CN112284167B - Phase-change energy storage material and preparation method thereof - Google Patents
Phase-change energy storage material and preparation method thereof Download PDFInfo
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- CN112284167B CN112284167B CN201910673201.0A CN201910673201A CN112284167B CN 112284167 B CN112284167 B CN 112284167B CN 201910673201 A CN201910673201 A CN 201910673201A CN 112284167 B CN112284167 B CN 112284167B
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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
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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
- C09K5/02—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
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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
- F28D20/028—Control arrangements therefor
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a phase change energy storage material, a preparation method thereof and a phase change energy storage device comprising the phase change energy storage material. The preparation method of the phase-change energy storage material is simple to operate, the raw materials are easy to obtain, the preparation method is easy to realize and is beneficial to large-scale popularization and implementation, and the phase-change energy storage device comprising the phase-change energy storage material is high in energy utilization rate and heat exchange efficiency, and the number of circulations of the phase-change energy storage material can be increased.
Description
Technical Field
The invention relates to the technical field of phase change materials, in particular to a phase change energy storage material and a preparation method thereof.
Background
In recent years, the phase change energy storage technology has gained more and more attention and development in the fields of renewable energy utilization, energy conservation, consumption reduction and the like, and the application thereof in heating, ventilation and air conditioning systems is more and more. The medium-low temperature phase change energy storage material used in the field of air conditioners is developed, cheap electric energy in the power utilization valley can be converted into heat energy to be stored in the phase change material, the heat is released in the power utilization peak, the power consumption in the peak period is reduced, and the peak clipping and valley filling effects are realized. In the currently known energy storage method, the solid-liquid phase change material has high heat storage density and stable phase change temperature, so that the solid-liquid phase change material is widely applied to heating, ventilating and air conditioning, solar energy cycle heat storage, environment-friendly home furnishing and the like.
The inorganic phase change material has wide application range, and has relatively great phase change heat and fixed melting point. Compared with organic phase-change materials, the crystalline hydrated salt has the advantages of higher heat conductivity coefficient, high density, high heat storage density per unit volume and the like. However, the crystalline hydrated salt has the disadvantages of large supercooling degree, phase separation, easy agglomeration and the like.
Disclosure of Invention
In order to overcome the above problems, the present inventors have made intensive studies, and have obtained a phase change energy storage material by adding a saturated solution of an inorganic hydrate to a phase change material of the inorganic hydrate, and the method for preparing the phase change energy storage material is simple, and by the method, a supercooling degree of the phase change energy storage material can be reduced, a phase separation phenomenon of the phase change material can be improved, and a phase change energy storage device including the phase change energy storage material has a high utilization rate and a high heat exchange efficiency, and can significantly increase the number of circulations of the phase change energy storage material, thereby completing the present invention.
The invention aims to provide a phase change energy storage material, which comprises an inorganic hydrate and a saturated solution of the inorganic hydrate, wherein the inorganic hydrate is selected from one or more of alkali hydrates and crystalline hydrated salts.
Wherein the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate and strontium hydroxide octahydrate.
Wherein the crystalline hydrated salt is selected from one or more of calcium chloride hexahydrate, aluminum potassium sulfate dodecahydrate, sodium sulfate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulfate pentahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate, and aluminum sulfate octadecahydrate.
Wherein the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.01-5), preferably 1: (0.1-2).
A second aspect of the present invention provides a method for preparing the phase change energy storage material according to the first aspect of the present invention, the method comprising the steps of:
and 3, cooling the melted mixture obtained in the step 2 to obtain the phase change energy storage material.
In the step 1, the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.01-5), preferably 1: (0.1-2).
In the step 1, the inorganic hydrate is one or more selected from alkali hydrate and crystalline hydrated salt.
Wherein, in the step 2, the heating temperature is 75-95 ℃, and preferably 80-90 ℃.
A third aspect of the invention provides a phase change energy storage material produced according to the method of the second aspect of the invention.
A fourth aspect of the invention provides a phase change energy storage device comprising a phase change energy storage material according to the first aspect of the invention or made according to the method of the second aspect of the invention.
