide. The four-step metal oxide energy storage mode of coupling the metal oxide redox reaction and the metal oxide carbothermic reduction-hydrolysis hydrogen production reaction not only can effectively improve the energy storage density, but also can effectively solve the defects of poor peak regulation capability, limited product diversified development, low fluctuation energy and the like caused by single design, small heat storage capacity and limited heat storage form of the conventional high-temperature solar heat storage system.
Description
Technical Field
The invention relates to the technical field of energy, in particular to a thermochemical energy storage device.
Background
The land surface area of China receives solar radiation energy equivalent to 4.9 trillion tons of standard coal every year, and areas such as Qinghai-Tibet plateau, North Gansu, North Ningxia and south Xinjiang are the areas with the most abundant solar energy resources, and the development potential exceeds 85 trillion kilowatt-hours/year. Therefore, the solar energy reserves are abundant and occupy an important position in the utilization of renewable energy sources in China. Compared with solar photovoltaic power generation, the solar photovoltaic power generation has a heat storage system, and the solar photovoltaic power generation depends on a heat storage system device with relatively low cost, can realize continuous, stable and controllable power output, has relatively flexible peak regulation capacity, and is a comprehensive link of future multi-energy subsystems.
Solar energy heat storage occupies an important position in a multi-energy complementary system, particularly solar thermal power generation replaces thermal power in the multi-energy complementary integrated system to serve as the roles of power peak regulation and clean energy, and has a positive effect on improving an energy structure. The output of the photo-thermal power generation system with energy storage is closely related to the configuration size of the heat storage capacity except the solar irradiation resource and the electric network charge, but the current high-temperature solar heat storage system has single design, only considers one thermochemical reaction, has small heat storage capacity and single heat storage form, and limits the diversified development of the utilization approach.
In solar thermal power generation, high-temperature heat storage is divided into sensible heat storage, latent heat storage and thermochemical heat storage according to different heat storage mechanisms, and compared with other two heat storage modes, the chemical energy heat storage has the advantages of large energy storage density, high energy storage temperature, long energy storage period, small heat loss, suitability for long-distance transportation and the like. At present, the research of middle-high temperature solar thermochemistry is mainly carried out to prepare clean fuel hydrogen, the hydrogen is prepared by two-step hydrolysis of metal oxide, and the temperature required by the first-step thermal decomposition of the metal oxide is high, so that the first-step thermal decomposition of the metal oxide is difficult to match with a heat source. Furthermore, metals and oxygen are easily complexed, and the resulting product requires rapid cooling for separation purposes and to avoid reoxidation, but rapid cooling results in significant solar heat loss.
Disclosure of Invention
The invention aims to provide a thermochemical energy storage device with large heat storage capacity, high energy storage density and diversified heat storage forms, aiming at the problems of single design, small heat storage capacity and single heat storage form of the existing high-temperature solar energy heat storage system.
The purpose of the invention is realized by the following technical scheme:
the invention provides a thermochemical energy storage device, comprising:
a particle transport device for transporting the heat storage particles;
the thermal decomposition reactor is internally provided with a slope for connecting an inlet and an outlet of the thermal decomposition reactor, and the inlet of the thermal decomposition reactor is connected with the outlet of the particle conveying device;
the first condenser is arranged on the thermal decomposition reactor and used for converging solar energy and acting the solar energy on a slope;
the inlet of the carbothermic reactor is connected with the outlet of the thermal decomposition reactor, and carbonaceous raw materials are arranged in the carbothermic reactor;
the two ends of the oxidation heat exchanger are respectively connected with the outlet of the carbothermic reduction reactor and the inlet of the particle conveying device;
the heat storage particles enter the thermal decomposition reactor and move downwards along the slope under the action of gravity; the heat storage particles comprise high-valence metal oxide particles, wherein the high-valence metal oxide particles react under the action of solar energy collected by the first condenser, are converted into low-valence metal oxide particles, and store heat energy;
the heat storage particles enter the carbon thermal reduction reactor from the thermal decomposition reactor to perform reduction reaction with the carbon raw material, wherein the low-valence metal oxide particles are converted into metal simple substance particles to further store heat energy;
the heat storage particles enter the oxidation heat exchanger from the carbon thermal reduction reactor, at least part or all of the heat storage particles are subjected to oxidation reaction to generate high-valence metal oxide particles, and heat is released;
the heat storage particles enter the particle transport device from the oxidation heat exchanger and are transported to the thermal decomposition reactor.
