CN108117860A - Enhanced thermal conduction type fuse salt composite phase-change material and regenerative apparatus and energy storage method - Google Patents
Enhanced thermal conduction type fuse salt composite phase-change material and regenerative apparatus and energy storage method Download PDFInfo
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- CN108117860A CN108117860A CN201711363462.XA CN201711363462A CN108117860A CN 108117860 A CN108117860 A CN 108117860A CN 201711363462 A CN201711363462 A CN 201711363462A CN 108117860 A CN108117860 A CN 108117860A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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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
- F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
- F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to high temperature heat utilization and technical field of energy storage more particularly to a kind of enhanced thermal conduction type fuse salt composite phase-change materials and regenerative apparatus and energy storage method；The raw material selection expanded graphite of the fuse salt composite phase-change material and Hitec ternary nitric acid fused salts；Expanded graphite additive amount is 20%, and loose porous expanded graphite is made all to be submerged in saturation nitrate solution；Then mixture is heated using 90 DEG C of constant temperature, stirred always using electric mixer during heating, until saturation nitrate solution in water be largely evaporated, then using constant temperature 120 DEG C mixture is heated, by remaining moisture evaporating completely, KNO is made in finally drying3‑NaNO2‑NaNO3/ expanded graphite composite phase-changing material；Invention enhances the heat conductivilitys of material；Accumulation is formed hold over system in the form of packed bed, improves industrial feasibility, heat accumulation subsystem of storage heater, ironmaking hot-blast stove and focusing solar power generation available for industrial furnace etc..
Description
Technical field
The present invention relates to high temperature heat utilization and technical field of energy storage more particularly to a kind of enhanced thermal conduction type fuse salt compound phases
Become material and regenerative apparatus and energy storage method.
Background technology
Important step of the energy storage as using energy source has especially important work to industrial energy saving and renewable energy utilization
With.Due to the defects of regenerative resource is intermittent and cannot stablize supply, between the supply and demand of the energy, often there are quantity
In upper, form and difference spatially, it is impossible to meet the requirement that industrialization continuously energizes on a large scale；Industry is the end of China's maximum
End is with energy consumer sector, and the proportion for accounting for national total energy consumption maintains 70% or so always, and energy utilization rate is significantly less than elder generation
Into country, one of the main reasons is that intermittent high-quality waste heat is not utilized effectively, it is therefore necessary to develop high-efficiency thermal storage skill
Art.
The performance and cost of heat storage technology, depending on heat transfer heat accumulating performance and storage/exothermic process design and
Two aspect of control, main development thinking are the high thermal storage density of exploitation, operation at high temperature, high storage/rate of heat release, low cost, ring
The heat accumulating of border close friend, the controllable heat storage type of evolution study the transmission of high-performance working medium and accumulation of heat mechanism.It is molten
Melt salt with the series of advantages such as thermal capacity is big, the high and low vapour pressure of temperature in use, low viscosity, chemical stability are good, have both accumulation of heat
With heat transmission function, thus fusion tray of thermal transmission and storage technology by be high temperature heat utilization field development priority.
There are thermal conductivity factor is low, phase transition process volume becomes for single inorganic molten salt or the mixture of several fuse salts
Change the shortcomings that larger, so as to influence its practical application.The Composite of material is one of inexorable trend of Materials, composite phase-change
The advantages of heat-storing material is conducive to combine sensible heat and latent heat storage material is the micropackaging anticorrosion technique of high temperature phase-change material
Provide newer thinking.Structural support material is advantageously implemented the stereotyped structure of complex, while heat conduction strengthening material is micro-
The diabatic process that mixed nanometer is easily achieved high temperature heat-storing material is adjustable, improves storage/rate of heat release of heat-storing material.Material
Compound preparation in multi-scale range is conducive to balance the architectural characteristic of composite construction heat-storing material, heat conductivility, heat storage performance
Relation between three, especially exploitation high-performance nano and micron composite structure heat-storing material centering high-temperature heat accumulation field, solar heat
The fields such as power generation, industrial afterheat recovery important in inhibiting.
Although Patent No. 01119014.0, patent name is for accumulation of heat or the preparation of the energy-saving composite material of cold-storage
Method discloses one kind by using phase-change material（PCM）Vacuum impregnation is carried out to the expanded graphite matrix of compression, prepares graphite
The method of the energy-saving composite material for being used for accumulation of heat or cold-storage of matrix and the PCM being impregnated in described matrix, this method are mainly
The matrix being immersed under atmospheric pressure and partially or completely in melting PCM or salting liquid is fixed in steeper
Portion evacuates steeper until the PCM filled in matrix reaches required addition afterwards, and this method is although simple and honest and clean
Valency, but the porosity of Graphite Bottom is too small, causes heat storage and cold accumulation ineffective.
Meanwhile the patent of Application No. 02133310. 6 discloses a kind of system of metal-base composite fused salt as heat accumulating material
Preparation Method, this method are intended to provide the sensible heat heat-storing material that a kind of porosity reaches 25-85%, but from the point of view of disclosed file, it should
Technical solution is very incomplete, and how the technical inspiration that we do not obtain any substance therefrom obtains porosity and reach
The sensible heat heat-storing material of 25-85%.