The invention has the following beneficial effects:
(1) according to the invention, the phase change energy storage material is obtained by adding the saturated solution of the inorganic hydrate into the phase change material of the inorganic hydrate, the supercooling degree of the phase change energy storage material is reduced, and the phase separation phenomenon is improved;
(2) the preparation method of the phase change energy storage material provided by the invention is also a method for reducing the supercooling degree of the phase change energy storage material;
(3) the phase change energy storage material provided by the invention has the advantages of simple preparation method, easily obtained raw materials, easiness in realization and suitability for large-scale popularization and implementation;
(4) the phase change energy storage device comprising the phase change energy storage material provided by the invention has high energy utilization rate and high heat exchange efficiency, and can be applied to the aspects of heating, ventilating and air conditioning, solar heat storage, floor heating systems, environment-friendly homes and the like.
Drawings
Fig. 1 is a schematic structural view of a phase change energy storage device according to a preferred embodiment of the present invention;
FIG. 2 shows the cooling curve obtained in Experimental example 2 of the present invention.
The reference numbers illustrate:
1-water inlet pipe;
2-water outlet pipe;
3, heat exchange tubes;
4-an energy storage box body;
41-phase change energy storage material
5-a condenser pipe;
51-a pressure relief valve;
6-a heater;
7-pressure temperature controller
8-an insulating layer;
9-a housing;
10-helical tube section.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
The invention provides a phase change energy storage material which comprises an inorganic hydrate and a saturated solution of the inorganic hydrate.
According to the invention, the phase change energy storage material is prepared from the inorganic hydrate and a saturated solution of the inorganic hydrate.
In the invention, the inorganic hydrate is an inorganic phase-change material.
According to the invention, the inorganic hydrate is preferably an alkaline hydrate or a crystalline hydrated salt.
According to the invention, the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate, strontium hydroxide octahydrate and the like.
According to the invention, the crystalline hydrated salt is preferably selected from one or more of calcium chloride hexahydrate, potassium aluminium sulphate dodecahydrate, sodium sulphate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulphate pentahydrate, magnesium sulphate heptahydrate, sodium sulphate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminium ammonium sulphate dodecahydrate, and aluminium sulphate octadecahydrate.
According to the invention, the saturated solution of inorganic hydrate is a saturated solution of an alkaline hydrate or a saturated solution of a crystalline hydrated salt.
In the invention, the inorganic hydrate such as alkali hydrate or crystalline hydrated salt and the like can be crystallized and agglomerated, namely, phase separation, when being cooled, and meanwhile, the volume expansion is easy to cause extrusion damage to equipment pipelines and the like, so that the equipment can not be normally used, and the cycle life of the phase-change material is reduced.
In the invention, the super-cooling degree of the inorganic hydrate can be obviously reduced by adding the saturated solution of the inorganic hydrate into the inorganic hydrate, the phase separation phenomenon of the inorganic hydrate is improved, the circulating times of the inorganic hydrate are increased, and the service life of the phase change material is prolonged.
According to the invention, in the phase change energy storage material, the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.1 to 5), preferably 1: (0.1 to 2), more preferably 1: (0.1 to 0.5), and more preferably 1: (0.3-0.5).
In the invention, the crystallized hydrated salt has larger phase transition heat and fixed melting point, when the temperature is increased, the crystallized hydrated salt loses the crystal water to dissolve and desorb the heat of the salt, and when the temperature is reduced, the reverse process is generated to absorb the crystal water to release the heat. The crystalline hydrated salt has the advantages of large heat conductivity coefficient, large density, high heat storage density per unit volume and the like. However, the crystallization of the crystalline hydrous salt has disadvantages of large supercooling degree, phase separation, corrosiveness, and the like, and in order to reduce the supercooling degree and suppress the occurrence of the phase separation phenomenon, it is necessary to improve by adding a certain amount of a nucleating agent and/or a thickening agent.
According to the invention, the phase change energy storage material further comprises a nucleating agent.
According to the invention, the nucleating agent is an inorganic nucleating agent and/or an organic nucleating agent,
wherein the inorganic nucleating agent is selected from one or more of quartz, disodium hydrogen phosphate dodecahydrate, borax, calcium chloride dihydrate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium sulfate, barium chloride, calcium fluoride, barium hydroxide, nano silicon dioxide, nano titanium dioxide or inorganic fibers,
according to the invention, the organic nucleating agent is an organic fibre.
