CN114806511A - Movable semi-packaged solid-liquid phase change heat storage material and preparation method and application thereof - Google Patents
Movable semi-packaged solid-liquid phase change heat storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a movable semi-packaged solid-liquid phase change heat storage material and a preparation method and application thereof. The invention uses the melt powder of the sparse solid-liquid phase change heat storage substrate as the packaging material, realizes the packaging of the phase change material in the form of melt marble or solid marble, can prevent the phase change material from leaking, can enable gas to pass through gaps between the powder on the surfaces of the melt marble or the solid marble to be used as a substance transfer channel, realizes the dual control of the components and the temperature of the hot fluid, and can be applied to energy storage and release and substance transfer.
Description
Technical Field
The invention belongs to the technical field of phase change heat storage, and relates to a movable non-fully-closed packaged phase change material formed by packaging a solid-liquid phase change material by using a powder packaging material, and a preparation method and application thereof.
Background
Phase change materials are materials that are capable of providing latent heat through a change in state of matter or phase at a fixed phase change temperature. The process of storing or releasing heat or cold by utilizing the phase-change material is called phase-change heat storage or release, and the mismatching of regulating and controlling energy supply on time and space is achieved.
The phase change material comprises a solid-liquid phase change material, a solid-gas phase change material, a liquid-gas phase change material and a solid-solid phase change material, wherein the solid-liquid phase change material is most widely applied because the solid-liquid phase change material can overcome the overlarge volume change of solid-gas phase change and liquid-gas phase change, and the energy storage efficiency and the raw material category are superior to those of solid-solid phase change heat storage.
However, in the solid-liquid phase change heat storage process, in order to prevent the phase change material from leaking, the phase change material is generally fixed in a packaging manner. Currently, the packaging methods can be simply classified into a fully-sealed package and a semi-sealed package according to whether or not there is a substance transfer. The fully-closed type packaging (fully packaging for short) is to completely coat the solid-liquid phase change material with the packaging material, so that the safety is high, liquid leakage is not easy to occur, the phase change material is completely arranged inside a packaging shell layer, and the heat capacity is high; however, the phase-change material cannot exchange substances with the outside, and is difficult to regulate and control humidity. Semi-closed type packaging (semi-packaging for short), namely non-fully closed type packaging, in the prior art, a common implementation mode of semi-packaging is to fix a solid-liquid phase-change material in a porous medium, although the packaging mode can enable the phase-change material to be directly contacted with a heat exchange medium for heat and mass transfer to realize temperature and humidity control of the environment, the load capacity of the phase-change material is limited by the porous medium, the average load capacity is only maintained at about 80%, the volume heat capacity of the phase-change heat exchange medium can be influenced, particularly in the humidity control and temperature control processes, the volume of the phase-change material is changed after moisture absorption, the thermophysical property changes to cause flowability change, and the phase-change material is easy to leak. Therefore, the packaging problem of the solid-liquid phase change heat storage material capable of realizing temperature and humidity control is difficult to solve by the existing packaging technology.
Disclosure of Invention
The invention aims to provide a movable semi-packaged solid-liquid phase change heat storage material and a preparation method thereof aiming at overcoming the problems of the existing semi-packaging mode. It is a further object of the present invention to provide the use of mobile semi-encapsulated solid-liquid phase change thermal storage materials for energy storage and release, and mass transfer.
The movable semi-packaged solid-liquid phase change heat storage material is a solid-liquid phase change heat storage base material melt marble formed by coating the sparse solid-liquid phase change heat storage base material melt powder on the surface of a solid-liquid phase change heat storage base material melt or a solid marble formed by phase change of the melt marble. The term "mobile encapsulation" refers to that the powder of the hydrophobic-liquid phase change heat storage substrate molten liquid on the surface of the marble can move freely with the change of external or internal conditions, and rearrange. The semi-encapsulation means that gaps exist among powder particles on the surfaces of the marbles, gas permeability is good, heat and mass transfer channels are provided, and mass transfer can be achieved.
The movable semi-packaged solid-liquid phase change heat storage material has elasticity in a molten state, is easy to cut, has single-layer or multi-layer surface powder, and ensures the stability of marbles.
