CN113701368B - Calcium hydroxide thermochemical energy storage system and application method thereof - Google Patents
Calcium hydroxide thermochemical energy storage system and application method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 153
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims abstract description 32
- 239000000920 calcium hydroxide Substances 0.000 title claims abstract description 32
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000010248 power generation Methods 0.000 claims abstract description 172
- 238000000498 ball milling Methods 0.000 claims abstract description 83
- 239000012530 fluid Substances 0.000 claims abstract description 45
- 239000011575 calcium Substances 0.000 claims abstract description 38
- 238000003860 storage Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- 239000002918 waste heat Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S60/00—Arrangements for storing heat collected by solar heat collectors
- F24S60/20—Arrangements for storing heat collected by solar heat collectors using chemical reactions, e.g. thermochemical reactions or isomerisation reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/28—Moving reactors, e.g. rotary drums
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
- F01D15/10—Adaptations for driving, or combinations with, electric generators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
- F03G6/00—Devices for producing mechanical power from solar energy
- F03G6/06—Devices for producing mechanical power from solar energy with solar energy concentrating means
- F03G6/065—Devices for producing mechanical power from solar energy with solar energy concentrating means having a Rankine cycle
- F03G6/067—Binary cycle plants where the fluid from the solar collector heats the working fluid via a heat exchanger
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/028—Steam generation using heat accumulators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22D—PREHEATING, OR ACCUMULATING PREHEATED, FEED-WATER FOR STEAM GENERATION; FEED-WATER SUPPLY FOR STEAM GENERATION; CONTROLLING WATER LEVEL FOR STEAM GENERATION; AUXILIARY DEVICES FOR PROMOTING WATER CIRCULATION WITHIN STEAM BOILERS
- F22D1/00—Feed-water heaters, i.e. economisers or like preheaters
- F22D1/003—Feed-water heater systems
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S50/00—Arrangements for controlling solar heat collectors
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- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
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Abstract
The invention discloses a calcium hydroxide thermochemical energy storage system and an application method thereof, wherein the calcium hydroxide thermochemical energy storage system comprises a tower-type solar heat collection device, a rotary ball-milling energy storage device and a steam Rankine power generation device; the tower type solar heat collecting device comprises a working medium fluid pump and a tower type solar heat collector; the rotary ball milling energy storage device comprises a CaO storage tank, Ca (OH)2A storage tank and a rotary ball milling reactor; the steam Rankine power generation device comprises a steam Rankine turbine, a steam power generation condenser, a steam power generation water pump, a steam power generation gate valve, a first steam power generation heat exchanger and a second steam power generation heat exchanger which are sequentially connected through a circulating pipeline; the steam Rankine power generation device also comprises a water treatment device; the system also includes a backup heat source device. The thermochemical energy storage system adopted by the system is Ca (OH)2And CaO stores energy through interconversion between heat energy and chemical energy, and three heat sources are flexibly distributed and adjusted, so that the solar thermal power station can continuously and efficiently operate.
Description
Technical Field
The invention belongs to the field of solar power generation, relates to a thermochemical energy storage system, and particularly relates to a calcium hydroxide thermochemical energy storage system and an application method thereof.
Background
Solar power generation has the advantages of wide source, no environmental pollution and the like, and is an ideal clean energy source capable of replacing fossil fuels. However, solar energy has characteristics of intermittency and instability, so that the energy is difficult to supply continuously and stably. Therefore, research in the field of energy storage science is urgently needed, wherein high-temperature energy storage is an efficient and potential technology for solving the problems of intermittency and instability of renewable energy sources. Among three main heat storage modes of sensible heat energy storage, latent heat energy storage and thermochemical energy storage, the thermochemical energy storage stores heat energy by utilizing reversible heat absorption and release reaction, has the remarkable advantages of high energy storage density, high reaction temperature, small long-term heat storage loss and the like, makes up the defects of other energy storage modes, and can effectively solve the problems of energy conversion, storage and regeneration. Ca (OH)2The CaO system is an ideal thermochemical energy storage system and has the remarkable advantages of large energy storage density (437 kWh/m 3), no toxicity, good safety, wide and cheap raw material sources, no side reaction and high reaction temperature (450-600 ℃), so that Ca (OH)2the/CaO system is used for high-temperature thermochemical energy storage in solar energy, and can well solve the problem that the power generation of a high-temperature solar thermal power station cannot be continuously and efficiently operated. For Ca (OH)2The research of the/CaO system for thermochemical energy storage is in the initial stage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention combines solar power generation with Ca (OH)2CaO thermochemical energy storage system and steam Rankine power generation system are combined, and a Ca (OH) -based system capable of continuously and stably running is provided2The CaO thermal chemical energy storage solar photo-thermal power generation application system effectively solves the problem of continuous solar power generation.