According to the invention, the nucleating agent is selected from inorganic fibers and/or organic fibers, and the organic fibers are selected from one or more of aramid fibers, polypropylene fibers, acrylic fibers, polyimide, nylon, polyethylene fibers, polypropylene fibers, poly-p-phenylene benzobisoxazole fibers, poly-p-benzimidazole fibers and poly-p-phenylene pyridobisimidazole fibers. Preferably one or more of aramid, polypropylene and nylon, such as polypropylene.
According to the invention, the nucleating agent can promote crystallization of inorganic hydrate such as crystalline hydrated salt, and the fibrous material is used as the nucleating agent, so that sedimentation is not easy to occur, the crystallization rate is high, and the phase change time of the phase change energy storage material is shortened.
In the invention, when the nucleating agent is organic fiber, in order to avoid the organic fiber floating on the liquid surface and influencing the nucleating efficiency, the organic fiber can be fixed on the bracket and then filled with the inorganic phase-change material.
According to the invention, the weight ratio of the nucleating agent to the inorganic hydrate is (0.1-10): 100, preferably (1-8): 100, more preferably (2.5 to 5): 100, e.g. 5: 100.
According to the invention, the inorganic composite phase change energy storage material also comprises a thickening agent, wherein the thickening agent is selected from one or more of super absorbent resin, fumed silica, polyacrylamide, hydroxymethyl cellulose, bentonite, sodium polyacrylate, gelatin, xanthan gum, starch and guar gum.
According to the invention, the weight ratio of the thickening agent to the inorganic hydrate is (0.01-5): 100, preferably (0.01 to 1): 100, more preferably (0.01 to 0.05): 100, e.g. 0.03: 100.
In a second aspect, the present invention provides a method for preparing the phase change energy storage material according to the first aspect, the method comprising the following steps:
According to the invention, in step 1, the inorganic hydrate is an inorganic phase-change material, preferably an alkali hydrate or a crystalline hydrated salt.
According to the invention, the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate, strontium hydroxide octahydrate and the like.
According to the invention, the crystalline hydrated salt is preferably selected from one or more of calcium chloride hexahydrate, potassium aluminium sulphate dodecahydrate, sodium sulphate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulphate pentahydrate, magnesium sulphate heptahydrate, sodium sulphate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminium ammonium sulphate dodecahydrate, and aluminium sulphate octadecahydrate.
According to the invention, the saturated solution of inorganic hydrate is a saturated solution of an alkaline hydrate or a saturated solution of a crystalline hydrated salt.
According to the invention, in the step 1, the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.1 to 5), preferably 1: (0.1-2), more preferably 1: (0.1 to 0.5), and more preferably 1: (0.2-0.5).
According to the invention, in the step 1, the inorganic hydrate and the saturated solution of the inorganic hydrate are weighed according to the weight ratio, the inorganic hydrate is added into a container, the saturated solution of the inorganic hydrate is added into the container, and the mixture is uniformly mixed to obtain the mixture.
According to the present invention, in step 1, the mixing manner of the inorganic hydrate and the saturated solution thereof is not particularly limited, and is a mixing manner commonly used in the art, such as mechanical stirring, ultrasonic, and the like.
According to the invention, in step 1, optionally also a nucleating agent, more preferably also a thickener, is added and mixed with the inorganic hydrate and the saturated solution of the inorganic hydrate to obtain a mixture.
According to the invention, in step 1, when the nucleating agent is an organic fiber, the nucleating agent is firstly added into a container, and then the energy storage main body material and the buffer are added, preferably, the energy storage main body material and the buffer are uniformly mixed and then added into the container containing the nucleating agent.
According to the invention, in step 1, when the nucleating agent is organic fiber, in order to prevent the organic fiber from floating on the upper layer of the solution to influence the nucleating effect, the organic fiber is fixed by adopting an anti-corrosion support, and then inorganic hydrate, saturated solution thereof and thickening agent are added into the organic fiber to prevent the organic fiber from floating, so that the organic fiber can be fully contacted with the inorganic hydrate and the saturated solution thereof, thereby increasing the contact area of the organic fiber with the energy storage main body material and the buffer, promoting the nucleation, improving the crystallization rate and shortening the phase change time.
And 2, heating the mixture obtained in the step 1 to be molten.
According to the invention, in step 2, the mixture obtained in step 1 is heated, preferably to melt, the inorganic hydrate undergoes a phase change from a solid phase to a liquid phase, and latent heat and sensible heat are stored.
