CN107502299B - Multi-phase medium phase-change heat storage material and preparation method thereof - Google Patents
Multi-phase medium phase-change heat storage material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a multi-phase medium phase-change heat storage material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) weighing 50-90 parts of phase-change material, 10-50 parts of flowable medium and 0-0.2 part of dispersing agent according to the mass parts, mixing, and heating to melt; (2) and cooling the melted mixture to room temperature under the disturbance condition to obtain the multi-phase medium phase-change heat storage material. Compared with the prior art, the multi-phase medium system can solve the problem that thermal resistance is increased due to agglomeration of the phase-change material, reduce supercooling and phase separation, improve cycle stability and the like.
Description
Technical Field
The invention relates to the technical field of phase-change heat storage materials, in particular to a multi-phase medium phase-change heat storage material and a preparation method thereof.
Background
With the development of human society, dioxide and monoxide (such as SO) emitted during the consumption of fossil energy2、CO2CO) and the like cause problems of greenhouse effect, extreme weather increase, environmental pollution and the like to the earth. Fossil energy belongs to non-renewable energy, the limited reserves thereof cannot meet the increasing demands of people, and the world energy supply is increasingly tense. However, energy storage systems have been developed to more effectively meet the social demands for efficient and environmentally friendly energy sources, where thermal energy storage technology is currently attractive. This is because the thermal storage system can compensate for the mismatch in time between energy demand and supply, and has broad application prospects in the fields of industrial waste heat recovery, power peak load shifting, solar heat collection, and the like.
Phase change energy storage materials, including organic phase change materials and inorganic phase change materials, have the advantage of high energy storage density and are widely concerned and used in the development of energy storage systems. Compared with organic phase change materials, the inorganic crystal water and salt phase change materials have the characteristics of large heat conductivity coefficient, large energy storage density, large phase change latent heat, low price and the like, so that the inorganic crystal water and salt phase change materials become an important class of medium-low temperature energy storage phase change materials. However, compared with metal and alloy phase-change materials, the thermal conductivity of the crystalline hydrated salt phase-change material is still small, so that the heat transfer performance is poor, and the storage speed of energy is seriously influenced. In order to improve the heat transfer performance of the heat exchanger, the problem is often overcome by designing a metal heat exchange coil with a large heat exchange area, which means that the high material cost is increased. In addition, hydrated salt phase change materials tend to suffer from undercooling and phase separation resulting in diminished long-term cycling performance. The factors limit the large-scale engineering application and industrialization process of the hydrated salt phase-change material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a multi-phase medium phase-change heat storage material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a multi-phase medium phase-change heat storage material comprises the following components in parts by weight: 50-90 parts of phase-change material, 10-50 parts of flowable medium and 0-0.2 part of dispersing agent.
As a preferred embodiment, the phase change material is an inorganic solid-liquid phase change material, preferably a hydrated salt type phase change material, including but not limited to one or a combination of several of sodium sulfate decahydrate, calcium chloride hexahydrate, barium hydroxide octahydrate, sodium acetate trihydrate, aluminum ammonium sulfate dodecahydrate, and aluminum potassium sulfate dodecahydrate.
As a preferred embodiment, the organic phase change material is preferably paraffin phase change material, fatty acid phase change material, polyol phase change material, including but not limited to paraffin, capric acid, lauric acid, pentanediol, or a combination of several thereof.
More preferably, the hydrated salt type phase-change material is one or a mixture of two or more selected from sodium sulfate decahydrate, calcium chloride hexahydrate, barium hydroxide octahydrate and sodium acetate trihydrate, and the mass proportion of the phase-change material with the least content is not more than 10% (the mass proportion refers to the total content of all the phase-change materials as the basis).
As a preferred embodiment, the flowable medium is a liquid phase, a gas-solid phase or a gas-liquid mixed phase. Wherein, the liquid phase includes but not limited to one or a plurality of combinations of water, white oil, heat conducting oil or dimethyl silicon oil, and the gas phase includes one or a plurality of combinations of air, nitrogen, argon and helium.