In addition, to disclose a kind of foamed-metal based high-temperature phase change heat storage compound for the patent of Application No. 200910074633.6
Material and preparation method thereof, the technology are mainly the solid-liquid phase change accumulation of heat when being attached with >=600 DEG C on foam metal framework material
Material " adheres to " than relatively difficult to achieve first, and " adhesive force " is difficult to be guaranteed simultaneously, and this method is difficult to be suitable for industrial production.
In addition, the patent of Application No. 201010527277.1 discloses a kind of preparation method of porous material substrate, it should
Method mainly mixes calcic raw material and silicon-containing material Ca: Si=1: 0.4~1 weighing in molar ratio, by raw material
20~40 times of addition water of total weight, stir and 4~12h are kept the temperature at 180~320 DEG C, obtain porous material material
Slurry；After slurry cooling, porous material substrate is made after drying, shaping in the Nano metal powder of addition 0%~5%, will
Porous material substrate is immersed in the inorganic salts phase-change material after melting completely, and phase-change material is made to be impregnated into the hole of porous material substrate
In road；Whether the higher difficulty of processing of this method cost is big, using the method for " immersion " in fact it is difficult to ensure that " being uniformly impregnated with ", quality
It is difficult to be guaranteed, influences heat transfer effect.
When carrying out heat exchange energy storage using fuse salt composite phase-change material, put and stored using fuse salt mesolimnion one-pot
Heat is a kind of liquid-solid joint sensible heat heat storage type, organically combines the low of the good heat conveyance performance of liquid and solid heat storage
Cost advantages using density and the cold and hot relation of temperature, form the very big natural layering of a temperature gradient, i.e., among tank
Mesolimnion, it is as separation layer so that more than mesolimnion melts saline solution and keeps high temperature, saline solution is melted below mesolimnion and keeps low
Temperature, with the continuous extraction of melting saline solution, mesolimnion can move up and down, and the fuse salt liquid energy of extraction enough keeps constant temperature, when oblique temperature
When layer reaches the top or bottom of tank, significant changes can occur for the temperature of the melting saline solution of extraction.In order to maintain temperature ladder in tank
Degree layering, just must be strictly controlled melting saline solution injection and discharging process, in tank reasonable filled solid heat storage medium and
The suitable layered equipment of configuration, such as floating import, ring shell heat exchanger, researcher have found to possess Suitable porous medium filler
The indirect hold over system of mesolimnion list tank has advantages for development very much.In heat storage technology field, except using siliceous sand, quartz, iron ore
Outside the natural solid-state heat storage medium such as stone, synthetically prepared porous functional material, packed bed are stored/put due to that can effectively improve
The thermal efficiency and regenerative capacity receive the extensive concern of researcher.
Research shows in mesolimnion list tank heat-accumulating process, the volumetric heat capacity of filler（ρc p）It is to influence device effective volume
An important factor for regenerative capacity, thermocline thickness.Using molten salts composite phase-change material in the temperature range of a very little
There is larger latent heat of phase change, that is, there is very big equivalent sensible heat to hold, be equivalent to and latent heat of phase change is converted to one very greatly
Sensible heat hold（c p）, so as to make up the deficiency of the solid-states heat storage medium such as traditional siliceous sand, quartz, iron ore, effectively improve
Regenerative capacity.
Therefore it provides a kind of enhanced thermal conduction type fuse salt composite phase-change material and mating high-temperature heat storage device and heat exchange
Energy storage method has important application value.
The content of the invention
The shortcomings that it is a primary object of the present invention to overcome the prior art and deficiency provide a kind of based on fuse salt compound phase
Become material, the technical solution of energy storage carried out using high-temperature heat storage device, it is espespecially a kind of using mesolimnion accumulation of heat list tank design concept as
Basis, with reference to the enhanced thermal conduction type fuse salt composite phase-change material and storage of the phase-transition heat-storage of porous substrate/fuse salt composite material
Thermal and energy storage method.
To achieve the above object, the present invention provides following technical solution：A kind of fuse salt composite phase-change of enhanced thermal conduction type
Material, the raw material of the fuse salt composite phase-change material include base material and phase-change material, and the base material is porous expansion material
Expanded graphite can be selected, after inflatable crystalline flake graphite drying process, by penetrating into microwave and graphite layers in graphite in material
Polar molecule interaction be converted into thermal energy so that in graphite each several part in a flash obtain heat and heat up, microwave
Frequency range for 200~250 GHz, microwave heating frequency is 2450 MHz, expansible graphite decompose rapidly at high temperature or
Person is vaporized so that graphite obtains expanded graphite along C axis is peeling-off；The phase-change material is fuse salt, and nitric acid can be selected
Salt, by potassium nitrate, sodium nitrite, sodium nitrate with 53:40:7 quality obtains Hitec ternary nitric acid fused salts than mixed preparing；It will
Ternary mixed nitrate prepared in mass ratio, which is poured into container, to be thoroughly mixed uniformly, adds in appropriate amount of deionized water, directly
It to saturation nitrate solution is configured to, adds the expanded graphite prepared and stirs, expanded graphite additive amount is
20%, loose porous expanded graphite is made all to be submerged in saturation nitrate solution；Then using 90 DEG C of constant temperature to mixture
It is heated, is stirred always using electric mixer during heating, until the water in saturation nitrate solution is largely evaporated, then
120 DEG C mixture is heated using constant temperature, by remaining moisture evaporating completely, KNO is made in finally drying3-NaNO2-
NaNO3/ expanded graphite composite phase-changing material.