According to the invention, in the step 2, the heating temperature is 70-100 ℃, preferably 75-95 ℃, more preferably 85-95 ℃, for example 85 ℃, 92 ℃.
And 3, cooling and forming to obtain the phase change energy storage material.
According to the invention, in step 3, the mixture is heated to melt and then cooled to be formed, preferably to room temperature (such as 25 ℃) to obtain the phase change energy storage material.
The preparation method of the energy storage phase-change material provided by the invention is also a method for reducing the supercooling degree of the phase-change energy storage material, and the method comprises the step of adding a saturated solution of the inorganic hydrate into the inorganic hydrate phase-change energy storage material so as to reduce the supercooling degree of the phase-change energy storage material.
The phase change energy storage material according to the first aspect of the present invention or prepared by the method according to the second aspect of the present invention improves supercooling and phase separation of inorganic hydrates such as crystalline hydrated salts during crystallization.
A third aspect of the invention provides a phase change energy storage material produced according to the method of the second aspect of the invention.
A fourth aspect of the invention provides a phase change energy storage device comprising a phase change energy storage material 41, the phase change energy storage material 41 preferably being a phase change energy storage material as described in the first aspect of the invention or as prepared by a method according to the second aspect of the invention.
According to the invention, the device comprises an energy storage box body 4 for containing the phase change energy storage material 41, the energy storage box body 4 is a closed container, preferably a closed container without welding spots, and the energy storage box body 4 is preferably made of a metal material, preferably a corrosion-resistant material such as a stainless steel material, an alloy material and the like.
According to the invention, as shown in fig. 1, in order to further enhance the heat preservation and insulation effect of the phase change energy storage material 41 in the energy storage box 4 and prevent heat dissipation loss, it is preferable that a heat preservation layer 8 is arranged outside the energy storage box, the heat preservation layer 8 is made of a heat preservation material, and the heat preservation material is preferably selected from one or more of polyurethane foam materials, polyphenyl heat preservation materials, rock wool heat preservation materials, vacuum heat preservation materials and perlite heat preservation materials.
According to the invention, the heat-insulating layer 8 is also covered with the shell 9, so as to protect the heat-insulating layer and further enhance the heat-insulating effect.
According to the invention, in order to prevent the phase change energy storage material from corroding the energy storage box body 4, an anti-corrosion layer is arranged on the inner wall of the energy storage box body 4, the anti-corrosion layer is an integrally formed container formed by anti-corrosion materials, and a plate material is subjected to hot melting welding or anti-corrosion coating, and the anti-corrosion material is preferably selected from any one or more of natural rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, fluorine rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, chlorinated polyethylene rubber, polypropylene, polytetrafluoroethylene, polyamide plastic, polyvinyl chloride, ABS, polycarbonate plastic, fluoroplastic, glass fiber reinforced plastic and resin.
According to the invention, the phase change energy storage device is also provided with a heater 6 for heating the phase change energy storage material.
According to a preferred embodiment of the present invention, the heater 6 extends into the phase change energy storage material 41 of the energy storage tank 4 to heat it.
According to a further preferred embodiment of the invention, the heater 6 is electrically heated, for example by resistance wire heating.
According to another preferred embodiment of the present invention, the heater 6 includes a heating coil, the heating coil is spirally embedded in the phase change energy storage material 41, a heat medium is introduced into the coil, and the phase change energy storage material is heated by introducing the heat medium into the heating coil, so as to complete heat exchange.
According to the invention, the heating coil is formed by connecting a plurality of U-shaped tubes in parallel or in series, so that the contact area between the heating coil and the phase-change material is increased, the phase-change material can be rapidly and uniformly heated, and the phase-change material is uniformly heated.
According to another preferred embodiment of the present invention, the heater 6 is a microwave heating device (such as a microwave heating furnace), and the phase change energy storage material 41 is heated by microwave heating, so that the phase change energy storage material 41 is heated uniformly by the microwave heating, the temperature of the phase change energy storage material 41 is not too high or too low, the number of phase change cycles is greater, and the service life of the phase change material is longer.
According to the invention, the phase-change energy storage device also comprises a pressure and temperature controller 7 for controlling the pressure and temperature of the energy storage box body 4, and the temperature and pressure of the phase-change material in the energy storage box body are monitored and controlled at any time, so that the stable operation of heat exchange is ensured.