In order to achieve the above object, the present invention provides a calcium hydroxide thermochemical energy storage system having the following features: the system comprises a tower-type solar heat collection device, a rotary ball-milling energy storage device and a steam Rankine power generation device;
the tower type solar heat collection device comprises a working medium fluid pump and a tower type solar heat collector; the rotary ball-milling energy storage device comprises a CaO storage tank, Ca (OH)2A storage tank and a rotary ball milling reactor; the rotary ball milling reactor comprises a solidA reaction channel with a solid particle feeding port, a solid particle discharging port, a steam inlet and a steam outlet, and a heat exchange channel with a lower end lower inlet, a lower end upper inlet, an upper end lower outlet and an upper end upper outlet;
the working medium fluid pump, the tower type solar heat collector and the lower inlet at the lower end of the rotary ball-milling reactor are sequentially connected through a pipeline to form a solar heat supply path; ca (OH)2The storage tank is connected with a solid particle feeding port of the rotary ball-milling reactor through a pipeline, and a solid particle discharging port is connected with the CaO storage tank through a pipeline to form an energy storage path;
the steam Rankine power generation device comprises a steam Rankine turbine, a steam power generation condenser, a steam power generation water pump, a steam power generation gate valve, a first steam power generation heat exchanger and a second steam power generation heat exchanger which are sequentially connected through a circulation pipeline to form a power generation circulation path; an upper outlet at the upper end of the rotary ball-milling reactor, a second steam power generation heat exchanger and a first steam power generation heat exchanger are sequentially connected through a pipeline to form a first energy storage power generation heat source path; the tower type solar heat collector, the second steam power generation heat exchanger and the first steam power generation heat exchanger are also sequentially connected through a pipeline to form a second energy storage power generation heat source path; an energy storage heating gate valve is arranged between the tower type solar thermal collector and the lower inlet of the lower end of the rotary ball-milling reactor, and an energy storage direct power generation gate valve is arranged between the tower type solar thermal collector and the second steam power generation heat exchanger; the first steam-electricity heat exchanger is connected with the working medium fluid pump through an energy storage pipeline to form an energy storage working medium circulation path;
the steam Rankine power generation device also comprises a water treatment device; the steam outlet of the rotary ball-milling reactor, the first steam power generation heat exchanger, the water treatment device and the steam power generation condenser are sequentially connected through pipelines to form a third energy storage power generation heat source path; a steam waste heat power generation gate valve is arranged between a steam outlet of the rotary ball-milling reactor and the first steam power generation heat exchanger;
an energy storage gate valve is arranged between the working medium fluid pump and the tower type solar heat collector;
the system also includes a backup heat source device; the working medium fluid pump, the standby heat source device, the second steam power generation heat exchanger and the first steam power generation heat exchanger are sequentially connected through a pipeline to form a first energy-releasing power generation heat source path; an energy release direct power generation gate valve is arranged between the working medium fluid pump and the standby heat source device; an air extraction device is arranged in the middle of the steam Rankine turbine and is connected with a steam inlet of the rotary ball milling reactor through a pipeline to form a steam production path; an energy release steam gate valve is arranged between the steam Rankine turbine and the steam inlet; the CaO storage tank is connected with a solid particle feeding port of the rotary ball-milling reactor through a pipeline, and a solid particle discharging port is connected with a Ca (OH)2 storage tank through a pipeline to form an energy release path; the working medium fluid pump is connected with the upper inlet at the lower end of the rotary ball-milling reactor through a pipeline, and the lower outlet at the upper end of the rotary ball-milling reactor, the second steam power generation heat exchanger and the first steam power generation heat exchanger are sequentially connected through a pipeline to form a second energy-releasing power generation heat source path; an energy-releasing heat-exchange power generation gate valve is arranged between the working medium fluid pump and the upper inlet at the lower end; the first steam-electricity heat exchanger is connected with the working medium fluid pump through an energy release pipeline to form an energy release working medium circulation path.