As a preferred embodiment, the dispersing agent is selected from one or more of copolymer solution containing acid groups, polycarboxylate solution, polyalcohol modified polymer, alpha-olefin sulfonate polymer and the like.
A preparation method of a multi-phase medium phase-change heat storage material comprises the following steps:
(1) weighing hydrated salt phase-change material, flowable medium and dispersant according to the formula of parts by weight, mixing, and heating to melt;
(2) and cooling the melted mixture to room temperature under the disturbance condition to obtain the multi-phase medium phase-change heat storage material.
As a preferred embodiment, the disturbance in step (2) includes but is not limited to one or more combinations of mechanical stirring, mechanical vibration, mechanical shaking, electromagnetic disturbance, ultrasonic wave or pump-conveyed liquid-phase medium circulation scouring.
The hydrous salt phase-change material is a latent heat type energy storage medium, the flowable medium is a heat exchange medium, and the dispersing agent can be attached to the surface of solid particles during liquid-solid phase change of the phase-change material so as to reduce the friction force among solid crystal particles and be beneficial to more uniformly dispersing the phase-change material particles. In the exothermic process, when the flowable medium is oil, the phase-change material is water-based due to the oil phase medium, and the crystallization process can form a water-in-oil state. The influence of the disturbance modes of mechanical stirring and pump-conveyed liquid-phase medium circulation flushing on crystallization of the phase-change material in the heat release process is described below. For the mechanical stirring mode, crystallization is gradually started along with the heat release of the liquid phase-change material, the liquid phase-change material can be dispersed in a liquid phase medium in a large amount of metastable liquid beads under the action of an oil phase medium and a dispersing agent and under the action of external force, and simultaneously the heat is transferred to the liquid phase medium, and after the heat release is finished, the temperature is reduced to be lower than the phase-change temperature, so that the crystallization is finished, and a large amount of fine crystal particles are formed. For the pump transportation liquid phase medium circulation scouring mode, along with the heat release of the liquid phase-change material, the oil phase medium enters from the bottom of the phase-change material under the action of the pump, and the liquid phase medium quickly floats to the upper part of the phase-change material due to the large density difference of two phases, so that the convection heat exchange is carried out in the process, and meanwhile, the floating disturbance of the liquid phase medium enables the phase-change material to finally crystallize to form a porous flow channel structure.
The pure inorganic salt phase-change material usually needs a heat exchanger with a large heat exchange area to effectively release the stored heat because of small heat conductivity coefficient. The multi-phase medium phase-change heat storage material provided by the invention directly exchanges heat in a convection way through the flowable medium and the phase-change material, and the phase-change material can form fine particles or porous flow channels, so that the heat exchange efficiency is improved. The disturbance modes such as mechanical stirring, electromagnetic disturbance, ultrasonic wave or pump conveying liquid phase medium circulation scouring and the like can improve supercooling and phase separation and improve circulation stability. In addition, the flowable medium and the dispersing agent can disperse the phase change material therein under turbulent conditions, and exothermically crystallize to finally form fine particles or a porous flow channel structure.
The hydrated salt phase-change material involved in the invention: preferably, two or more phase-change materials are compounded, the phase-change material with a small addition amount can play a role of a nucleating agent, and the mass is preferably within 10 percent generally, so that the influence on the heat storage performance of the main phase-change material is small, and the heat release crystallization of the main phase-change material is facilitated to form fine particles to exchange heat with a flowable medium.
Flowable media: preferably, the liquid phase medium is compounded with the hydrated salt phase change material, wherein the liquid phase medium accounts for 10-50 parts, and the liquid phase medium accounts for 50-90 parts. For example, in a mechanical stirring mode, the mass ratio of the hydrous salt phase-change material to the liquid-phase medium can be selected to be 70: 30; under the circulating flushing mode of conveying the liquid-phase medium by a pump, the mass ratio of the hydrated salt phase-change material to the liquid-phase medium can be selected from 85: 15. If the liquid phase medium is too little, the liquid phase medium can completely fill the phase change material accumulation gap, and the pipeline circulation heat output cannot be finished.