The solid-liquid phase change heat storage base material can be selected according to application requirements, and the phase change temperature of the solid-liquid phase change heat storage base material is within the range of 20-600 ℃. The solid-liquid phase change heat storage base material is at least one of a crystalline hydrate, a molten salt, a eutectic salt, a urea, sulfur, paraffin, an alcohol, a polymer, and the like, but the present invention is not limited to the above-exemplified range. In preferred implementations, the crystalline hydrate includes, but is not limited to, iron nitrate nonahydrate, sodium silicate pentahydrate, iron trichloride hexahydrate, sodium acetate trihydrate, and the like. Such molten salts include, but are not limited to, sodium nitrate, potassium nitrate, lithium nitrate, and the like. The eutectic salts include, but are not limited to, 50% lithium chloride-50% aluminum trichloride, sodium nitrate-erythritol, solar salts, potassium iodide-lithium iodide, and the like. Such ureas include, but are not limited to, thiourea, urea phosphates, and the like. Such alcohols include, but are not limited to erythritol, polyethylene glycol, erythritol, sorbitol, and the like. The solid-liquid phase change heat storage base material is in a powder state in an initial state.
The powder of the solvophobic-liquid phase-change thermal storage substrate melt in the present invention may be at least one of a metal powder, a metal oxide powder, and an inorganic non-metal powder modified with the solvophobic-liquid phase-change thermal storage substrate melt, and an organic polymer powder of the solvophobic-liquid phase-change thermal storage substrate melt, but the present invention is not limited to the above exemplified ranges. Including but not limited to iron powder, copper powder, gold powder, and the like. The metal oxide powder includes, but is not limited to, ferroferric oxide powder, copper oxide powder, titanium dioxide powder, and the like. The inorganic non-metal powder includes, but is not limited to, silicon dioxide powder, talc powder, graphene powder, carbon nanotubes, and the like. The organic polymer powder of the solvophobic-liquid phase change thermal storage substrate melt includes, but is not limited to, polypropylene powder, polytetrafluoroethylene powder, polystyrene powder, and the like. The size of the solid-liquid phase change heat storage substrate molten liquid powder can be in the nanometer level, the micron level, the millimeter level and the like. The shape of the solid-liquid phase change thermal storage base material melt powder may be at least one of a sheet, a sphere, a block, and the like.
The invention relates to a preparation method of a movable semi-packaged solid-liquid phase change heat storage material, which takes solid-liquid phase change heat storage base material powder and solid-liquid phase change heat storage base material melt powder as raw materials, the solid-liquid phase change heat storage base material powder and the solid-liquid phase change heat storage base material melt powder are measured according to the mass ratio of (1-1000):1, and melt marbles are prepared through a melting coating or pre-mixing melting process, as shown in figure 1.
The melting and coating process comprises the following steps: heating and melting solid-liquid phase change heat storage substrate powder on a solid-liquid phase change heat storage substrate melting liquid heating plate which is higher than a solid-liquid phase change heat storage substrate melting point and lower than a solid-liquid phase change heat storage substrate decomposition temperature to obtain solid-liquid phase change heat storage substrate melt, and then rolling the solid-liquid phase change heat storage substrate melt on the solid-liquid phase change heat storage substrate melting liquid powder arranged on the solid-liquid phase change heat storage substrate melting liquid heating plate to enable the solid-liquid phase change heat storage substrate melting liquid powder to be coated on the surface of the solid-liquid phase change heat storage substrate melt to form a melt marble;
the premixing and melting process comprises the following steps: the solid-liquid phase change heat storage base material powder and the sparse solid-liquid phase change heat storage base material molten liquid powder are uniformly mixed to form a mixture, the mixture is placed on a sparse solid-liquid phase change heat storage base material molten liquid heating plate which is higher than the solid-liquid phase change heat storage base material melting point and lower than the solid-liquid phase change heat storage base material decomposition temperature, the mixture is heated and melted, the solid-liquid phase change heat storage base material powder in the mixture is melted and aggregated into solid-liquid phase change heat storage base material melt, and the sparse solid-liquid phase change heat storage base material molten liquid powder is coated on the surface of the solid-liquid phase change heat storage base material melt to form a melt marble.