Further, the present invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following features: the rotary ball-milling energy storage device also comprises an energy storage heat exchanger; the energy storage heat exchanger is a powder heat exchanger; the energy storage heat exchanger is arranged at Ca (OH)2Between the storage tank and the solid particle feeding port of the rotary ball-milling reactor, and between the solid particle discharging port and the CaO storage tank.
Further, the present invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following features: the rotary ball-milling energy storage device further comprises an energy releasing heat exchanger; the energy releasing heat exchanger is a powder heat exchanger; the energy-releasing heat exchanger is arranged between the CaO storage tank and the solid particle feed inlet of the rotary ball-milling reactor, and between the solid particle discharge outlet and Ca (OH)2Between the storage tanks.
Further, the invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following characteristics: the rotary ball-milling energy storage device also comprises a cyclone separator; the cyclone separator is arranged between a steam outlet of the rotary ball-milling reactor and a steam waste heat power generation gate valve; the bottom of the cyclone separator is connected with the energy storage heat exchanger through a pipeline.
Further, the present invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following features: wherein, Ca (OH)2The conveying of the solid particles and the CaO solid particles adopts a spiral feeding mode.
Further, the invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following characteristics: wherein, a plurality of steel balls are arranged in the rotary ball-milling reactor.
Further, the present invention provides a calcium hydroxide thermochemical energy storage system, which can also have the following features: wherein, the rotary ball-milling reactor adopts 314 stainless steel materials.
The invention also provides an application method of the calcium hydroxide thermochemical energy storage system, which is characterized in that: comprises an energy storage stage and an energy release stage; the energy storage stage comprises a solar heat supply path, an energy storage path, a first energy storage and power generation heat source path, a second energy storage and power generation heat source path, a third energy storage and power generation heat source path, a power generation circulating path and an energy storage working medium circulating path; the energy releasing stage comprises a first energy releasing and power generating heat source path, a power generating circulation path, a steam production path, an energy releasing path, a second energy releasing and power generating heat source path and an energy releasing working medium circulation path.
Further, the invention provides an application method of the calcium hydroxide thermochemical energy storage system, which can also have the following characteristics: wherein, the energy storage stage: when the solar radiation is sufficient, the solar radiation energy is converted into the heat energy of the fluid working medium through the tower type solar heat collector, the fluid working medium enters the rotary ball-milling reactor in a countercurrent manner through the energy storage heating gate valve to heat Ca (OH)2Solid particles are subjected to decomposition reaction; along with the deepening of the decomposition reaction, the decomposition product CaO solid particles enter a CaO storage tank; decomposition product H2O, preheating feed water of the steam Rankine cycle in the first steam power generation heat exchanger, and enabling the feed water to flow into a steam power generation condenser after entering a water treatment device so as to fully utilize heat; in addition, the fluid working medium passing through the tower type solar heat collector can also pass through the energy storage direct power generation gate valve and directly passes through the second steam power generation heat exchanger and the first steam power generation heat exchangerAnd the heat exchanger heats the steam Rankine cycle working medium to generate power.
Further, the invention provides an application method of the calcium hydroxide thermochemical energy storage system, which can also have the following characteristics: wherein, the energy releasing stage: when solar radiation is insufficient and energy is released for power generation for the first time, the energy-releasing direct power generation gate valve is opened, and working medium fluid passes through the standby heat source device and heats a steam Rankine cycle working medium through the second steam power generation heat exchanger and the first steam power generation heat exchanger to generate power; then opening an energy release steam gate valve to extract steam, leading the steam to enter a rotary ball milling reactor to carry out synthetic reaction with CaO solid particles flowing into the reactor, and releasing a large amount of heat; after the synthesis reaction starts, opening an energy-releasing heat exchange power generation gate valve, closing an energy-releasing direct power generation gate valve, switching the heat source of the working fluid from a standby heat source device to the heat released by the synthesis reaction in the rotary ball-milling reactor, and transferring the heat to a steam Rankine power generation device to realize power supply; after the initial release of energy, the synthesis product Ca (OH) is used2And the solid particle reaction waste heat is heated by the energy release heat exchanger and then the CaO solid particle flows are fed.