According to the invention, the phase change energy storage device comprises a heat exchanger, wherein the heat exchanger comprises a water inlet pipe 1, a heat exchange pipe 3 and a water outlet pipe 2.
According to the invention, the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2 are integrally formed pipelines, or the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2 are connected in a welding mode, and the welding position is outside the heat storage pool 4, so that the problems that welding spots welded by a plurality of sections of pipelines are contacted with a phase-change material, the welding spots are corroded, and a working medium in the pipelines is contacted with the phase-change energy storage material, so that the heat exchange process cannot be better carried out are avoided.
According to the invention, the heat exchanger also comprises a working medium, and the working medium sequentially passes through the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2.
According to the invention, the heat exchange tube 3 is embedded in the phase change energy storage material 41, when the working medium flows through the heat exchange tube 3, the phase change energy storage material 41 and the working medium perform heat exchange, preferably, the phase change energy storage material 41 transfers the heat stored in the phase change energy storage material to the working medium, and the working medium takes away the heat to complete the heat exchange.
In the present invention, in order to better exchange heat between the phase change material 41 and the working medium, the heat exchange tube 3 needs to contact the phase change material to the maximum extent so as to exchange heat.
According to a preferred embodiment of the present invention, the heat exchange tube 3 is composed of one to a plurality of straight tubes connected in parallel.
According to another preferred embodiment of the present invention, the heat exchange tube 3 is a spiral tube.
According to another preferred embodiment of the present invention, the heat exchange tube 3 is formed by one or more U-shaped tubes connected in parallel or in series, so that heat exchange can be performed more sufficiently, and the heat exchange efficiency can be improved.
According to the invention, in order to prevent the phase change material from corroding the water inlet pipe 1 and the water outlet pipe 2, especially the heat exchange pipe 3 in the heat exchanger, the water inlet pipe 1, the water outlet pipe 2 and the heat exchange pipe 3 are preferably made of carbon steel, stainless steel, aluminum and aluminum alloy, copper and copper alloy and the like, and more preferably, the water inlet pipe 1, the water outlet pipe 2 and the heat exchange pipe 3 need to be subjected to anti-corrosion treatment, for example, the outer wall of the pipe is coated with an anti-corrosion coating.
According to a preferred embodiment of the present invention, when the nucleating agent is an organic fiber in the phase change energy storage material 41, in order to prevent the organic fiber from floating on the upper layer of the liquid too lightly to affect the nucleation efficiency, it is preferable to first provide an anti-corrosion support in the energy storage tank of the phase change energy storage device, fix the organic fiber on the anti-corrosion support in a knotting and winding manner, preferably weave the organic fiber into a network structure on the anti-corrosion support, and then fill the inorganic hydrated salt phase change material and the buffer agent, thereby obtaining the phase change energy storage material of the present invention.
According to the invention, the anti-corrosion bracket is made of a stainless steel material, and preferably an anti-corrosion coating is coated on the surface of the stainless steel material to prevent the phase change energy storage material from corroding or damaging the anti-corrosion bracket.
According to the invention, the corrosion protection support has a frame structure, preferably a rectangular parallelepiped frame structure or a spiral frame structure, the rectangular parallelepiped frame structure being woven with organic fibers on at least one face into a network-like structure, more preferably with organic fibers on the upper and/or lower base of the frame structure.
According to the invention, one or more anti-corrosion support structures can be arranged to increase the contact area of the nucleating agent and the energy storage main body material, so as to improve the nucleation rate.
In the phase change energy storage material comprising the crystalline hydrated salt, the crystalline hydrated salt absorbs heat in the phase change process, the crystal water is evaporated, the crystalline hydrated salt needs to absorb the crystal water during heat release, and if the moisture removed by the crystalline hydrated salt cannot be combined with the crystalline hydrated salt in time, the crystalline hydrated salt cannot continue to undergo the phase change process, so that the cycle number of the phase change energy storage material is influenced. Therefore, there is a need to reduce evaporation of moisture from phase change energy storage materials during phase change.
According to the invention, a condensate return device is connected above the top of the energy storage tank 4, preferably the condensate return device is connected to the top of the energy storage tank 4.