In the preparation method of the movable semi-packaged solid-liquid phase change heat storage material, the melt coating process is to adhere the solid-liquid phase change heat storage base material melt powder to the surface of the melt to coat the solid-liquid phase change heat storage base material to form melt marbles by moving the solid-liquid phase change heat storage base material melt; the premixing and melting process is characterized in that solid-liquid phase change heat storage base materials are melted and gathered into a melt, so that solid-liquid phase change heat storage base material melt powder spontaneously migrates from the melt to a gas-liquid interface to wrap the solid-liquid phase change heat storage base materials to form melt marbles. The dosage of the solid-liquid phase change heat storage substrate molten liquid powder is mainly related to the particle size and the density of the solid-liquid phase change heat storage substrate molten liquid powder. When the sparse solid-liquid phase change thermal storage substrate molten liquid powder is micron silica powder, the mass ratio of the sparse solid-liquid phase change thermal storage substrate molten liquid powder to the solid-liquid phase change thermal storage substrate is preferably 1: 2-1: 20. if the use amount of the sparse solid-liquid phase change heat storage substrate molten liquid powder is too small, the sparse solid-liquid phase change heat storage substrate molten liquid powder is difficult to effectively cover the surface of the solid-liquid phase change heat storage material melt, so that the phase change material in the melt marble is exposed or overflows.
The preparation method of the movable semi-packaged solid-liquid phase change heat storage material has no limitation on the material of the heating plate, and can be one or a plurality of metal plates, alloy plates, inorganic non-metal plates and the like with good heat conductivity, or the metal plates, the alloy plates, the inorganic non-metal plates and the like are stacked together. The heating plate is modified to ensure that the surface of the heating plate has super-sparse solid-liquid phase change heat storage base material molten liquid property, so that the solid-liquid phase change heat storage base material molten liquid is prevented from adhering to the surface, the molten liquid is difficult to shrink automatically into balls, and the surface of the sparse solid-liquid phase change heat storage base material molten liquid heating plate (especially a super-hydrophobic heating plate) has better corrosion resistance. The heating plate may also be replaced by a closed heating device. For a closed heating device, to adhere a sufficient amount of the solvophobic-liquid phase change thermal storage substrate melt powder, the closed heating device may be shaken slightly to increase the amount of contact of the solvophobic-liquid phase change thermal storage substrate melt powder with the solid-liquid phase change thermal storage substrate.
In the preparation method of the movable semi-packaged solid-liquid phase change heat storage material, in the premixing and melting process, the mixing mode of the solid-liquid phase change heat storage base material melting liquid powder and the solid-liquid phase change heat storage base material can be shaking, ball milling and dispersing, mechanical stirring, oscillating mixing and the like.
The movable semi-packaged solid-liquid phase change heat storage material provided by the invention can be applied to the field of phase change heat storage, realizes the release and storage of energy, and can generate the transfer of substances. The phase change heat storage field comprises energy storage and release in the fields of solar energy, electric energy, wind energy, nuclear energy, geothermal energy, industrial waste heat, fossil fuel and the like. According to the invention, through substance transfer, dual control of hot fluid components and temperature can be realized. The substance in the substance transfer may be not only water but also at least one of hydrogen sulfide, carbon dioxide, sulfur gas oxide, nitrogen gas oxide, volatile organic compound, and other gases, but the present invention is not limited to the above-described exemplary range. The gaseous oxides of sulfur include, but are not limited to, SO 2 、SO 3 Etc.; the gaseous oxides of nitrogen include, but are not limited to, N 2 O、NO 2 、N 2 O 3 Etc.; the volatile organic compounds include but are not limited to formaldehyde, acetone, and the like.