The invention has the beneficial effects that:
the invention utilizes thermochemical reversible reaction Ca (OH)2And the/CaO system realizes the storage and release of heat energy. The water vapor is used as a heat exchange medium and a reaction medium in the process. Ca (OH)2The CaO thermochemical energy storage system is combined with the steam Rankine power generation device to realize continuous power supply of electric energy in the absence of sunlight and smooth a power curve of a solar thermal power station. Simultaneously, Ca (OH) is effectively utilized2Decomposition reaction product H2Reaction waste heat carried by the O is recycled by utilizing the heat exchanger, so that comprehensive cascade utilization of energy is realized, and the efficiency of the energy storage system is obviously improved.
The invention provides a calcium hydroxide thermochemical energy storage method and solar heat collection driving
Reversible reaction, the energy received being stored in the form of chemical energy in its decomposition products CaO and H2And (4) in O. Has the advantages of high energy storage density,The solar thermal power station has the characteristics of high circulation efficiency, environmental friendliness, simple structure, flexible control under variable working conditions and reliable application, and can solve the problem that the solar thermal power station cannot continuously and efficiently operate during power generation.
The calcium hydroxide thermochemical energy storage application system provided by the invention is combined with the tower type solar heat collection device, the standby heat source device and the steam Rankine power generation device, the energy release process is started through the standby heat source device, the operation process can be effectively combined in various modes, and the applicability and the flexibility of the system are improved.
The calcium hydroxide thermochemical energy storage application system provided by the invention can regulate and control the energy storage and release by regulating and controlling the temperature and pressure of water vapor entering a reactor, namely Ca (OH)2CaO solid particle decomposition/synthesis reaction; the heat energy released by the reaction is more efficiently utilized by matching the level of the released heat energy. The low energy utilization rate caused by mismatching and nonuniformity of heat utilization caused by time or place is solved by the energy conversion utilization concept of thermal energy-chemical energy-thermal energy.
Drawings
FIG. 1 is a general schematic of the system of the present invention and its workflow;
FIG. 2 is a schematic diagram of the energy storage phase of the system workflow of the present invention;
FIG. 3 is a schematic diagram of the energy release stage of the system workflow of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
As shown in fig. 1, the invention provides a calcium hydroxide thermochemical energy storage system, which comprises a tower-type solar heat collection device, a rotary ball milling energy storage device and a steam rankine power generation device.
The tower type solar heat collector comprises a working medium fluid pump 1 and a tower type solar heat collector 5.
The rotary ball milling energy storage device comprises a CaO storage tank 10, Ca (OH)2A storage tank 9 and a rotary ball milling reactor 13.
The rotary ball milling reactor 13 includes a reaction channel having a solid particle feed inlet, a solid particle discharge outlet, a steam inlet and a steam outlet, and a heat exchange channel having a lower end lower inlet, a lower end upper inlet, an upper end lower outlet and an upper end upper outlet. Wherein, the rotary ball-milling reactor 13 adopts a ball-milling rotary mode to reduce agglomeration and sintering; a plurality of steel balls are arranged in the rotary ball-milling reactor 13, and the function of the steel balls is to promote the solid particles to be fully crushed and fully react; the rotary ball-milling reactor 13 is made of 314 stainless steel materials so as to meet the requirements of the particularity of medium-high temperature energy storage on the safety, reliability, maintainability, manufacturability and the like of the system.
The working medium fluid pump 1, the tower type solar heat collector 5 and the lower inlet of the lower end of the rotary ball-milling reactor 13 are connected in sequence through pipelines to form a solar heat supply path.
Ca(OH)2The storage tank 9 is connected with a solid particle feeding port of the rotary ball-milling reactor 13 through a pipeline, and a solid particle discharging port is connected with the CaO storage tank 10 through a pipeline to form an energy storage path.
Preferably, the rotary ball milling energy storage device further comprises an energy storage heat exchanger 12. The energy storage heat exchanger 12 is a powder heat exchanger. The energy storage heat exchanger 12 is arranged at Ca (OH)2Between the storage tank 9 and the solid particle inlet of the rotary ball milling reactor 13, and between the solid particle outlet and the CaO storage tank 10, CaO is discharged and preheated Ca (OH)2Feeding and recycling reaction waste heat.
The steam rankine power generation device includes a steam rankine turbine 17, a steam power generation condenser 18, a steam power generation water pump 19, a steam power generation gate valve 20, a first steam power generation heat exchanger 15, and a second steam power generation heat exchanger 16, which are connected in this order through a circulation line, and constitutes a power generation circulation path.