The fuse salt composite phase-change material with the shell of high thermal conductivity coefficient and intensity is packaged, high heat conduction is made
The fused salt heat-storing sphere of performance.
The porous expanding material selects expanded graphite or foamed ceramics or foam metal.
The fuse salt selects nitrate or chloride or carbonate one or more of mixtures therein.
A kind of high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material, the device include device
Body, heat-storing sphere accumulation system, input-output system, wherein heat-storing sphere accumulation system are arranged on inside device body, and input is defeated
Going out system includes upper and bottom section, is above partially installed on the top of device body, and lower part is mounted on the bottom of device body
Portion；The device body is the tank structure of both ends open, and tank body includes shell and inner cavity, and tank body upper port is in input and output
Homogenizing plate is installed, tank body lower port is equipped with stream branch above input-output system lower part in system below part
Support, flowing supporting rack includes support base and support orifice plate, and support base is mounted on the cover board of input-output system lower part,
Orifice plate is supported to be mounted on support base；The heat-storing sphere accumulation system is made of several heat-storing sphere assembled units, heat-storing sphere group
It closes unit to be made of multiple heat-storing spheres for being packaged with fuse salt composite phase-change material, different phase transition temperatures can be encapsulated inside heat-storing sphere
Fuse salt composite phase-change material, heat-storing sphere is deposited in the form of packed bed in tank body based on mesolimnion list tank accumulation of heat design concept
Chamber forms heat-storing sphere assembled unit, is separated between heat-storing sphere assembled unit by homogenizing plate, homogenizing plate is uniformly to offer through hole
Metallic plate, tank inner chamber is mounted in the form of embedded, ensure heat-exchange working medium can it is horizontal, equably from through hole from top to down or
It flows from bottom to top.
The top of the input-output system, which is set up separately, is equipped with pipeline configuration, and bottom is arranged to end cover structure, the top of tank body
Port is provided with upper end cover structure, is fixedly connected with the end cap of input system with the upper end cover of tank body by bolt, heat-exchange working medium
It inputs or exports from pipeline opening.
The lower part of the input-output system is provided with pipeline configuration, and the part being connected with tank body is arranged to cover board knot
Structure matches with tank base, and cover board and tank base are sealedly and fixedly connected by the way of welding.
The high-temperature heat storage device external connection is equipped with heat insulation system, including attemperator and heating unit.
A kind of energy storage method based on enhanced thermal conduction type fuse salt composite phase-change material, it is described to comprise the following steps：
（1）Stage regenerator：When heat-accumulating process starts, there are the relatively low fluid of temperature and based on oblique in regenerative apparatus chamber body
Warm layer list tank accumulation of heat design concept is deposited in the heat-storing sphere assembled unit that tank inner chamber is formed in the form of packed bed, from outside
High temperature heat-exchange working medium is inputted from the upper part of input-output system, flow through after homogenizing plate it is horizontal, equably flow from top to bottom it is past
Tank inner chamber injects, and heat-exchange working medium and the heat-storing sphere assembled unit of heat-storing sphere accumulation bed type carry out heat exchange, and heat storage is existed
In heat-storing sphere, the original cryogen of tank inner chamber stores according to the difference of amount of stored heat, by mesolimnion/it is exothermic in a manner of, part or
All flowed out from the homogenizing plate of bottom；It subsequently enters next heat-storing sphere assembled unit and carries out heat exchange, until flowing through bottommost
Heat-storing sphere assembled unit carry out heat exchange finish, accordingly, complete heat-accumulating process after heat-exchange working medium, completely or partially stay in
In tank, a part of heat is stored in the form of sensible heat.The cryogen flowed out and heat-exchange working medium are replaced from input-output system lower part
The pipeline outflow divided, after external collecting apparatus or heating unit are heated, continues to execute above-mentioned cycling, until accumulation of heat
Journey terminates.
（2）Exothermic phase：When exothermic phase starts, there are the fluids and base that temperature is higher in regenerative apparatus chamber body
The heat-storing sphere assembled unit that tank inner chamber formed is deposited in the form of packed bed in mesolimnion list tank accumulation of heat design concept, from outer
The low-temperature heat exchange working medium in portion is inputted from the lower part of input-output system, flow through after homogenizing plate it is horizontal, equably flow from the bottom up
It moves past tank inner chamber to inject, heat-exchange working medium and the heat-storing sphere assembled unit progress heat exchange of heat-storing sphere accumulation bed type, in heat-storing sphere
The heat of portion's storage is released to heat-exchange working medium, and original high temperature fluid stores/heat release according to the difference of thermal discharge with mesolimnion in tank
Mode, partly or entirely distributed from the top of input-output system；Next heat-storing sphere assembled unit is subsequently entered to carry out
Heat exchange finishes until the heat-storing sphere assembled unit for flowing through top carries out heat exchange, accordingly, completes changing after exothermic process
Hot working fluid is completely or partially stayed in tank.The high temperature fluid and heat-exchange working medium for replacing outflow are put by external heating equipment
After heat, above-mentioned cycling is continued to execute, until exothermic process terminates.