In summary, the invention provides a novel movable semi-packaging technology of solid-liquid phase change heat storage material, wherein the loose solid-liquid phase change heat storage base material molten liquid powder is coated on the surface of the solid-liquid phase change heat storage material melt to form a melt marble, and the melt marble releases latent heat in the cooling process and undergoes phase change to form a solid marble. The sparse solid-liquid phase change heat storage base material molten liquid powder on the surface of the melt marble is in an independent state, and is migrated and rearranged along with the volume expansion or contraction of the melt marble, but is always positioned on the surface of the melt marble to form a compact or loose packaging shell layer to bind the phase change heat storage material, so that leakage is prevented; after the melt marble is converted into a solid marble, the volume change is small, and the loose solid-liquid phase change heat storage base material molten liquid powder is still coated on the surface of the solid-liquid phase change heat storage material; gaps exist between the melt marble and the sparse solid-liquid phase change heat storage substrate molten liquid powder on the surface of the solid marble, the gas permeability is good, and a heat and mass transfer channel is provided.
The movable semi-packaged solid-liquid phase change heat storage material and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the loose solid-liquid phase change heat storage base material molten liquid powder is used as a packaging material, the movable semi-packaged solid-liquid phase change heat storage material is obtained through a melting coating or premixing melting process, the movable semi-packaged solid-liquid phase change heat storage material is of a marble structure, the loose solid-liquid phase change heat storage base material molten liquid powder on the surface of the movable semi-packaged solid-liquid phase change heat storage material can migrate and rearrange along with the expansion or contraction of the phase change material, when the volume of the phase change material is contracted, the surface powder is arranged tightly, and when the volume of the phase change material is expanded, the surface powder is arranged loosely; but the surface powder can stably exist in a gas-liquid two-phase interface or a gas-solid two-phase interface, so that leakage is prevented, and plastic fatigue damage of the traditional packaging material does not exist.
(2) Because the sparse solid-liquid phase change heat storage base material molten liquid powder is used as the packaging material, the obtained movable semi-packaged solid-liquid phase change heat storage material has non-adhesiveness and elasticity, does not coalesce when colliding with each other, and can automatically recover to the original shape after deformation.
(3) Because the solid-liquid phase change heat storage base material molten liquid powder is used as the packaging material, the melt marble is obtained through the melting coating or premixing melting process, and the melt marble is cooled to form the solid marble, the solid-liquid phase change heat storage material in the packaging mode improves the heat exchange efficiency compared with the fully packaged solid-liquid phase change heat storage material.
(4) According to the movable semi-packaged solid-liquid phase change heat storage material, gaps exist among the solid-liquid phase change heat storage base material molten liquid powder on the surface, and a heat and mass transfer channel is provided, so that the material transfer can be carried out between the movable semi-packaged solid-liquid phase change heat storage material and a heat exchange medium, and the dual control of the components and the temperature of a hot fluid is realized.
(5) The invention takes the sparse solid-liquid phase change heat storage base material molten liquid powder as the packaging material to realize the movable semi-packaging of the solid-liquid phase change heat storage base material, is completely different from the packaging technology of any existing phase change material, and provides a brand new technical scheme for the packaging of the phase change energy storage material.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a mobile semi-encapsulated solid-liquid phase change thermal storage material according to the present invention; wherein, (a) corresponds to a melting and coating process, and (b) corresponds to a premixing and melting process.
FIG. 2 is a photograph of the beads of example 1 and four prepared marbles; wherein a is water bead, b is polytetrafluoroethylene-coated water marble, c is polytetrafluoroethylene-coated iron nitrate nonahydrate marble, d is polytetrafluoroethylene-coated sodium silicate pentahydrate marble, and e is polytetrafluoroethylene-coated polyethylene glycol marble.
FIG. 3 is a photograph of a melt marble obtained by coating different solid-liquid phase change thermal storage substrate melts with a powder of a sparse solid-liquid phase change thermal storage substrate melt in examples 1-8; wherein, (a1) is a photograph obtained by a melt coating process, and (a2) is a photograph obtained by a pre-mix melting process.
FIG. 4 is a photograph of melt marbles prepared from erythritol and modified silica in different mass ratios in example 8 using a premixed melting process; wherein the mass ratio of (a) erythritol to modified silicon dioxide is 5: 1; (b) the mass ratio of the erythritol to the modified silicon dioxide is 10: 1; (c) the mass ratio of the erythritol to the modified silicon dioxide is 15: 1; (d) the mass ratio of the erythritol to the modified silicon dioxide is 20: 1; (e) the mass ratio of the erythritol to the modified silicon dioxide is 30: 1; (f) the mass ratio of the erythritol to the modified silicon dioxide is 50: 1; (g) the mass ratio of the erythritol to the modified silicon dioxide is 2: 1; (h) is an enlarged photograph of a portion of the marbles in (g).