Preferably, the surface of the slope in the thermal decomposition reactor is formed with a plurality of wave-shaped protrusions in the width direction, and the heat storage particles move in the corrugated grooves formed between the adjacent protrusions, thereby increasing the residence time of the high valence metal oxide in the thermal decomposition reactor and enabling the reduction reaction of the high valence metal oxide to be more complete.
Preferably, the thermochemical energy storage device provided by the invention further comprises: a first particle storage tank connected between the particle transport device and the thermal decomposition reactor; a second particle storage tank connected between the thermal decomposition reactor and the carbothermic reactor; the third particle storage tank is connected and arranged between the carbothermic reactor and the oxidation heat exchanger; the first particle storage tank, the second particle storage tank and the third particle storage tank are used for temporarily storing heat storage particles.
Preferably, the thermal decomposition reactor is connected with an oxidation heat exchanger; in the thermal decomposition reactor, when the high valence metal oxide particles are converted into low valence metal oxide particles, the released oxygen is supplied to the oxidation heat exchanger; in the oxidation heat exchanger, the heat storage particles and oxygen supplied by the thermal decomposition reactor generate oxidation reaction heat.
Preferably, the thermochemical energy storage device provided by the invention further comprises: the oxygen storage tank is connected and arranged between the thermal decomposition reactor and the oxidation heat exchanger; the vacuum pump is connected and arranged between the thermal decomposition reactor and the oxygen storage tank; the oxygen storage tank is used for temporarily storing oxygen; the vacuum pump is used for extracting gas from the thermal decomposition reactor and sending the gas into the oxygen storage tank.
Preferably, the thermochemical energy storage device provided by the invention further comprises: a first heat regenerator and an air pump; a tail gas channel and an air channel are arranged in the first heat regenerator, the tail gas channel is connected with the oxidation heat exchanger, one end of the air channel is connected with the air pump, and the other end of the air channel is connected with the oxidation heat exchanger; the tail gas generated by the oxidation heat exchanger passes through the tail gas channel, and the air pumped by the air pump is heated by the tail gas and enters the oxidation heat exchanger.
Still further, the thermochemical energy storage apparatus provided by the present invention preferably further comprises an oxidation reactor; the oxidation reactor is connected and arranged between the carbothermic reduction reactor and the oxidation heat exchanger; the oxidation reactor is provided with a water vapor inlet for introducing water vapor; the heat storage particles enter the oxidation reactor from the carbothermic reduction reactor, wherein the metal simple substance particles react with the water vapor to generate low-valence metal oxide particles and first combustible gas; the heat storage particles enter the oxidation heat exchanger from the oxidation reactor.
Preferably, the thermochemical energy storage device provided by the invention further comprises a second heat regenerator and a water pump, wherein a combustible gas channel and a water vapor channel are arranged in the second heat regenerator, the combustible gas channel is connected with the carbothermic reduction reactor, one end of the water vapor channel is connected with the water pump, and the other end of the water vapor channel is connected with a water vapor inlet of the oxidation reactor; the first combustible gas generated by the carbothermic reactor passes through the combustible gas channel, the feed water of the water pump is heated and evaporated by the first combustible gas, and the generated steam enters the oxidation reactor through the steam inlet.