An upper outlet at the upper end of the rotary ball milling reactor 13, a second steam power generation heat exchanger 16 and a first steam power generation heat exchanger 15 are sequentially connected through a pipeline to form a first energy storage power generation heat source path. The tower type solar heat collector 5, the second steam power generation heat exchanger 16 and the first steam power generation heat exchanger 15 are also connected in sequence through pipelines to form a second energy storage power generation heat source path. An energy storage heating gate valve 7 is arranged between the tower type solar thermal collector 5 and the lower inlet of the lower end of the rotary ball-milling reactor 13, and an energy storage direct power generation gate valve 8 is arranged between the tower type solar thermal collector 5 and the second steam power generation heat exchanger 16. The first steam-electric heat exchanger is connected with the working medium fluid pump 1 through an energy storage pipeline to form an energy storage working medium circulation path.
The steam rankine power plant also includes a water treatment plant 22. The steam outlet of the rotary ball milling reactor 13, the first steam power generation heat exchanger 15, the water treatment device 22 and the steam power generation condenser 18 are connected in sequence through pipelines to form a third energy storage power generation heat source path. A steam waste heat power generation gate valve 21 is arranged between a steam outlet of the rotary ball milling reactor 13 and the first steam power generation heat exchanger 15.
Preferably, the rotary ball mill energy storage device further comprises a cyclone 14. The cyclone separator 14 is arranged between the steam outlet of the rotary ball milling reactor 13 and the steam waste heat power generation gate valve 21. The bottom of the cyclone separator 14 is connected with the energy storage heat exchanger 12 through a pipeline, namely an energy storage reaction product H2Separating the steam in the O from the CaO solid particles, wherein the separated steam is used for generating power, and the CaO solid particles are used for preheating the Ca (OH) fed in2。
The energy storage mode provides energy required by power generation for the steam Rankine power generation device through the first energy storage power generation heat source path, the second energy storage power generation heat source path and the third energy storage power generation heat source path respectively.
An energy storage gate valve 2 is arranged between the working medium fluid pump 1 and the tower type solar heat collector 5 to control the energy storage stage.
The system also comprises a backup heat source device 6.
The working medium fluid pump 1, the standby heat source device 6, the second steam power generation heat exchanger 16 and the first steam power generation heat exchanger 15 are sequentially connected through pipelines to form a first energy-releasing power generation heat source path. An energy-releasing direct power generation gate valve 3 is arranged between the working medium fluid pump 1 and the standby heat source device 6.
An air extraction device is arranged in the middle of the steam Rankine turbine 17 and is connected with a steam inlet of the rotary ball milling reactor 13 through a pipeline to form a steam production path. An energy release steam gate valve 23 is arranged between the steam Rankine turbine 17 and the steam inlet.
The CaO storage tank 10 is connected with a solid particle feeding port of the rotary ball-milling reactor 13 through a pipeline, and a solid particle discharging port is connected with the Ca (OH)2 storage tank 9 through a pipeline to form an energy release path.
Preferably, the rotary ball milling energy storage device further comprises an energy release heat exchanger 11. The energy releasing heat exchanger 11 is a powder heat exchanger. The energy-releasing heat exchanger 11 is arranged between the CaO storage tank 10 and a solid particle feeding port of the rotary ball milling reactor 13, and between a solid particle discharging port and Ca (OH)2Ca (OH) is added between the storage tanks 92Discharging, preheating CaO feeding, and recycling reaction waste heat.
The working medium fluid pump 1 is connected with an upper inlet at the lower end of the rotary ball-milling reactor 13 through a pipeline, and a lower outlet at the upper end of the rotary ball-milling reactor 13, the second steam power generation heat exchanger 16 and the first steam power generation heat exchanger 15 are sequentially connected through a pipeline to form a second energy-releasing power generation heat source path. An energy-releasing heat-exchange power generation gate valve 4 is arranged between the working medium fluid pump 1 and the upper inlet at the lower end.
The energy releasing mode provides energy required by power generation for the steam Rankine power generation device through the first energy releasing power generation heat source path and the second energy releasing power generation heat source path respectively.
The first steam-electric heat exchanger is connected with the working medium fluid pump 1 through an energy release pipeline to form an energy release working medium circulation path.