FIG. 5 is a thermal infrared analysis chart of the phase transition heat exchange process of the melt marble in example 8.
FIG. 6 is a photograph showing a cyclic phase transition process of the mobile semi-encapsulated solid-liquid phase change thermal storage material prepared by using erythritol as a phase transition thermal storage substrate in example 8; wherein, (a) the solidification time of the erythritol from the melt to the solid, and (b) the erythritol is changed from the solid state to the molten state by heating.
FIG. 7 is a photograph of a molten marble prepared by mixing erythritol and modified ferroferric oxide powder according to different mass ratios in example 9; wherein, the left column and the right column with the same proportion are obtained by shooting the same sample from different angles.
FIG. 8 is a schematic diagram showing the mass change of the mobile semi-encapsulated solid-liquid phase change thermal storage material prepared by using erythritol as a phase change thermal storage base material in the processes of moisture absorption and drying in example 8; the mass ratio of the erythritol to the hydrophobically modified silicon dioxide powder is 15: 1.
Detailed Description
The technical solution of the present invention is further described below by way of examples with reference to the accompanying drawings.
Since the phase change heat storage substrates used in the following examples all have strong polarity, the solid-liquid phase change heat storage substrate melt powder used in the following examples is a nonpolar hydrophobic powder.
The following examples use open super hydrophobic heating plates. The method for modifying the heating plate comprises the following steps: soaking the purchased copper plate in 1M HCl to clean, and removing surface oxides; then, ultrasonically cleaning the copper plate in acetone, ethanol and distilled water for 10min respectively; then soaking the cleaned copper plate into the LHCl with the concentration of 1mol/LHCl for 5 min; the copper plate was rinsed with deionized water and dried with cold air. The dried copper plate has a concentration of 1mol/L NaOH and a concentration of 0.05mol/LK 2 S 2 O 8 Soaking and etching in the solution for 30min, taking out the etched copper plate from the solution, and placing in deionized waterAnd (4) rinsing. Then, the etched copper plate was modified with a1 wt% fluorosilane (FAS-17) ethanol solution for 6 hours. And finally, heating the modified copper plate in an oven at 80 ℃ for 30min to obtain the super-hydrophobic heating plate.
The following examples describe the method of hydrophobizing a needle: coating polyvinyl alcohol adhesive on the surfaces of the glass needle and the stainless steel needle, and then adhering commercial polytetrafluoroethylene nano powder to obtain the hydrophobic needle.
The preparation method of hydrophobically modified micron-sized silica (called hydrophobically modified silica for short) in the following examples: mixing a fluorosilicone alcohol solution (concentration of 1 wt%) with silica powder (about 25 microns), the ratio of the volume of the fluorosilicone alcohol solution to the mass of the silica powder being 1:1 (the volume unit of the fluorosilane alcohol solution is mL, and the mass unit of the silicon dioxide powder is g), then placing the mixed solution in a centrifugal tube and closing, shaking the centrifugal tube to completely soak the silicon dioxide powder in the fluorosilane alcohol solution, and modifying for 12 hours; then solid-liquid separation is carried out, the fluorosilane alcohol solution is removed, and the modified silicon dioxide is placed in an oven with the temperature of 80 ℃ and dried for more than 12 hours.
The preparation method of hydrophobically modified ferroferric oxide (referred to as hydrophobically modified ferroferric oxide) in the following examples: adding a fluorosilane alcohol solution (with the concentration of 1 wt%) into the micro-nano powder of the commercial ferroferric oxide, wherein the fluorosilane alcohol solution is added in an amount of submerging all the ferroferric oxide powder, then placing the mixed solution into a centrifuge tube and closing the centrifuge tube, shaking the centrifuge tube to disperse the ferroferric oxide powder in the fluorosilane solution, and modifying for 12 hours; and then removing the fluorosilane alcohol solution, and placing the modified ferroferric oxide powder in an oven at 80 ℃ for drying for more than 12 hours.