Preferably, the thermochemical energy storage device provided by the invention further comprises a combustible gas storage tank, wherein the combustible gas storage tank is respectively connected with the carbothermic reduction reactor and the oxidation reactor; when the heat storage particles enter the carbothermic reduction reactor, the low-valence metal oxide particles and the carbonaceous raw material undergo a reduction reaction to be converted into metal simple substance particles, and a first combustible gas is generated at the same time and is sent into a combustible gas storage tank to be stored; when the heat storage particles enter the oxidation reactor, the metal simple substance particles react with the water vapor to generate low-valence metal oxide particles and second combustible gas, and the second combustible gas is sent to the combustible gas storage tank for storage.
In summary, compared with the prior art, the invention has the following technical effects:
1. the thermochemical energy storage device provided by the invention realizes a four-step metal oxide energy storage process by coupling the metal oxide redox reaction and the metal oxide carbothermic reduction-hydrolysis hydrogen production reaction, increases the heat storage energy of solar thermochemical energy, improves the output function of a power system, and stores solar energy in the form of thermochemical energy in reduced metal oxide particles and clean fuel hydrogen simultaneously, thereby realizing the diversified development of the thermochemical energy storage mode and providing convenient conditions for a multi-energy complementary integrated system.
2. The high-valence metal oxide pyrolysis reactor adopts a simple inclined plane type reactor, the device is simple, oxygen in the pyrolyzer is pumped by a vacuum pump, so that the oxygen partial pressure in the reactor is kept at a lower level, the reaction rate is improved, and meanwhile, the inclined plane adopts a corrugated form, so that the retention time of metal oxide in the reactor is prolonged, and the metal oxide is completely reacted.
3. Compared with the two-step metal oxide hydrolysis hydrogen production, the metal oxide carbon thermal reduction-hydrolysis hydrogen production has the advantages of low reaction temperature, automatic hydrogen separation and the like, and can avoid the problems of difficult matching of the heat source of the two-step metal oxide hydrolysis hydrogen production, easy compounding of metal and oxygen, difficult separation and the like.
4. From the angle of the second law of thermodynamics, the solar energy metal oxide particle four-step thermochemical energy storage method realizes the cascade utilization of chemical energy and reduces the energy consumption
And (4) loss.
Therefore, the solar metal oxide four-step thermochemical energy storage process realized by the thermochemical energy storage device provided by the invention can not only avoid the problems of higher temperature, easy recombination of products and the like required by hydrogen production of metal oxide, but also reduce energy loss and improve energy storage density, and in addition, can effectively solve the defects of poor peak regulation capability, limited diversified development of products, low fluctuation capability and the like caused by single design, small heat storage capacity and limited heat storage form of the conventional high-temperature solar energy storage system.
Drawings
FIG. 1 is a schematic view of a thermochemical energy storage device according to an embodiment of the invention;
FIG. 2 is a schematic view of a ramp disposed in a thermal decomposition reactor in a thermochemical energy storage device according to an embodiment of the invention.
Description of reference numerals:
1-a first particle reservoir; 2-slope; 3-a thermal decomposition reactor; 4-a first condenser; 5-a second particle reservoir; 6-a second condenser; 7-carbothermic reactor; 8-a second regenerator; 9-a combustible gas storage tank; 10-an oxidation reactor; 11-a third particle reservoir; 12-a first heat regenerator; 13-a valve; 14-an oxygen storage tank; 15-a vacuum pump; 16-an oxidation heat exchanger; 17-a particle transport device; 18-a heat exchange conduit; 19-a water pump; 20-air pump.
Detailed Description
(constitution of thermochemical energy storage apparatus)
The invention is further described below with reference to the accompanying drawings, fig. 1 being a schematic view of a thermochemical energy storage device.
As shown in fig. 1, the thermochemical energy storage device comprises at least: a thermal decomposition reactor 3, a carbothermic reactor 7, an oxidation heat exchanger 16, and a particle transport device 17. The particle transport device 17 is used for transporting heat storage particles. A slope 2 connecting the inlet and the outlet of the thermal decomposition reactor 3 is provided in the thermal decomposition reactor 3, and the inlet of the thermal decomposition reactor 3 is connected to the outlet of the particle transport device 17. A first condenser 4 is arranged on the thermal decomposition reactor 3, and the first condenser 4 converges solar energy and acts on the slope 2; the inlet of the carbothermic reduction reactor 7 is connected with the outlet of the thermal decomposition reactor 3, and carbonaceous raw materials are arranged in the carbothermic reduction reactor 7; both ends of the oxidation heat exchanger 16 are connected to the outlet of the carbothermic reactor 7 and the inlet of the particle transporting device 17, respectively.