In this system, Ca (OH)2The conveying of the solid particles and the CaO solid particles adopts a spiral feeding mode.
The application method of the calcium hydroxide thermochemical energy storage system comprises an energy storage stage and an energy release stage. The energy storage stage comprises a solar heat supply path, an energy storage path, a first energy storage and power generation heat source path, a second energy storage and power generation heat source path, a third energy storage and power generation heat source path, a power generation circulating path and an energy storage working medium circulating path. The energy releasing stage comprises a first energy releasing and power generating heat source path, a power generating circulation path, a steam production path, an energy releasing path, a second energy releasing and power generating heat source path and an energy releasing working medium circulation path.
In particular, the thermochemical energy storage system adopted by the system is Ca (OH)2and/CaO, storing and releasing energy through mutual conversion between heat energy and chemical energy, wherein the energy storage chemical reaction process and the energy release chemical reaction process are realized in the rotary ball milling reactor 13. When the sun irradiation is sufficient, Ca (OH)2Solid bodyThe particles and the high-temperature fluid working medium flowing through the tower type solar heat collector 5 perform partition wall heat exchange to generate endothermic decomposition reaction, and the received heat is stored in decomposition products CaO and H in the form of chemical energy2And (4) in O. When heat is required, CaO and H2The reverse synthetic reaction of O takes place, CaO and H are reacted2The chemical energy stored in O is converted back into heat energy and released.
As shown in fig. 2, the energy storage phase: when the solar radiation is sufficient, the solar radiation energy is converted into the heat energy of the fluid working medium through the tower type solar heat collector 5, the fluid working medium flows through the energy storage heating gate valve 7 and enters the rotary ball milling reactor 13 in a countercurrent manner to heat Ca (OH)2Solid particles are subjected to decomposition reaction at the temperature of 450-600 ℃. As the decomposition reaction progresses, the decomposition product CaO solid particles are fed into the energy storage heat exchanger 12 and Ca (OH) after the decomposition product CaO solid particles are fed2The solid particle flow fully exchanges heat and finally enters the CaO storage tank 10. Decomposition product H2O first enters the cyclone 14 to remove solid particles that may be present therein, and H in order to make full use of the residual heat of the reaction2The O is then preheated in the first steam-power-generation heat exchanger 15 to feed water of the steam rankine cycle, and after entering the water treatment device 22, the water flows into the steam-power-generation condenser 18 to make full use of the heat. Moreover, the fluid working medium passing through the tower type solar heat collector 5 can also pass through the energy storage direct power generation gate valve 8, and the steam Rankine cycle working medium is directly heated through the second steam power generation heat exchanger 16 and the first steam power generation heat exchanger 15 to generate power. By controlling the energy storage heating gate valve 7 and the energy storage direct power generation gate valve 8, two modes of energy storage and steam Rankine power generation can exist simultaneously or can be operated independently.
As shown in fig. 3, the energy release phase: when solar radiation is insufficient and energy is released for power generation for the first time, the energy-releasing direct power generation gate valve 3 is opened, working medium fluid passes through the standby heat source device 6, and the steam Rankine cycle working medium is heated through the second steam power generation heat exchanger 16 and the first steam power generation heat exchanger 15 to generate power. Then, the energy release steam gate valve 23 is opened to extract steam, so that the steam enters the rotary ball milling reactor 13 to perform a synthesis reaction with the CaO solid particles flowing into the reactor, and a large amount of heat is released. After the synthesis reaction begins, the energy-releasing heat-exchanging power generation gate valve 4 is opened, and the energy-releasing is closed directlyAnd in the power generation gate valve 3, the heat source of the working fluid is switched from the standby heat source device 6 to the heat released by the synthesis reaction in the rotary ball milling reactor 13, and the heat is transferred to the steam Rankine power generation device to realize power supply. After the initial release of energy (generation), the synthesis product Ca (OH) is used2The solid particle reaction waste heat is heated in the energy release heat exchanger 11, and then the CaO solid particle flow is fed, so that the reaction waste heat is not wasted, and the heat is fully utilized.