Example 1
In this example, polytetrafluoroethylene powder is used as the melt powder of the hydrophobic solid-liquid phase change thermal storage base material, and water beads, ferric nitrate nonahydrate, sodium silicate pentahydrate and polyethylene glycol are used as the solid-liquid phase change thermal storage base materials, respectively, to prepare the movable semi-encapsulated solid-liquid phase change thermal storage material.
The preparation steps of this example are as follows:
(1) 0.025g of polytetrafluoroethylene hydrophobic powder (purchased from outsourced) is uniformly spread on the surface of a super-hydrophobic heating plate, and then 0.017g of ferric nitrate nonahydrate, 0.026g of sodium silicate pentahydrate, 0.011g of polyethylene glycol and 10 microliter of water drop are respectively weighed and placed on the polytetrafluoroethylene hydrophobic powder spread on the surface of the heating plate.
(2) And heating the heating plate to 60 ℃ to melt the ferric nitrate nonahydrate, the sodium silicate pentahydrate and the polyethylene glycol, and stirring the molten ferric nitrate nonahydrate, the molten sodium silicate pentahydrate and the polyethylene glycol melt and the water beads by using a hydrophobic needle in the melting process, so that the molten ferric nitrate nonahydrate, the molten sodium silicate pentahydrate and the polyethylene glycol melt and the water beads can be adhered with polytetrafluoroethylene powder to form melt marbles.
(3) The melt marble formed in the step (2) has poor sphericity, and the melt marble with good sphericity can be obtained by further extruding and cutting the melt marble through a hydrophobic needle, as shown in fig. 2.
The extrusion cutting of the melt marble in the step (3) can also be controlled by controlling the initial feeding amount, so that the difficulty in controlling the size and quality of the marble caused by cutting is avoided.
Example 2
In the embodiment, the hydrophobically modified silica powder is used as the melt powder of the solid-liquid phase change heat storage base material, and the sulfur is used as the solid-liquid phase change heat storage base material to prepare the movable semi-encapsulated solid-liquid phase change heat storage material.
The steps of this embodiment are as follows:
(1) 0.021g of hydrophobically modified silicon dioxide powder is uniformly spread on the surface of a super-hydrophobic heating plate, and then 0.021g of sulfur powder is weighed and placed on the hydrophobically modified silicon dioxide powder spread on the surface of the heating plate.
(2) And heating the heating plate to 130 ℃ to melt the sulfur, and stirring the sulfur melt by using a hydrophobic needle in the melting process to enable the sulfur melt to be adhered with the hydrophobic modified silicon dioxide powder to form melt marble.
(3) And (3) the melt marble formed in the step (2) has poor sphericity, and the melt marble with good sphericity can be obtained by further extruding and cutting the melt marble through a hydrophobic needle.
The extrusion cutting of the melt marble in the step (3) can also be controlled by controlling the initial feeding amount, so that the difficulty in controlling the size and quality of the marble caused by cutting is avoided.
Example 3
In the embodiment, hydrophobically modified silica powder is used as melt powder of a hydrophobic solid-liquid phase change heat storage base material, and ferric nitrate nonahydrate and ferric trichloride hexahydrate are used as solid-liquid phase change heat storage base materials to prepare the movable semi-packaged solid-liquid phase change heat storage material.
The steps of this embodiment are as follows:
(1) according to the mass ratio of the solid-liquid phase change heat storage base material to the sparse solid-liquid phase change heat storage base material molten liquid powder of 15:1, respectively mixing ferric nitrate nonahydrate and ferric trichloride hexahydrate with hydrophobically modified silicon dioxide powder, and then weighing 10mg of the mixed materials and placing the materials on the surface of a super-hydrophobic heating plate.
(2) And heating the heating plate to 60 ℃, melting and spontaneously aggregating ferric nitrate nonahydrate and ferric trichloride hexahydrate in the mixed material into a spherical shape, and adhering the hydrophobically modified silicon dioxide powder in the mixed material to the surface of the spherical melt to form the melt marble.