Preferably, the thermochemical energy storage device further comprises an oxidation reactor 10, the oxidation reactor 10 is connected and arranged between the carbothermic reduction reactor 7 and the oxidation heat exchanger 16, and the oxidation reactor 7 is provided with a water vapor inlet.
Further preferably, the thermal decomposition reactor 3 is connected to an oxidation heat exchanger 16.
In addition, the thermochemical energy storage device can also include several storage tanks for temporarily storing heat storage particles or for temporarily storing gas, including: a first particle tank 1 connected between the particle transporting means 17 and the thermal decomposition reactor 3; a second particle tank 5 connected between the thermal decomposition reactor 3 and the carbothermic reactor 7; a third particle storage tank 11 connected and disposed between the carbothermic reactor 7 and the oxidation heat exchanger 16; the first particle storage tank 1, the second particle storage tank 5 and the third particle storage tank 11 are all used for temporarily storing heat storage particles. The thermochemical energy storage device further comprises: an oxygen storage tank 14 connected between the thermal decomposition reactor 3 and the oxidation heat exchanger 16; a vacuum pump 15 connected between the thermal decomposition reactor 3 and the oxygen storage tank 14. In addition, the method also comprises the following steps: and a combustible gas storage tank 9 respectively connected with the carbothermic reactor 7 and the oxidation reactor 10.
(operation mode of thermochemical energy storage apparatus)
The operation of the thermochemical energy storage device configured as described above will be exemplified.
The heat storage particles enter the thermal decomposition reactor 3 from the first particle storage tank 1, the thermal decomposition reactor 3 is a triangular cavity, and the heat storage particles move downwards along the slope 2 under the action of gravity. The heat storage particles comprise particles of a higher valence metal oxide, in this embodiment, tricobalt tetroxide (Co)3O4) For example. High valence metal oxide Co3O4The particles are subjected to a reduction reaction under the action of the solar energy collected by the first condenser 4 to generate a low-valence metal oxide CoO and oxygen, and the solar energy heat is converted into a chemical energy form for storage, as shown in the reaction equation (1).
2Co3O4→6CoO+O2 (1)
The oxygen generated by the above reaction is stored in an oxygen storage tank 14 through a vacuum pump 15, and the generated low-valence metal oxide CoO enters a second particle storage tank 5 through a particle outlet of the thermal decomposition reactor 3 to be used as a raw material for the carbothermic reduction reaction of the metal oxide.
The heat storage particles enter the carbothermic reduction reactor 7 from the second particle storage tank 5, and are subjected to reduction reaction with coke, natural gas or other carbonaceous raw materials to generate metal simple substances or metal oxides with lower valence states and combustible gas. The carbothermic reduction reaction of the metal oxide in this step is an endothermic reaction, and therefore, the carbothermic reduction reactor 7 may be provided with the second condenser 6, and the sunlight focused by the second condenser 6 is irradiated in the carbothermic reduction reactor 7 to provide the heat required for the reaction. The carbonaceous material in the present embodiment is methane (CH)4) For example, the low valence state metal oxide CoO particles are converted into elemental metal Co particles, and further the solar heat energy is converted into chemical energy form for storage, as shown in reaction equation (2):
CoO+CH4→Co+CO+2H2 (2)
the heat storage particles enter the oxidation reactor 10 from the carbothermic reduction reactor 7 to perform a displacement reaction with the water vapor, and the high-temperature water vapor oxidizes the metal oxide or the metal simple substance with lower valence state into the metal oxide with lower valence state, and simultaneously generates cleanHydrogen is the fuel. In this embodiment, the elemental metal Co particles react with water vapor to form reduced-valence metal oxide CoO particles and a first combustible gas H2As shown in equation (3):
Co+H2O→CoO+H2 (3)
the hydrogen generated by the above reaction and the combustible gas generated in the carbothermic reactor 7 enter the combustible gas tank 9, and the low valence state metal oxide CoO particles enter the third particle storage tank 11 for storage.