Dispersing agent: excessive addition of the dispersing agent can not increase the dispersing effect of the phase-change material, but can cause poor fluidity of a multi-phase system and influence crystallization and heat exchange of the phase-change material.
Compared with the prior art, the multi-phase system prepared by the invention can form fine crystal particles or a solid containing a porous flow channel under disturbance in the solid-liquid phase change process, on one hand, the heat transfer in the heat charge and discharge process is enhanced by a direct heat convection mode with a flowable medium, and the problem of thermal resistance increase caused by agglomeration of a crystalline hydrated salt phase change material is effectively solved, on the other hand, the multi-phase system is relatively small in supercooling and phase separation, and relatively good in circulation stability.
Drawings
Fig. 1 is a heat release diagram of a phase change heat storage material of embodiment 1 of the present invention;
fig. 2 is a heat release diagram of a phase change heat storage material of embodiment 2 of the present invention;
FIG. 3 is a graph of heat release data for a heat exchange coil with a large heat exchange area built in.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The raw materials in the following examples are all common commercial products unless otherwise specified.
Example 1
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 330kg of barium hydroxide octahydrate, 3.33kg of sodium acetate trihydrate, 145kg of white oil and 0.33kg of the acidic group-containing copolymer solution were added to a suitable vessel to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under the mechanical stirring to obtain the multi-phase medium phase-change heat storage material containing a large amount of phase-change material particles.
FIG. 1 is a graph of the exotherm data for the heterogeneous media material described in example 1. The container for holding the multiphase medium material is a barrel, and heat is released after the phase change material is completely melted by filling heat. In the heat releasing process, the stirrer is used to stir the multiphase medium material at low rotation speed and with double-layer three-blade slurry, and the liquid phase medium completes the heat exchange circulation via oil pump and plate heat exchanger. As can be seen from FIG. 1, as the temperature of the phase change material is reduced, the phase change material has a remarkable exothermic platform at 76 ℃ and has no phenomenon of supercooling. The temperature of the liquid phase medium-1 represents the temperature of the liquid phase medium after heat exchange with the phase-change material, and is very close to the temperature of the phase-change material, which indicates that the liquid phase medium and the phase-change material have good heat exchange. From the point of view of heat release power, the heat release power of the water side can reach 28kW at the maximum in the initial stage, and can be kept above 10kW during the phase change. When the heat release is finished, the temperature of the liquid phase medium is close to that of the phase-change material, and the fact that the heat of the phase-change material is fully released is indicated. The phase change material releases heat and becomes a great deal of fine particle crystals. Compared with the heat release data of the heat exchange coil with a large heat exchange area arranged in the attached drawing 3, in the embodiment 1, the stirring condition can not only inhibit the supercooling phenomenon of the phase-change material, but also enable the lifting effect of the temperature-1 of the liquid-phase medium to be equivalent to the lifting effect of the constant-power heat release on the outlet water temperature of the heat exchange coil in the attached drawing 3 without the arranged heat exchange coil, and the heat resistance of the phase-change material in the embodiment 1 is low, and the heat exchange efficiency is high.
Example 2
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 330kg of barium hydroxide octahydrate, 3.33kg of sodium acetate trihydrate, 145kg of white oil and 0.33kg of the acidic group-containing copolymer solution were added to a suitable vessel to obtain a mixture. (2) Heating the mixture to melt. (3) And circularly flushing the melted mixture in white oil conveyed by a pump from bottom to top, and cooling to room temperature to obtain the multi-phase medium phase-change heat storage material containing the porous flow channel.