The melt marble is extruded and cut by the hydrophobic needle or the mixing proportion and the adding amount of the initial materials are controlled, so that the size of the melt marble can be controlled.
Example 4
In this example, hydrophobically modified silica powder was used as the melt powder of the hydrophobic solid-liquid phase change thermal storage base material, and sulfur was used as the solid-liquid phase change thermal storage base material to prepare the mobile semi-encapsulated solid-liquid phase change thermal storage material.
The steps of this embodiment are as follows:
(1) mixing the hydrophobically modified silicon dioxide powder and the sulfur powder according to the mass ratio of 1:15, and weighing 10mg of the mixed material to be placed on the surface of a super-hydrophobic heating plate.
(2) And heating the heating plate to 130 ℃, melting sulfur in the mixed material and spontaneously aggregating the sulfur into balls, and adhering the hydrophobically modified silicon dioxide powder in the mixture to the surface of the spherical melt to form melt marbles.
The size of the melt beads can be controlled by adding amounts of the mixing materials or by controlling the ratio of the mixing materials.
Example 5
In the embodiment, hydrophobically modified silica powder is used as the melt powder of the hydrophobic solid-liquid phase change heat storage base material, and lithium nitrate and sodium nitrate are used as the solid-liquid phase change heat storage base materials respectively to prepare the movable semi-packaged solid-liquid phase change heat storage material.
The steps of this embodiment are as follows:
(1) 0.02g of hydrophobically modified silica powder was spread on the surface of a superhydrophobic heating plate, and 0.01g of lithium nitrate powder and 0.01g of sodium nitrate powder were weighed respectively on the hydrophobically modified silica powder spread on the surface of the heating plate.
(2) Heating the heating plate to 270 ℃, wherein the temperature can fluctuate within the range of 270-290 ℃, sealing the heating area by using a quartz glass cover, melting and spontaneously aggregating the lithium nitrate powder and the sodium nitrate powder into balls, slightly shifting by using a preheated hydrophobic glass needle, and spontaneously adhering the hydrophobic modified silicon dioxide powder to the surfaces of the lithium nitrate and the sodium nitrate melts along with the rolling of the melts to form melt marbles.
(3) And closing the heating plate, reducing the temperature of the heating plate to change the lithium nitrate and sodium nitrate melt marbles into solid marbles, heating the solid marbles to 270 ℃ again to change the solid marbles into melt marbles again, and realizing the energy storage and release of heat through phase change.
The hydrophobically modified silicon dioxide powder used in the step (1) can be replaced by hydrophobically modified ferroferric oxide powder.
In the step (2), a plurality of independent lithium nitrate and sodium nitrate melt marbles can be obtained by cutting, and the heat exchange area is increased.
Example 6
In the embodiment, the hydrophobically modified silica powder is used as the melt powder of the hydrophobic solid-liquid phase change heat storage base material, and the lithium nitrate and the sodium nitrate are used as the solid-liquid phase change heat storage base material to prepare the movable semi-packaged solid-liquid phase change heat storage material.
The steps of this embodiment are as follows:
(1) according to the mass ratio of the solid-liquid phase change heat storage base material to the solid-liquid phase change heat storage base material melt powder of 15:1, mixing the hydrophobically modified silicon dioxide powder with lithium nitrate and sodium nitrate respectively, and then weighing 10mg of the mixed material to be placed on the surface of a super-hydrophobic heating plate.
(2) And heating the heating plate to 270 ℃, melting and spontaneously aggregating lithium nitrate and sodium nitrate in the mixed material into balls, and adhering the hydrophobic modified silicon dioxide powder in the mixed material to the surface of the spherical melt to form the melt marble.
(3) And closing the heating plate, reducing the temperature of the heating plate to change the lithium nitrate and sodium nitrate melt marbles into solid marbles, heating the solid marbles to 270 ℃ again to change the solid marbles into melt marbles, and realizing the energy storage and release of heat through phase change.
Controlling the quality of the mixed material in the step (2) to obtain lithium nitrate and sodium nitrate melt marbles with different sizes; in the step (2), a plurality of independent lithium nitrate and sodium nitrate melt marbles can be obtained by cutting, and the heat exchange area is increased.