The heat-storing sphere assembled unit can be according to the composite phase-change material fusing point height ladder that heat-storing sphere encapsulates in tank body
Grade distribution.
The beneficial effects of the invention are as follows：The base material that composite phase-change material of the invention uses first is expanded graphite, expansion
Graphite is that the high aperture rate expansion of high-performance is prepared in frequency by controlling the microwave in microwave bulking and microwave heating frequency
Graphite, while using Hitec ternary nitric acid fused salts as phase-change material is mixed with work by control base material and phase-change material
Skill parameter obtains KNO3-NaNO2-NaNO3/ expanded graphite composite phase-changing material enhances the heat conductivility of material；It uses simultaneously
Stainless steel spherical housing material is to KNO3-NaNO2-NaNO3/ expanded graphite composite phase-changing material is packaged, due to swollen
It is larger to overcome fuse salt volume change in storage/exothermic process to the characterization of adsorption and fixed effect of fuse salt for swollen graphite
Defect can will be filled up completely composite phase change heat-accumulation material in package casing, the presence because of gap is avoided to reduce heat transfer efficiency, so as to
Prepare high thermal conductivity fused salt heat-storing sphere；Then the heating installed by rationally designing high-temperature heat storage device and external connection
Heat-insulation system, in the form of packed bed accumulation is formed hold over system, in operation using fuse salt composite phase-change material latent heat with
The energy storage method of the sensible heat storage thermal energy of fluid, this latent heat/sensible heat hybrid system had both remain hidden heat energy storage density greatly and energy
The advantages of amount output is stablized and sensible heat energy-accumulating medium can be with heat exchanging fluid direct contact heat transfer, and overcome latent heat storage system
It needs to expend a large amount of canisters, tubing and there are the shortcomings that fused salt corrosion, industrial feasibility is improved, available for industrial furnace
Heat accumulation subsystem of storage heater, ironmaking hot-blast stove and focusing solar power generation etc..
Description of the drawings
Fig. 1 is the cross section structure schematic diagram of heat-storing sphere in the present invention.
Fig. 2 is the decomposition texture schematic diagram of high temperature regenerative apparatus of the present invention.
Fig. 3 is the assembling structure schematic diagram of high temperature regenerative apparatus of the present invention.
Fig. 4 is the principle schematic of heat-accumulating process in the present invention.
Fig. 5 is the principle schematic of exothermic process in the present invention.
Attached drawing marks explanation：1- device bodies, 11- shells, 12- inner cavities, 13- upper end covers, 2- heat-storing sphere accumulation systems,
21- heat-storing spheres, 211- composite phase-change materials, 212 stainless steel casings, 3- input-output systems, the upper parts of 31-, 32- lower parts,
311- end caps, 321- cover boards, 33- pipelines, 4- homogenizing plates, 5- support bases, 6- support orifice plates.
Specific embodiment
Below in conjunction with the Figure of description 1-5 specific embodiments that the present invention will be described in detail：
As shown in Figure 1, a kind of fuse salt composite phase-change material of enhanced thermal conduction type, the former material of the fuse salt composite phase-change material
Material includes base material and phase-change material, and base material uses porous expanding material, such as foamed ceramics or foam metal or expanded graphite.Pin
The defects of relatively low to fuse salt thermal conductivity factor, selecting expanded graphite, the fuse salt as phase-change material is selected as porous substrate
Nitrate or chloride or carbonate one or more of mixtures therein, by experimental results demonstrate Hitec ternary nitric acid melts
Salt has outstanding physics and chemical attribute, so Hitec ternary nitric acid fused salts are selected as phase-change material, then by made from
Base material and phase-change material prepare expanded graphite/ternary nitric acid fuse salt composite phase change heat-accumulation material by saturated water solution method.
The base material is expanded graphite, micro- in graphite by penetrating into after inflatable crystalline flake graphite drying process
Ripple and the interaction of the polar molecule of graphite layers are converted into thermal energy, so that each several part obtains in a flash heat same in graphite
And heat up, the frequency range of microwave is 200~250 GHz, and microwave heating frequency is 2450 MHz, and expansible graphite is at high temperature
It is rapid to decompose or vaporize so that graphite obtains expanded graphite along C axis is peeling-off；Pass through many experiments in this preparation method
It draws the relation of test parameters and expanded graphite performance, high property is obtained by the frequency range and microwave heating frequency that control microwave
Energy, the expanded graphite of high porosity.The phase-change material is fuse salt, and nitrate can be selected by potassium nitrate, sodium nitrite, nitre
Sour sodium is with 53:40:7 quality obtains Hitec ternary nitric acid fused salts than mixed preparing；Ternary prepared in mass ratio is mixed
Nitrate, which is poured into container, to be thoroughly mixed uniformly, appropriate amount of deionized water is added in, until being configured to saturation nitrate solution.