According to the invention, the condensation reflux equipment comprises a condensation pipe 5, one end of the condensation pipe 5 is communicated with the top of the heat storage pool 4, preferably, the axis of the condensation pipe 5 is vertical to the upper surface of the top of the heat storage pool 4, water vapor generated after phase change of a phase change material in the heat storage pool 4 can enter the condensation pipe 5, the other end of the condensation pipe 5 is provided with a pressure release valve 51, the pressure release valve 51 can maintain the pressure of the heat storage pool 4, and when the vapor pressure in the heat storage pool 4 is too large, the pressure release valve 51 is opened to release the pressure, so that the pressure in the heat storage pool 4 is prevented from being too large.
According to the invention, the water inlet pipe 1 is provided with a spiral pipe section 10, the spiral pipe section 10 is sleeved on the condensation pipe 5, namely the condensation pipe 5 penetrates through the spiral pipe section 10, and preferably the spiral pipe section 10 is wound on the condensation pipe 5.
In the invention, a heater 6 heats a phase change energy storage material 41 in an energy storage box body, such as a phase change energy storage material comprising crystalline hydrated salt, the crystalline hydrated salt absorbs heat to lose crystalline water, stores heat, the crystalline water is evaporated to enter a condenser pipe 5, after a working medium with a lower temperature is introduced into a heat exchanger, the working medium enters a heat exchange pipe 3 through a water inlet pipe 1, when the working medium flows through the water inlet pipe 1, the crystalline water in the condenser pipe 5 is condensed into liquid due to the lower temperature of the water inlet pipe 1, the liquid falls into the phase change energy storage material in the energy storage box body 4 through the condenser pipe 5, and when the working medium flows through the heat exchange pipe 3, the heat exchange is carried out between the heat exchange pipe 3 and the phase change energy storage material 41, the phase change energy storage material 41 releases heat, and the working medium absorbs heat and enters a water outlet pipe 2, thereby completing heat exchange.
In the invention, by utilizing the convection principle, the water vapor evaporated from the heat storage tank 4 is evaporated and enters the condensation pipe 5, and the water vapor directly flows back to the heat storage tank 4 from the condensation pipe 5 after being condensed by the working medium of the spiral pipe section 10.
According to the invention, the volume occupied by the phase change energy storage material 41 in the energy storage box body 4 is not more than 3/4 of the volume of the energy storage box body 4, so that when the phase change occurs, the volume expansion is prevented from filling the energy storage box body 4, and the phase change cannot be continuously caused.
The method for storing energy and supplying heat by adopting the phase-change energy storage device comprises the following steps:
and 3, introducing a working medium into the water inlet pipe 1, condensing and refluxing the crystal water in the condenser 5 into the phase change energy storage material 41, and allowing the working medium to flow through the heat exchange pipe 3 to finish heat exchange.
According to the invention, step 1, a phase change energy storage device is prepared or installed, said phase change energy storage device being as described in the fourth aspect of the invention.
According to the invention, in step 2, the energy storage process (heat storage process): the phase change energy storage material 41 is heated by the heater 6, the phase change energy storage material 41 is kept at a constant temperature for a certain time after being heated to a set temperature, the constant temperature time is obtained according to energy required by heat storage, in the process, the phase change energy storage material 41, such as crystalline hydrated salt, generates phase change, crystal water in the phase change energy storage material 41 evaporates and enters the condenser pipe 5, for example, the crystalline hydrated salt loses the crystal water, the crystal water evaporates and enters the condenser pipe 5, the phase change energy storage material 41 stores all phase change latent heat and partial sensible heat, and heating is stopped after the temperature reaches the set temperature.
According to the invention, in step 3, the energy supply process (exothermic process): the low-temperature working medium (such as cold water) is introduced into a water inlet pipe 1 of the heat exchanger, the working medium flows through a spiral pipe section 10 of the water inlet pipe 1, the spiral pipe section 10 is wound on a condensation pipe 5, the working medium in the spiral pipe section 10 can condense the water vapor in the condensation pipe 5, the water vapor is condensed, liquefied and released heat, the heat is transferred to the working medium, so that the utilization rate of energy is improved, the water vapor is liquefied and flows back to a phase change energy storage material 41 of an energy storage box body 4 through the condensation pipe 5, the working medium in the heat exchanger flows through a heat exchange pipe 3 through the water inlet pipe 1, the heat exchange is carried out between the working medium and the phase change energy storage material 41 through the heat exchange pipe 3, the phase change material of crystallized hydrated salt is combined with the crystallized water which flows back from the condensation pipe 5, phase change is carried out, the heat is released, the working medium which obtains the heat flows out through a water outlet pipe 2, the heat exchange is completed for use, and the heat release is stopped when the temperature of the working medium which flows out from the water outlet pipe 2 is low to a set temperature, the exothermic process is preferably stopped when the temperature is not higher than the temperature of the working medium entering through the inlet conduit 1.