When solar irradiation is sufficient in the daytime, the tower-type solar heat collector 5 absorbs heat, and the photo-thermal power generation process and the energy storage process are directly completed by the heat exchange fluid working medium, the steam Rankine power generation device and the rotary ball-milling energy storage device. The night system starts the unit by adopting the standby heat source device 6, extracts water vapor and leads the water vapor into the rotary ball-milling reactor 13 to complete the energy release process, reversely converts the stored chemical energy into heat energy and releases the heat energy for power generation, and the standby heat source device 6 and the rotary ball-milling energy storage device are combined to stably generate power. The three heat sources are flexibly distributed and adjusted, and the solar thermal power station can continuously and efficiently operate.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A calcium hydroxide thermochemical energy storage system characterized by:
the system comprises a tower-type solar heat collection device, a rotary ball-milling energy storage device and a steam Rankine power generation device;
the tower type solar heat collection device comprises a working medium fluid pump and a tower type solar heat collector;
the rotary ball-milling energy storage device comprises a CaO storage tank, Ca (OH)2A storage tank and a rotary ball milling reactor; the rotary ball milling reactor comprises a reaction channel with a solid particle feeding hole, a solid particle discharging hole, a steam inlet and a steam outlet, and a heat exchange channel with a lower end lower inlet, a lower end upper inlet, an upper end lower outlet and an upper end upper outlet;
the working medium fluid pump, the tower type solar heat collector and the lower inlet at the lower end of the rotary ball-milling reactor are sequentially connected through a pipeline to form a solar heat supply path;
Ca(OH)2the storage tank is connected with a solid particle feeding port of the rotary ball-milling reactor through a pipeline, and a solid particle discharging port is connected with the CaO storage tank through a pipeline to form an energy storage path;
the steam Rankine power generation device comprises a steam Rankine turbine, a steam power generation condenser, a steam power generation water pump, a steam power generation gate valve, a first steam power generation heat exchanger and a second steam power generation heat exchanger which are sequentially connected through a circulation pipeline to form a power generation circulation path;
an upper outlet at the upper end of the rotary ball-milling reactor, a second steam power generation heat exchanger and a first steam power generation heat exchanger are sequentially connected through a pipeline to form a first energy storage power generation heat source path; the tower type solar heat collector, the second steam power generation heat exchanger and the first steam power generation heat exchanger are also sequentially connected through pipelines to form a second energy storage power generation heat source path; an energy storage heating gate valve is arranged between the tower type solar thermal collector and the lower inlet of the lower end of the rotary ball-milling reactor, and an energy storage direct power generation gate valve is arranged between the tower type solar thermal collector and the second steam power generation heat exchanger; the first steam-electricity heat exchanger is connected with the working medium fluid pump through an energy storage pipeline to form an energy storage working medium circulation path;
the steam Rankine power generation device also comprises a water treatment device;
a steam outlet of the rotary ball milling reactor, the first steam power generation heat exchanger, the water treatment device and the steam power generation condenser are sequentially connected through pipelines to form a third energy storage power generation heat source path; a steam waste heat power generation gate valve is arranged between a steam outlet of the rotary ball-milling reactor and the first steam power generation heat exchanger;
an energy storage gate valve is arranged between the working medium fluid pump and the tower type solar heat collector;
the system also includes a backup heat source device;
the working medium fluid pump, the standby heat source device, the second steam power generation heat exchanger and the first steam power generation heat exchanger are sequentially connected through a pipeline to form a first energy-releasing power generation heat source path; an energy release direct power generation gate valve is arranged between the working medium fluid pump and the standby heat source device;
an air extraction device is arranged in the middle of the steam Rankine turbine and is connected with a steam inlet of the rotary ball milling reactor through a pipeline to form a steam production path; an energy release steam gate valve is arranged between the steam Rankine turbine and the steam inlet;
the CaO storage tank is connected with a solid particle feed inlet of the rotary ball milling reactor through a pipeline, and a solid particle discharge outlet is connected with Ca (OH) through a pipeline2The storage tanks are connected to form an energy release path;
the working medium fluid pump is connected with the upper inlet at the lower end of the rotary ball-milling reactor through a pipeline, and the lower outlet at the upper end of the rotary ball-milling reactor, the second steam power generation heat exchanger and the first steam power generation heat exchanger are sequentially connected through a pipeline to form a second energy-releasing power generation heat source path; an energy-releasing heat-exchange power generation gate valve is arranged between the working medium fluid pump and the upper inlet at the lower end;
the first steam-electricity heat exchanger is connected with the working medium fluid pump through an energy release pipeline to form an energy release working medium circulation path.