The heat storage particles enter the oxidation heat exchanger 16 from the third particle storage tank 11, and at least part or all of the CoO particles are subjected to oxidation reaction with air flowing in from the oxygen storage tank 14 in the oxidation heat exchanger 16 to release heat, as shown in the reaction equation (4);
6CoO+O2→2Co3O4 (4)
the heat storage particles from the oxidation heat exchanger 16 enter the particle transport device 17 and are transported to the first particle storage tank 1 for temporary storage, thereby completing the heat storage particle cycle.
In the operation process of the thermochemical energy storage device, the second particle storage tank 5 and the third particle storage tank 11 are arranged, so that the oxidation heat release reaction in the oxidation heat exchanger 16 can be continuously and stably operated, and the solar energy in the day can be stored to be used at night. In addition, the combustible gas stored in the combustible gas storage tank 9 is high-grade solar fuel, can be efficiently utilized by means of advanced acting equipment such as gas-steam combined cycle and the like, can be integrated with a chemical production process, realizes diversified output of products, is used in a coupling mode, improves the heat storage capacity of the system, and increases the adjusting capacity.
(further preferred embodiment of constitution of thermochemical energy storage apparatus)
Further preferred embodiments of the configuration of the thermochemical energy storage device and technical effects thereof will be explained below.
Further preferably, in order to complete the reaction of the high-valence metal oxide, a plurality of wavy line-shaped projections are formed on the surface of the slope 2 provided in the thermal decomposition reactor 3 in the width direction, as shown in FIG. 2. So that the residence time of the higher-valence metal oxide in the thermal decomposition reactor 3 can be increased to achieve the purpose of allowing the higher-valence metal oxide to react completely. Meanwhile, the oxygen generated in the thermal decomposition reactor 3 is pumped out using the vacuum pump 15, so that the oxygen partial pressure is maintained at a stable low level, and the reaction rate is increased.
In order to better control the heat release rate in the oxidation heat exchanger 16, especially for the time period without solar energy at night, oxygen-enriched air obtained by mixing air in the external environment with pure oxygen is introduced through the gas inlet of the oxidation heat exchanger 16, the oxygen in the air and the low-valence metal oxide perform an exothermic reaction, and unreacted gas is discharged from the gas outlet of the oxidation heat exchanger 16.
In addition, the thermochemical energy storage apparatus of the present invention may further include several regenerative structures, such as the first regenerator 12 and the air pump 20; a tail gas channel and an air channel are arranged in the first heat regenerator 12, the tail gas channel is connected with the oxidation heat exchanger 16, one end of the air channel is connected with the air pump, and the other end of the air channel is connected with the oxidation heat exchanger 16; the tail gas generated by the oxidation heat exchanger 16 passes through the tail gas channel, and the air pumped by the air pump 20 is heated by the tail gas and enters the oxidation heat exchanger 16. The medium steam input into the oxidation reactor 10 exchanges heat with the combustible gas exhausted from the oxidation reactor 10 and the carbothermic reduction reactor 7 in the heat regenerator 12, so that the temperature of the steam is increased, and the reaction rate is increased.
For another example: the system comprises a second heat regenerator 8 and a water pump 19, wherein a combustible gas channel and a steam channel are arranged in the second heat regenerator 8, the combustible gas channel is connected with the carbon thermal reduction reactor 7, one end of the steam channel is connected with the water pump 19, and the other end of the steam channel is connected with a steam inlet of the oxidation reactor 10; the first combustible gas produced by the carbothermic reactor 7 and the second combustible gas produced by the oxidation reactor 10 pass through the combustible gas channel, the feed water of the water pump is heated and evaporated by the first combustible gas and the second combustible gas, and the generated water vapor enters the oxidation reactor 10 through the water vapor inlet. The air input from the environment exchanges heat with the residual gas exhausted from the gas outlet of the oxidation heat exchanger 16 in the heat regenerator 8, so that the air temperature is increased, and the heat loss is reduced.