The phase change energy storage device and the method for storing energy and supplying heat by using the phase change energy storage device can improve the energy utilization rate, prevent the temperature of the energy storage device from being overhigh, prevent the water from volatilizing, prevent the inorganic salt from being dehydrated and then being incapable of continuing the phase change process, improve the cycle times of the energy storage material and prolong the service life of the phase change material.
Examples
Example 1
Weighing 100g of potassium aluminum sulfate dodecahydrate and 30g of saturated solution of potassium aluminum sulfate dodecahydrate, adding into a reaction vessel, and uniformly stirring and mixing to obtain a mixture;
heating the mixture in an oil bath at 100 ℃ until the potassium aluminum sulfate dodecahydrate is completely melted;
and stopping heating, and naturally cooling and forming the reaction container containing the melted mixture in an oil bath to obtain the phase change energy storage material.
Example 2
Weighing 100g of potassium aluminum sulfate dodecahydrate and 20g of saturated solution of potassium aluminum sulfate dodecahydrate, adding into a reaction vessel, and uniformly stirring and mixing to obtain a mixture;
heating the mixture in an oil bath at 100 ℃ until the potassium aluminum sulfate dodecahydrate is completely melted;
and stopping heating, and naturally cooling and forming the reaction container containing the melted mixture in an oil bath to obtain the phase change energy storage material.
Example 3
Weighing 100g of barium hydroxide octahydrate, 5g of polypropylene fiber and 40g of saturated solution of barium hydroxide octahydrate;
weaving polypropylene fibers into a net shape on an anti-corrosion support, placing the net shape in a reaction container, then adding saturated solution of barium hydroxide octahydrate and barium hydroxide octahydrate into the container, and uniformly mixing to obtain a mixture;
Heating the mixture in an oil bath to 85 ℃ until the barium hydroxide octahydrate is completely melted;
and stopping heating, and naturally cooling and forming the reaction container containing the melted mixture in an oil bath to obtain the phase change energy storage material.
Example 4
Weighing 100g of barium hydroxide octahydrate, 5g of polypropylene fiber, 40g of saturated solution of barium hydroxide octahydrate and 3g of gelatin;
weaving polypropylene fibers into a net shape on an anti-corrosion support, placing the net shape in a container, then adding saturated solution of barium hydroxide octahydrate and gelatin into the container, and uniformly mixing to obtain a mixture;
heating the mixture in an oil bath to 85 ℃ until the barium hydroxide octahydrate is completely melted;
stopping heating, and naturally cooling and forming the container containing the melted mixture in an oil bath to obtain the inorganic composite phase change energy storage material.
Example 5
The utility model provides a phase change energy storage equipment, the device includes the energy storage box, the phase change energy storage material that embodiment 3 made is held in the energy storage box, the coating has the anticorrosion coating on the energy storage box inner wall, during heater and pressure temperature controller inserted the phase change energy storage material of energy storage box, phase change energy storage equipment still includes the heat exchanger, the heat exchanger includes inlet tube, heat exchange tube and outlet pipe, the heat exchange tube is buried underground in phase change material, inlet tube, heat exchange tube and outlet pipe are stainless steel, the outer wall coating has the anticorrosion coating. Be equipped with the condensation reflux equipment at the top in heat accumulation pond, the condensation reflux equipment includes the condenser pipe, and the one end and the heat accumulation pond of condenser pipe are linked together. The water inlet pipe is provided with a spiral pipe section, and the condensation pipe penetrates through the spiral pipe section, namely the spiral pipe section is wound on the condensation pipe.
The phase-change material is heated by the heater, the phase-change material loses crystal water, the phase-change material stores heat, the crystal water enters the condenser pipe through the evaporation pipe, and the phase-change material stops heating when the temperature reaches the set temperature.