Expanded graphite/ternary nitric acid fuse salt composite phase change heat-accumulation material is prepared using saturated water solution method：In beaker
The saturation nitrate solution prepared is added in, the expanded graphite prepared is added and stirs, expanded graphite addition
It measures as 20%, loose porous expanded graphite is made all to be submerged in saturation nitrate solution；Then beaker is put into 90 DEG C
Heating water bath in water-bath is stirred always during heating using electric mixer, until the big portion of water in saturation nitrate solution
Divide and be evaporated, then beaker is put into 120 DEG C of constant temperature electric heatings sets, by remaining moisture evaporating completely, be then placed in electric heating constant temperature drum
Wind drying box is dried；The bulk sample that drying and processing is obtained is ground into little particle, that is, KNO is made3-NaNO2-NaNO3/ expansion
Graphite composite phase-change material 211 is finally packaged with high thermal conductivity coefficient and the stainless steel casing of intensity 212, high heat conduction is made
The fused salt heat-storing sphere 21 of performance, since expanded graphite is to the characterization of adsorption and fixed effect of fuse salt, overcome fuse salt store/
The defects of volume change is larger in exothermic process can will be filled up completely composite phase change heat-accumulation material in encapsulation stainless steel casing 212,
Avoiding the presence because of gap reduces heat transfer efficiency, so as to prepare high thermal conductivity fused salt heat-storing sphere 21.In preparation process, it can lead to
The additive amount of regulation and control expanded graphite is crossed, prepares different thermal conductivity factors and the composite phase-change material 211 of thermal storage density；In the present invention
In experiment, ternary mixed nitrate fuse salt thermal conductivity factor is 0.824 Wm-1·K-1, after expanded graphite is added in, effectively improve
The heat conductivility of composite phase-change material 211, the sample thermal conductivity factor that expanded graphite additive amount is 20% reach 5.49 Wm-1·
K-1, 6.66 times are improved, and good thermal stability is shown in thermal cycle test.
As Figure 2-3, a kind of high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material, it is described
Device includes device body 1, heat-storing sphere accumulation system 2, input-output system 3, and wherein heat-storing sphere accumulation system 2 is arranged on device
Inside body 1, input-output system 3 includes upper part 31 and lower part 32, and upper part 31 is mounted on the top of device body 1,
Lower part 32 is mounted on the bottom of device body 1；The device body 1 is the tank structure of both ends open, and tank body includes outer
Shell 11 and inner cavity 12, shell 11 are cylinder or rectangular parallelepiped structure, and 11 upper and lower ends of shell are defeated with inputting by pipeline 33 respectively
Go out system 3 to be connected, tank body upper port lower section of part 31 on input-output system 3 is equipped with homogenizing plate 4, and tank body lower port exists
The top of 3 lower part 32 of input-output system, which is equipped with, flows supporting rack, and flowing supporting rack includes support base 5 and support orifice plate 6,
Support base is mounted on the cover board 321 of 3 lower part 32 of input-output system, and support orifice plate 6 is mounted on support base 5；Flow
Plate 4 and support orifice plate 6 are mounted on tank inner chamber 12 in the form of embedded, ensured using the metallic plate for being uniformly machined with through hole
Heat-exchange working medium energy is horizontal, is equably flowed from top to down or from bottom to top from through hole；The heat-storing sphere accumulation system 2 is by several
21 assembled unit of heat-storing sphere is formed, and 21 assembled unit of heat-storing sphere is by multiple accumulation of heats for being packaged with fuse salt composite phase-change material 211
Ball 21 forms, and 21 inside of heat-storing sphere can encapsulate the fuse salt composite phase-change material 211 of different phase transition temperatures, according to 21 envelope of heat-storing sphere
The 211 fusing point height terraced distribution of composite phase-change material of dress, heat-storing sphere 21 are based on mesolimnion list tank accumulation of heat design concept to fill
Bed form is deposited in tank inner chamber 12 and forms 21 assembled unit of heat-storing sphere, is divided between 21 assembled unit of heat-storing sphere by homogenizing plate 4
Every homogenizing plate 4 forms the level of heat-exchange working medium, Uniform Flow passage, and plays certain structural support effect, prevents heat-storing sphere
21 mutual crimp；The upper part 31 of input-output system 3 is provided with 33 structure of pipeline, and bottom is arranged to 311 knot of end cap
Structure, the upper port of tank body are provided with 13 structure of upper end cover, by bolt by the upper end cover of the end cap 311 of input system and tank body
13 are fixedly connected, and in order to improve installation and leakproofness, are placed between the end cap 311 of input system and the upper end cover 13 of tank body
There is washer, heat-exchange working medium is from 33 mouthfuls of inputs of pipeline or exports；The lower part 32 of input-output system 3 is provided with 33 structure of pipeline,
The part being connected with tank body is arranged to 321 structure of cover board, matches with tank base, by the way of welding by cover board 321 with
Tank base is sealedly and fixedly connected, and heat-exchange working medium is from 33 mouthfuls of inputs of pipeline or exports；The high-temperature heat storage device external connection
Heat insulation system is installed, including attemperator and heating unit, in entire high-temperature heat storage device is wrapped in by attemperator
Heat loss is reduced in face, realizes insulation effect；The main function of heating unit is to be managed to cementing out in input-output system 3
Heat-exchange working medium in road 33 is heated, and since the solidification point of Hitec nitric acid fuse salts is 143 DEG C, fuse salt fluid is in temperature
Just solidification is generated during less than solidification point, it is necessary to take necessity to 3 pipeline 33 of input-output system, regenerative apparatus body 1 and attachment
Preheating and heat tracing measure, to avoid frozen plug phenomenon.