FIG. 2 is a graph of the exotherm data for the multiphase dielectric material of example 2. The container for holding the multiphase medium material is a barrel, and heat is released after the phase change material is completely melted by filling heat. In the heat release process, the liquid-phase medium is pumped by an oil pump to circularly wash from bottom to top to complete the heat exchange circulation. As can be seen from FIG. 3, as the temperature of the phase change material decreases, there is a significant exothermic plateau at 76 ℃ and no significant supercooling. The temperature of the liquid phase medium-1 represents the temperature of the liquid phase medium after heat exchange with the phase-change material, and is very close to the temperature of the phase-change material, which indicates that the liquid phase medium and the phase-change material have good heat exchange. After heat release is finished, the phase-change material forms a porous flow channel structure, and the apparent density of the phase-change material is smaller than that of the liquid-phase medium. Compared with the heat release data of the built-in heat exchange coil with a large heat exchange area shown in the attached drawing 3, the experimental test result of the embodiment 2 shows that the effect of increasing the temperature-1 of the liquid-phase medium without the built-in heat exchange coil can be still achieved by only pumping the liquid-phase medium to circularly wash and disturb from bottom to top, and is equivalent to the effect of constant-power heat release on the temperature of the water outlet of the heat exchange coil shown in the attached drawing 3, so that the phase-change material of the embodiment 2 is low in thermal resistance and high in heat exchange efficiency.
Example 3
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 330kg of barium hydroxide octahydrate and 220kg of water were added to a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under the mechanical stirring to obtain the multi-phase medium phase-change heat storage material containing a large amount of phase-change material particles. As the phase-change material is dissolved in water, the phase-change material solubility is reduced along with the heat release process from high temperature to low temperature in the multi-phase system, so that the phase-change material is crystallized and precipitated in the water solution, a mortar pump is preferably selected in the heat exchange process of the multi-phase system, a sleeve type heat exchanger is preferably selected in the heat exchanger, the inner pipeline of the multi-phase system is conveyed by the mortar pump, and the outer pipeline is reversely conveyed by a water pump or an oil pump to achieve the aim of convective heat exchange.
Example 4
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) and adding 24kg of sodium sulfate decahydrate, 24kg of calcium chloride hexahydrate, 2kg of sodium acetate trihydrate, 50kg of heat transfer oil and 0.01kg of polycarboxylate solution into a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under the mechanical stirring to obtain the multi-phase medium phase-change heat storage material containing a large amount of phase-change material particles.
Example 5
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 70kg of sodium sulfate decahydrate, 30kg of heat transfer oil, 0.1kg of polycarboxylate solution and 0.1kg of polyol-modified polymer were put in a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
Example 6
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 90kg of sodium sulfate decahydrate, 10kg of white oil, 0.1kg of alpha-olefin sulfonate (AOS) polymer were added to a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under the action of ultrasound to obtain the multi-phase medium phase-change heat storage material.
Example 7
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 59.5kg of barium hydroxide octahydrate, 0.5kg of sodium acetate trihydrate, 20kg of heat transfer oil, 20kg of white oil, 0.1kg of polycarboxylate solution and 0.08kg of polyol modified polymer are added into a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
Example 8
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 59.5kg of barium hydroxide octahydrate, 0.5kg of sodium acetate trihydrate, 15kg of heat conducting oil, 15kg of white oil, 15kg of simethicone, 0.1kg of polycarboxylate solution and 0.08kg of alpha-olefin sulfonate polymer are added into a proper container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
Example 9
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 50kg of paraffin wax, 15kg of white oil and 0.1kg of polycarboxylate solution were added to a suitable vessel to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
Example 10
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 50kg of capric acid, 20kg of lauric acid, 15kg of heat transfer oil, 15kg of white oil and 0.1kg of polycarboxylate solution are added into a suitable container to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
Example 11
A multi-phase medium phase-change heat storage material is prepared by the following steps: (1) 50kg of pentanediol, 15kg of white oil, 0.1kg of polycarboxylate solution were added to a suitable vessel to obtain a mixture. (2) Heating the mixture to melt. (3) And cooling the melted mixture to room temperature under electromagnetic disturbance to obtain the multi-phase medium phase-change heat storage material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (4)
1. The preparation method of the multi-phase medium phase-change heat storage material is characterized in that the phase-change heat storage material comprises the following components in parts by mass: 50-90 parts of phase change material, 10-50 parts of flowable medium and 0-0.2 part of dispersing agent;
the phase-change material is a hydrated salt phase-change material selected from one or a combination of more of sodium sulfate decahydrate, calcium chloride hexahydrate, barium hydroxide octahydrate or sodium acetate trihydrate;
the flowable medium is one or a combination of more of white oil, heat conduction oil or dimethyl silicone oil;
the preparation method comprises the following steps:
(1) weighing the phase-change material, the flowable medium and the dispersing agent according to the formula in parts by weight, mixing, and heating to melt;
(2) and cooling the melted mixture to room temperature under the disturbance condition to obtain the multi-phase medium phase-change heat storage material.