In the above embodiment, the high-valence metal oxide includes one or more of high-valence oxides of iron, manganese, cobalt, copper, barium, or the like, or multi-metal oxides. The working medium heated by the oxidation heat exchanger comprises one or more of air, water, hydrogen, helium, nitrogen, carbon dioxide and the like. The skilled person can select the above according to the needs, which does not limit the technical solution of the present invention.
Compared with the prior art, the solar energy thermochemical heat storage system has the advantages that the four-step metal oxide energy storage mode of coupling the metal oxide redox reaction and the metal oxide carbothermic reduction-hydrolysis hydrogen production reaction is adopted, the solar energy is stored in the reduced metal oxide particles and the clean fuel hydrogen simultaneously in the form of thermochemical energy, the diversified development of the thermochemical energy storage mode is realized, and the convenient condition is provided for the coupling of a multi-energy complementary integrated system. In addition, the metal oxide carbon thermal reduction-hydrolysis hydrogen production is carried out in a medium temperature environment, and the method has the advantages of low reaction temperature, automatic hydrogen separation and the like, and can avoid the problem of hydrogen production by two-step hydrolysis of the metal oxide. Finally, from the perspective of the second law of thermodynamics, the thermochemical energy storage device of the invention realizes the cascade utilization of chemical energy, and reduces the energy consumption
And (4) loss.
It will be appreciated by those of ordinary skill in the art that in the embodiments described above, numerous technical details are set forth in order to provide a better understanding of the present application. However, the technical solutions claimed in the claims of the present application can be basically implemented without these technical details and various changes and modifications based on the above-described embodiments, and thus, in practical applications, the above-described embodiments may be variously changed in form and detail without departing from the spirit and scope of the present invention.
Claims (9)
1. A thermochemical energy storage device, comprising:
a particle transport device for transporting the heat storage particles;
a thermal decomposition reactor, wherein a slope connecting an inlet and an outlet of the thermal decomposition reactor is arranged in the thermal decomposition reactor, and the inlet of the thermal decomposition reactor is connected with the outlet of the particle conveying device;
the first condenser is arranged on the thermal decomposition reactor and used for converging solar energy and acting the solar energy on the slope;
the inlet of the carbon thermal reduction reactor is connected with the outlet of the thermal decomposition reactor, and a carbonaceous raw material is arranged in the carbon thermal reduction reactor;
the oxidation reactor is connected with the outlet of the carbothermic reduction reactor, and a steam inlet is formed in the oxidation reactor and used for introducing steam;
the two ends of the oxidation heat exchanger are respectively connected with the outlet of the oxidation reactor and the inlet of the particle conveying device;
the heat storage particles enter the thermal decomposition reactor and move downwards along the slope under the action of gravity; the heat storage particles comprise high-valence metal oxide particles, wherein the high-valence metal oxide particles react under the action of the solar energy collected by the first condenser, are converted into low-valence metal oxide particles, and store heat energy;
the heat storage particles enter the carbon thermal reduction reactor from the thermal decomposition reactor to perform reduction reaction with the carbon raw material, wherein the low-valence metal oxide particles are converted into metal simple substance particles to further store heat energy;
the heat storage particles enter the oxidation reactor from the carbothermic reduction reactor, wherein the metal simple substance particles react with water vapor to generate low-valence metal oxide particles and second combustible gas;
the heat storage particles enter the oxidation heat exchanger from the oxidation reactor, and at least part or all of the heat storage particles are subjected to oxidation reaction to generate high-valence metal oxide particles so as to release heat;
the heat storage particles enter the particle transport device from the oxidation heat exchanger and are transported to the thermal decomposition reactor.