As illustrated in figures 4-5, a kind of energy storage method based on enhanced thermal conduction type fuse salt composite phase-change material, it is described including with
Lower step：
（1）Stage regenerator：When heat-accumulating process starts, there are temperature relatively low fluids and base in 1 inner cavity 12 of regenerative apparatus body
21 assembled unit of heat-storing sphere that tank inner chamber 12 formed is deposited in the form of packed bed in mesolimnion list tank accumulation of heat design concept, is stored
Hot-bulb 21 not exclusively fills inner cavity 12 completely, and the enhanced thermal conduction type fuse salt that 21 inside of heat-storing sphere can encapsulate different phase transition temperatures is answered
Phase-change material 211 is closed, 21 assembled unit of heat-storing sphere can be high according to its 211 fusing point of internal composite phase-change material in device body 1
Low terraced distribution, the high temperature heat-exchange working medium from external equipment are inputted from input system, and heat-exchange working medium is according to different application occasion
Temperature requirement can choose conduction oil, fuse salt liquid etc., molten heat transmission fluid is according to use temperature range, optional nitric acid
Salt, chloride, carbonate system etc., using Hitec nitric acid fuse salt fluids as heat-exchange working medium in this experiment, heat-exchange working medium is from defeated
Enter system entrance, flow through after homogenizing plate 4 it is horizontal, equably flow and injected toward tank inner chamber 12 from top to bottom, heat-exchange working medium is with storing
21 assembled unit of heat-storing sphere that hot-bulb 21 accumulates bed type carries out heat exchange, by heat storage in heat-storing sphere 21, tank inner chamber 12
Original cryogen stores according to the difference of amount of stored heat, by mesolimnion/it is exothermic in a manner of, partly or entirely from the homogenizing plate of bottom
4 outflows；It subsequently enters next 21 assembled unit of heat-storing sphere and carries out heat exchange, until the heat-storing sphere 21 for flowing through bottommost combines list
Member carries out heat exchange and finishes, and accordingly, completes the heat-exchange working medium after heat-accumulating process, completely or partially stays in tank, with sensible heat shape
Formula stores a part of heat.The cryogen and heat-exchange working medium for replacing outflow are flowed out from 3 pipeline 33 of input-output system, by outer
After portion's collecting apparatus or heating unit are heated, above-mentioned cycling is continued to execute, until heat-accumulating process terminates；More particularly exist
There are temperature when heat-accumulating process starts, in regenerative apparatus to beT 0Low temperature Hitec nitric acid fuse salt fluids and heat-storing sphere 21 accumulate
Bed, is carved at the beginningτ=0 starts, and the temperature from external equipment isT in（T in >T 0）, speed beu inHigh temperature heat-exchange working medium
（Hitec nitric acid fuse salts）It is inputted from the input system of tank body upper end, by the shunting of homogenizing plate 4 and 21 stacking bed progress of heat-storing sphere
Heat exchange, by heat storage in heat-storing sphere 21, in tank original cryogen according to the difference of amount of stored heat, stored with mesolimnion/
Exothermic mode is partly or entirely flowed out from bottom；Accordingly, the heat-exchange working medium after heat-accumulating process is completed, is completely or partially stayed
In tank, a part of heat is stored in the form of sensible heat.The cryogen and heat-exchange working medium for replacing outflow pass through external collecting apparatus
Or above-mentioned cycling is continued to execute after heating devices heat, until heat-accumulating process terminates.
（2）Exothermic phase：When exothermic phase starts, there are the higher fluids of temperature in 1 inner cavity 12 of regenerative apparatus body
And the heat-storing sphere 21 that tank inner chamber 12 formed is deposited in the form of packed bed based on mesolimnion list tank accumulation of heat design concept and combines list
Member, the low-temperature heat exchange working medium from external equipment are inputted from input system, flow through after support orifice plate 6 it is horizontal, equably from lower past
On flow and inject toward tank inner chamber 12,21 assembled unit of heat-storing sphere that heat-exchange working medium accumulates bed type with heat-storing sphere 21 carries out hot friendship
Change, the heat of 21 internal reservoir of heat-storing sphere is released to heat-exchange working medium, in tank original high temperature fluid according to the difference of thermal discharge, with
Mesolimnion storage/exothermic mode, partly or entirely flows out from upper end；It subsequently enters next 21 assembled unit of heat-storing sphere and carries out heat
It exchanges, is finished until 21 assembled unit of heat-storing sphere for flowing through top carries out heat exchange, accordingly, complete changing after exothermic process
Hot working fluid is completely or partially stayed in tank；The high temperature fluid and heat-exchange working medium for replacing outflow are put by external heating equipment
After heat, above-mentioned cycling is continued to execute, until exothermic process terminates；More particularly, when exothermic phase starts, exist in tank body
Temperature isT 0High temperature Hitec nitric acid fuse salt fluids and heat-storing sphere 21 it is stacking bed, carve at the beginningτ=0 starts, and temperature isT in
（T in <T 0）, speed beu inLow-temperature heat exchange working medium（Hitec nitric acid fuse salts）It is uniformly inputted from tank body bottom, with heat-storing sphere 21
Stacking bed carry out heat exchange, the heat of 21 internal reservoir of heat-storing sphere are released to heat-exchange working medium, in tank original high temperature fluid according to
The difference of thermal discharge, stored by mesolimnion/it is exothermic in a manner of, partly or entirely flowed out from upper end；Accordingly, after completing exothermic process
Heat-exchange working medium, completely or partially stay in tank, the high temperature fluid and heat-exchange working medium for replacing outflow are put by external heating equipment
Above-mentioned cycling is continued to execute after heat, until exothermic process terminates.