2. The method as claimed in claim 1, wherein the phase change material is a combination of multiple phase change materials, and the mass ratio of the phase change material with the least content is not more than 10%.
3. The method for preparing the multi-phase medium phase-change heat storage material as claimed in claim 1, wherein the dispersant is one or more selected from the group consisting of acid group-containing copolymer solution, polycarboxylate solution, polyol modified polymer, and alpha-olefin sulfonate polymer.
4. The method for preparing the multi-phase medium phase-change heat storage material as claimed in claim 1, wherein the disturbance in the step (2) comprises one or more of mechanical stirring, mechanical vibration, mechanical shaking, electromagnetic disturbance, ultrasonic wave or cyclic flushing of liquid-phase medium transported by a pump;
and (3) adopting one or a combination of a water pump, an oil pump, a mortar pump and a diaphragm pump for pump transportation in the step (2).
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| CN106978148A (en) * | 2017-05-05 | 2017-07-25 | 江苏启能新能源材料有限公司 | A kind of multiphase medium phase-change heat-storage material and preparation method thereof |
| DE102017008115A1 (en) * | 2017-08-26 | 2019-02-28 | Hans-Jürgen Maaß | Storage of thermal energy with phase change material |
| CN108084972A (en) * | 2018-01-18 | 2018-05-29 | 上海交通大学 | Low temperature hydrated salt phase-change heat accumulation medium and its preparation and application |
| CN109439286A (en) * | 2018-10-09 | 2019-03-08 | 中山市陶净科技有限公司 | Can fast cooling composition |
| CN110387216B (en) * | 2019-08-15 | 2021-09-03 | 广东工业大学 | Long-term stable supercooling phase change heat storage material and preparation method and application thereof |
| CN115418195B (en) * | 2022-08-18 | 2024-09-13 | 嘉兴赛曼泰克新材料有限公司 | Composite phase-change heat storage material for lithium battery pack thermal management and preparation method thereof |
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| CN101285664A (en) * | 2007-04-09 | 2008-10-15 | 李建民 | Supercritical phase-change intensified heat diffusion method and its heat-transfer medium and applications |
| CN101880520A (en) * | 2010-06-09 | 2010-11-10 | 中国科学院深圳先进技术研究院 | Inorganic hydrated salt silica phase-change material and preparation method thereof |
| CN105505329A (en) * | 2015-12-29 | 2016-04-20 | 华南理工大学 | Method for reducing condensate depression of hydrous salt phase change material by adding antisolvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285664A (en) * | 2007-04-09 | 2008-10-15 | 李建民 | Supercritical phase-change intensified heat diffusion method and its heat-transfer medium and applications |
| CN101880520A (en) * | 2010-06-09 | 2010-11-10 | 中国科学院深圳先进技术研究院 | Inorganic hydrated salt silica phase-change material and preparation method thereof |
| CN105505329A (en) * | 2015-12-29 | 2016-04-20 | 华南理工大学 | Method for reducing condensate depression of hydrous salt phase change material by adding antisolvent |
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