2. The calcium hydroxide thermochemical energy storage system of claim 1 wherein:
the rotary ball-milling energy storage device also comprises an energy storage heat exchanger;
the energy storage heat exchanger is a powder heat exchanger;
the energy-storage heat exchanger is arranged at Ca (OH)2Between the storage tank and the solid particle feeding port of the rotary ball-milling reactor, and between the solid particle discharging port and the CaO storage tank.
3. The calcium hydroxide thermochemical energy storage system of claim 1 wherein:
the rotary ball-milling energy storage device further comprises an energy releasing heat exchanger;
the energy releasing heat exchanger is a powder heat exchanger;
the energy-releasing heat exchanger is arranged between the CaO storage tank and the solid particle feed inlet of the rotary ball-milling reactor, and between the solid particle discharge outlet and Ca (OH)2Between the storage tanks.
4. The calcium hydroxide thermochemical energy storage system of claim 2 wherein:
the rotary ball-milling energy storage device also comprises a cyclone separator;
the cyclone separator is arranged between a steam outlet of the rotary ball milling reactor and the steam waste heat power generation gate valve; the bottom of the cyclone separator is connected with the energy storage heat exchanger through a pipeline.
5. The calcium hydroxide thermochemical energy storage system of claim 1 wherein:
wherein, Ca (OH)2The conveying of the solid particles and the CaO solid particles adopts a spiral feeding mode.
6. The calcium hydroxide thermochemical energy storage system of claim 1 wherein:
wherein, a plurality of steel balls are arranged in the rotary ball-milling reactor.
7. The calcium hydroxide thermochemical energy storage system of claim 1 wherein:
wherein, the rotary ball-milling reactor adopts 314 stainless steel materials.
8. Method of use of the calcium hydroxide thermochemical energy storage system according to any of claims 1 to 7, characterized in that:
comprises an energy storage stage and an energy release stage;
the energy storage stage comprises a solar heat supply path, an energy storage path, a first energy storage and power generation heat source path, a second energy storage and power generation heat source path, a third energy storage and power generation heat source path, a power generation circulating path and an energy storage working medium circulating path;
the energy releasing stage comprises a first energy releasing and power generating heat source path, a power generating circulation path, a steam production path, an energy releasing path, a second energy releasing and power generating heat source path and an energy releasing working medium circulation path.
9. The method of using a calcium hydroxide thermochemical energy storage system according to claim 8, wherein:
wherein, the energy storage stage: when the solar radiation is sufficient, the solar radiation energy is converted into the heat energy of the fluid working medium through the tower type solar heat collector, the fluid working medium enters the rotary ball-milling reactor in a countercurrent manner through the energy storage heating gate valve to heat Ca (OH)2Solid particles are subjected to decomposition reaction; along with the deepening of the decomposition reaction, the decomposition product CaO solid particles enter a CaO storage tank; decomposition product H2O, preheating feed water of the steam Rankine cycle in the first steam power generation heat exchanger, and enabling the feed water to flow into a steam power generation condenser after entering a water treatment device so as to fully utilize heat; and moreover, the fluid working medium passing through the tower type solar heat collector can also pass through the energy storage direct power generation gate valve, and the steam Rankine cycle working medium is directly heated through the second steam power generation heat exchanger and the first steam power generation heat exchanger to generate power.
10. The method of using a calcium hydroxide thermochemical energy storage system according to claim 8, wherein:
wherein, the energy releasing stage: when solar radiation is insufficient and energy is released for power generation for the first time, the energy-releasing direct power generation gate valve is opened, and working medium fluid passes through the standby heat source device and heats a steam Rankine cycle working medium through the second steam power generation heat exchanger and the first steam power generation heat exchanger to generate power; then opening an energy release steam gate valve to extract steam, leading the steam to enter a rotary ball milling reactor to carry out synthetic reaction with CaO solid particles flowing into the reactor, and releasing a large amount of heat; after the synthesis reaction starts, opening an energy-releasing heat exchange power generation gate valve, closing an energy-releasing direct power generation gate valve, switching the heat source of the working fluid from a standby heat source device to the heat released by the synthesis reaction in the rotary ball-milling reactor, and transferring the heat to a steam Rankine power generation device to realize power supply; after the initial release of energy, the synthesis product Ca (OH) is used2And the solid particle reaction waste heat is heated by the energy release heat exchanger and then the CaO solid particle flows are fed.
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