Present invention can apply to high temperature heat utilization occasion, such as using fuse salt as the focusing sun of heat transfer heat storage medium
Energy heat generating system substitutes the double tank heat storage types of traditional fuse salt.
The above is only presently preferred embodiments of the present invention, is not intended to limit the scope of the present invention, one's own profession
The technical staff of industry under the inspiration of the technical program, can make some deformations and modification, every technology according to the invention
Any modification, equivalent variations and the modification that essence makees above embodiment still fall within the scope of technical solution of the present invention
It is interior.
Claims (10)
1. a kind of fuse salt composite phase-change material of enhanced thermal conduction type, it is characterised in that：The fuse salt composite phase-change material
Raw material include base material and phase-change material, and the base material is porous expanding material, expanded graphite can be selected, by inflatable scale
After graphite dry processing, thermal energy is converted by the polar molecule interaction for penetrating into microwave in graphite and graphite layers,
So that each several part heats up with heat is obtained in a flash in graphite, the frequency range of microwave is 200~250 GHz, microwave
Heating frequency is 2450 MHz, and expansible graphite is decomposed rapidly or vaporized so that graphite is peeling-off along C axis at high temperature
Obtain expanded graphite；The phase-change material be fuse salt, can be selected nitrate, by potassium nitrate, sodium nitrite, sodium nitrate with
53:40:7 quality obtains Hitec ternary nitric acid fused salts than mixed preparing；By ternary mixed nitrate prepared in mass ratio
It pours into container and is thoroughly mixed uniformly, add in appropriate amount of deionized water, until being configured to saturation nitrate solution, add system
The expanded graphite got ready simultaneously stirs, and expanded graphite additive amount is 20%, and loose porous expanded graphite is made all to flood
In saturation nitrate solution；Then mixture is heated using 90 DEG C of constant temperature, electric mixer one is used during heating
Straight stirring, until the water in saturation nitrate solution is largely evaporated, then using constant temperature 120 DEG C mixture is heated, will
KNO is made in remaining moisture evaporating completely, finally drying3-NaNO2-NaNO3/ expanded graphite composite phase-changing material.
2. the fuse salt composite phase-change material of enhanced thermal conduction type according to claim 1, it is characterised in that：Described is melted
Melt salt composite phase-change material to be packaged with the shell of high thermal conductivity coefficient and intensity, the fused salt heat-storing sphere of high thermal conductivity is made.
3. the fuse salt composite phase-change material of enhanced thermal conduction type according to claim 1, it is characterised in that：Described is porous
Expanding material selects expanded graphite or foamed ceramics or foam metal.
4. the fuse salt composite phase-change material of enhanced thermal conduction type according to claim 1, it is characterised in that：The melting
Salt selects nitrate or chloride or carbonate one or more of mixtures therein.
A kind of 5. high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material, which is characterized in that the dress
It puts including device body, heat-storing sphere accumulation system, input-output system, wherein heat-storing sphere accumulation system is arranged in device body
Portion, input-output system include upper and bottom section, are above partially installed on the top of device body, and lower part is mounted on device
The bottom of body；The device body is the tank structure of both ends open, and tank body includes shell and inner cavity, and tank body upper port exists
Homogenizing plate is installed, tank body lower port is installed in the top of input-output system lower part on input-output system below part
Have and flow supporting rack, flowing supporting rack includes support base and support orifice plate, and support base is mounted on input-output system lower part
Cover board on, support orifice plate be mounted on support base on；The heat-storing sphere accumulation system is made of several heat-storing sphere assembled units,
Heat-storing sphere assembled unit is made of multiple heat-storing spheres for being packaged with fuse salt composite phase-change material, and difference can be encapsulated inside heat-storing sphere
The fuse salt composite phase-change material of phase transition temperature, heat-storing sphere are accumulated based on mesolimnion list tank accumulation of heat design concept in the form of packed bed
Heat-storing sphere assembled unit is formed in tank inner chamber, is separated between heat-storing sphere assembled unit by homogenizing plate, homogenizing plate is uniformly to open
Metallic plate equipped with through hole is mounted on tank inner chamber in the form of embedded, ensure heat-exchange working medium can it is horizontal, equably from through hole from
On flow down or from bottom to top.