Let in cold water in the inlet tube, when cold water passed through the pipeline section that inlet tube and screwed pipe contacted, cold water can carry out the condensation to the crystal water in the screwed pipe, the crystal water after the condensation flows back to the phase change material in the heat accumulation pond by the condenser pipe in, cold water passes through the heat exchange tube, takes place the heat exchange with phase change material, phase change material obtains crystal water, gives out the heat, and cold water obtains the heat and becomes hot water and flows out from the outlet pipe for the use.
Comparative example
Comparative example 1
Weighing 100g of aluminum potassium sulfate dodecahydrate, and adding the weighed 100g of aluminum potassium sulfate dodecahydrate into a reaction container;
heating the mixture by adopting an oil bath at 100 ℃ until barium hydroxide octahydrate is completely melted;
and stopping heating, and naturally cooling and forming the container containing the melted mixture in an oil bath to obtain the phase change energy storage material.
Examples of the experiments
Experimental example 1
The phase change energy storage materials obtained in examples 1-2 and comparative example 1 were heated to 100 ℃ to completely melt aluminum potassium sulfate dodecahydrate, and then naturally cooled, and the delamination phenomenon of examples 1-2 and comparative example 1 was observed.
The phase change energy storage materials obtained in the examples 1 and 2 are observed to have no delamination phenomenon, i.e. no phase separation, in the process of temperature reduction. The phase change energy storage material obtained in comparative example 1 has a delamination phenomenon, which shows that the phase separation phenomenon of the inorganic salt can be improved by adding a saturated solution of the inorganic salt to the inorganic salt.
Experimental example 2
The temperature test of the phase change energy storage material prepared in example 1 and the cooling process of the reference glycerin results in a temperature drop curve as shown in fig. 2, wherein the temperature difference curve is a change curve of the temperature difference between the temperature of the phase change energy storage material obtained in example 1 and the temperature of the reference glycerin at the same time along with time, and as can be seen from fig. 2, the temperature drop curve of example 1 has a temperature jump in the temperature drop process, which is caused by the crystallization and heat release of barium hydroxide in the temperature drop process, and the supercooling crystallization temperature (supercooling point) is 53 ℃.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. The phase change energy storage material is characterized by comprising an inorganic hydrate and a saturated solution of the inorganic hydrate, wherein the inorganic hydrate is selected from one or more of an alkali hydrate and a crystalline hydrated salt;
the alkali hydrate is selected from one or more of barium hydroxide monohydrate, barium hydroxide octahydrate and strontium hydroxide octahydrate;
the crystalline hydrated salt is selected from one or more of aluminum potassium sulfate dodecahydrate, sodium sulfate decahydrate, sodium thiosulfate pentahydrate, magnesium sulfate heptahydrate, disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate and aluminum sulfate octadecahydrate;
the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.01-5);
the phase change energy storage material also comprises a nucleating agent and a thickening agent, wherein the nucleating agent is organic fiber;
the weight ratio of the nucleating agent to the inorganic hydrate is (0.1-10): 100, respectively;
the thickener is one or more selected from super absorbent resin, fumed silica, polyacrylamide, hydroxymethyl cellulose, bentonite, sodium polyacrylate, gelatin, xanthan gum, starch and guar gum;
the weight ratio of the thickening agent to the inorganic hydrate is (0.01-5): 100.
2. The phase change energy storage material of claim 1,
the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.1-2).
3. A method for preparing a phase change energy storage material according to claim 1 or 2, comprising the steps of:
step 1, mixing an inorganic hydrate and a saturated solution of the inorganic hydrate to obtain a mixture;
step 2, heating the mixture obtained in the step 1 to be molten;
and 3, cooling the melted mixture obtained in the step 2 to obtain the phase change energy storage material.
4. The method according to claim 3, wherein in step 1, the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.01-5).
5. The method according to claim 4, wherein in step 1, the mass ratio of the inorganic hydrate to the saturated solution of the inorganic hydrate is 1: (0.1-2).
6. The method according to claim 3, wherein in the step 1, the inorganic hydrate is selected from one or more of alkali hydrate and crystalline hydrated salt.
7. The method according to claim 3, wherein the heating temperature in step 2 is 75-95 ℃.
8. The method according to claim 7, wherein the heating temperature in step 2 is 80 to 90 ℃.
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