2. The thermochemical energy storage device of claim 1 wherein: the surface of the slope is provided with a plurality of wavy line-shaped bulges in the width direction, and the heat storage particles move in corrugated grooves formed between the adjacent bulges.
3. The thermochemical energy storage device of claim 1 wherein: the thermochemical energy storage device further comprises:
a first particle storage tank connectively disposed between the particle transport device and the thermal decomposition reactor;
a second particle storage tank connected between the thermal decomposition reactor and the carbothermic reactor;
a third particle storage tank connected and arranged between the carbothermic reactor and the oxidation heat exchanger;
the first particle storage tank, the second particle storage tank and the third particle storage tank are used for temporarily storing the heat storage particles.
4. The thermochemical energy storage device of claim 1 wherein:
the thermal decomposition reactor is connected with the oxidation heat exchanger;
in the thermal decomposition reactor, while the high valence metal oxide particles are converted into low valence metal oxide particles, the released oxygen is supplied to the oxidation heat exchanger;
in the oxidation heat exchanger, the heat storage particles and the oxygen supplied by the thermal decomposition reactor generate oxidation reaction heat.
5. The thermochemical energy storage device of claim 4 wherein: the thermochemical energy storage device further comprises:
the oxygen storage tank is connected and arranged between the thermal decomposition reactor and the oxidation heat exchanger;
a vacuum pump connected between the thermal decomposition reactor and the oxygen storage tank;
the oxygen storage tank is used for temporarily storing oxygen;
and the vacuum pump is used for extracting gas from the thermal decomposition reactor and sending the gas into the oxygen storage tank.
6. The thermochemical energy storage device of claim 1 wherein: the thermochemical energy storage device also comprises a first heat regenerator and an air pump;
a tail gas channel and an air channel are arranged in the first heat regenerator, the tail gas channel is connected with the oxidation heat exchanger, one end of the air channel is connected with the air pump, and the other end of the air channel is connected with the oxidation heat exchanger;
and tail gas generated by the oxidation heat exchanger passes through the tail gas channel, and air pumped by the air pump is heated by the tail gas and enters the oxidation heat exchanger.
7. The thermochemical energy storage device of claim 1 wherein: the thermochemical energy storage device further comprises a second heat regenerator and a water pump, wherein a combustible gas channel and a steam channel are arranged in the second heat regenerator, the combustible gas channel is connected with the carbothermic reduction reactor, one end of the steam channel is connected with the water pump, and the other end of the steam channel is connected with a steam inlet of the oxidation reactor;
the first combustible gas generated by the carbothermic reactor passes through the combustible gas channel, the feed water of the water pump is heated and evaporated by the first combustible gas and the second combustible gas, and the generated water vapor enters the oxidation reactor through the water vapor inlet.
8. The thermochemical energy storage device of claim 1 wherein: the thermochemical energy storage device also comprises a combustible gas storage tank, and the combustible gas storage tank is respectively connected with the carbothermic reduction reactor and the oxidation reactor;
when the heat storage particles enter the carbothermic reduction reactor, the low-valence metal oxide particles and the carbonaceous raw material undergo a reduction reaction to be converted into metal simple substance particles, and a first combustible gas is generated at the same time and is sent into the combustible gas storage tank to be stored;
when the heat storage particles enter the oxidation reactor, the metal simple substance particles react with the water vapor to generate low-valence metal oxide particles and second combustible gas, and the second combustible gas is sent into the combustible gas storage tank to be stored.
9. The thermochemical energy storage device of claim 1 wherein: the thermochemical energy storage device also comprises a combustible gas storage tank, and the combustible gas storage tank is connected with the carbothermic reduction reactor;
when the heat storage particles enter the carbothermic reduction reactor, the low-valence metal oxide particles and the carbonaceous raw material undergo a reduction reaction to be converted into metal simple substance particles, and a first combustible gas is generated at the same time and is sent into the combustible gas storage tank to be stored.
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