6. a kind of high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material according to claim 5,
It is characterized in that：The top of the input-output system, which is set up separately, is equipped with pipeline configuration, and bottom is arranged to end cover structure, tank body it is upper
Portion port is provided with upper end cover structure, is fixedly connected with the end cap of input system with the upper end cover of tank body by bolt, and exchange heat work
Matter is inputted or exported from pipeline opening.
7. a kind of high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material according to claim 5,
It is characterized in that：The lower part of the input-output system is provided with pipeline configuration, and the part being connected with tank body is arranged to cover
Harden structure matches with tank base, and cover board and tank base are sealedly and fixedly connected by the way of welding.
8. a kind of high-temperature heat storage device based on enhanced thermal conduction type fuse salt composite phase-change material according to claim 5,
It is characterized in that：The high-temperature heat storage device external connection is equipped with heat insulation system, is filled including attemperator and heating
It puts.
9. a kind of energy storage method based on enhanced thermal conduction type fuse salt composite phase-change material, it is characterised in that：It is described including following
Step：
（1）Stage regenerator：When heat-accumulating process starts, there are the relatively low fluid of temperature and based on oblique in regenerative apparatus chamber body
Warm layer list tank accumulation of heat design concept is deposited in the heat-storing sphere assembled unit that tank inner chamber is formed in the form of packed bed, from outside
High temperature heat-exchange working medium is inputted from the upper part of input-output system, flow through after homogenizing plate it is horizontal, equably flow from top to bottom it is past
Tank inner chamber injects, and heat-exchange working medium and the heat-storing sphere assembled unit of heat-storing sphere accumulation bed type carry out heat exchange, and heat storage is existed
In heat-storing sphere, the original cryogen of tank inner chamber stores according to the difference of amount of stored heat, by mesolimnion/it is exothermic in a manner of, part or
All flowed out from the homogenizing plate of bottom；It subsequently enters next heat-storing sphere assembled unit and carries out heat exchange, until flowing through bottommost
Heat-storing sphere assembled unit carry out heat exchange finish, accordingly, complete heat-accumulating process after heat-exchange working medium, completely or partially stay in
In tank, a part of heat is stored in the form of sensible heat；
The cryogen and heat-exchange working medium for replacing outflow are flowed out from the pipeline of input-output system lower part, are set by external thermal-arrest
After standby or heating unit is heated, above-mentioned cycling is continued to execute, until heat-accumulating process terminates；
（2）Exothermic phase：When exothermic phase starts, there are the higher fluid of temperature and based on oblique in regenerative apparatus chamber body
Warm layer list tank accumulation of heat design concept is deposited in the heat-storing sphere assembled unit that tank inner chamber is formed in the form of packed bed, from outside
Low-temperature heat exchange working medium is inputted from the lower part of input-output system, flow through after homogenizing plate it is horizontal, equably flow from the bottom up it is past
Tank inner chamber injects, and the heat-storing sphere assembled unit of heat-exchange working medium and heat-storing sphere accumulation bed type carries out heat exchange, the storage of heat-storing sphere inside
The heat deposited is released to heat-exchange working medium, and original high temperature fluid stores/exothermic side with mesolimnion according to the difference of thermal discharge in tank
Formula is partly or entirely distributed from the top of input-output system；It subsequently enters next heat-storing sphere assembled unit and carries out hot friendship
It changes, is finished until the heat-storing sphere assembled unit for flowing through top carries out heat exchange, accordingly, complete the heat exchange work after exothermic process
Matter is completely or partially stayed in tank；
The high temperature fluid flowed out and heat-exchange working medium are replaced after external heating equipment carries out heat release, continues to execute above-mentioned cycling,
Until exothermic process terminates.
10. a kind of energy storage method based on enhanced thermal conduction type fuse salt composite phase-change material according to claim 9, special
Sign is：The composite phase-change material fusing point height step that the heat-storing sphere assembled unit can encapsulate in tank body according to heat-storing sphere
Distribution.
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| CN109825259A (en) * | 2019-03-06 | 2019-05-31 | 吴荣娣 | A kind of fuse salt heat accumulation capsule and preparation method thereof and heat-storing device |
| CN110513166A (en) * | 2019-08-23 | 2019-11-29 | 中国科学院上海应用物理研究所 | Back-heating type replaces energy-storing and power-generating system |
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| CN109631648A (en) * | 2018-11-02 | 2019-04-16 | 山东大学 | A kind of novel phase change thermal storage heat exchanger and working method |
| CN109297339A (en) * | 2018-12-05 | 2019-02-01 | 上海宝钢节能环保技术有限公司 | A kind of preparation method of full liquid type steam accumulator and its composite phase-change heat-storage material |
| CN109825259A (en) * | 2019-03-06 | 2019-05-31 | 吴荣娣 | A kind of fuse salt heat accumulation capsule and preparation method thereof and heat-storing device |
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| CN111121512A (en) * | 2020-02-24 | 2020-05-08 | 中国科学院理化技术研究所 | Solid phase cold accumulator |
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| CN114166887A (en) * | 2022-02-14 | 2022-03-11 | 西安石油大学 | Test experiment platform for thickness of thermocline of fused salt single-tank heat storage system |
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