Example 7
In this example, a hydrophobically modified silica powder was used as a hydrophobic-liquid phase change heat storage base material melt powder, and erythritol (C) 4 H 10 O 4 ) The movable semi-packaged solid-liquid phase change heat storage material is prepared as a solid-liquid phase change heat storage base material.
The steps of this embodiment are as follows:
(1) 0.015g of hydrophobically modified silica powder was spread on the surface of a superhydrophobic heating plate, and 0.015g of erythritol was weighed and placed on the hydrophobically modified silica powder spread on the surface of the heating plate.
(2) And heating the heating plate to 140 ℃, melting erythritol and spontaneously aggregating the erythritol into balls, slightly shifting the erythritol by using a preheated hydrophobic stainless steel needle, and spontaneously transferring the hydrophobic modified silicon dioxide powder from the heating plate to the surface of the erythritol melt along with the rolling of the melt to wrap the erythritol to form melt marbles.
(3) And closing the heating plate, and reducing the temperature of the heating plate to cool the melt marble, wherein the erythritol melt marble has a supercooling phenomenon, and the melt state is still maintained even if the temperature is lower than the phase transition temperature (140 ℃). The melt marble is rapidly changed in phase by touching the melt marble with a hydrophobic needle, and latent heat is released to form a solid marble.
In the step (2), a plurality of independent erythritol fused marbles can be obtained by cutting, so that the heat exchange area is increased.
Example 8
In this example, a hydrophobically modified silica powder was used as a hydrophobic-liquid phase change heat storage base material melt powder, and erythritol (C) 4 H 10 O 4 ) The movable semi-packaged solid-liquid phase change heat storage material is prepared as a solid-liquid phase change heat storage base material.
The steps of this embodiment are as follows:
(1) mixing erythritol and hydrophobically modified silicon dioxide powder according to the mass ratio of 15:1 to form a mixed material.
(2) Weighing two parts of 0.015g of mixed material, and respectively placing the mixed material on the surface of a super-hydrophobic heating plate; and heating the heating plate to 140 ℃, melting erythritol in the mixed material and spontaneously aggregating to form spheres, and spontaneously adhering the hydrophobic modified silicon dioxide powder to the surface of the erythritol spherical melt to form two melt marbles.
(3) Closing the heating plate, and reducing the temperature of the heating plate to cool the melt marble, wherein the erythritol melt marble has a supercooling phenomenon, and even if the temperature is lower than the phase transition temperature (for example, the temperature of the heating plate is reduced to 67.3 ℃), the melt marble still keeps a melt state and does not undergo phase transition (see fig. 5); the melt marble rapidly changes phase by touching it with a hydrophobic needle and releases latent heat, with less than 1s of time to transform from the melt marble to a solid marble (see fig. 6).
(4) The erythritol melt marble obtained in step (2) was subjected to liquid → solid, solid → liquid phase change operation repeatedly for 10 times, and the result showed that the melt marble was still able to exist stably.
The hydrophobic powder spread in the step (1) can be replaced by hydrophobic modified SiO with different particle sizes 2 Hydrophobic modification of powders, e.g. of nanometric scaleSilica powder or micron-sized hydrophobically modified silica powder having a larger particle size.
The mass ratio of the erythritol to the hydrophobically modified silica powder in step (1) is adjusted within the range of 2:1 to 50:1, and a melt marble in the range of 0.3mm to 1.8mm can be obtained (as shown in fig. 4).
The quality of the mixed materials in the step (2) can be adjusted to obtain melt marbles with different sizes, and a plurality of independent erythritol melt marbles can also be obtained by cutting, so that the heat exchange area is increased.
Example 9
In the embodiment, the hydrophobic modified ferroferric oxide powder is used as a solid-liquid phase change heat storage base material molten liquid material, and the erythritol is used as a solid-liquid phase change heat storage base material to prepare the movable semi-packaged solid-liquid phase change heat storage material.
The steps of this embodiment are as follows:
(1) mixing the hydrophobically modified ferroferric oxide particles and the erythritol according to the mass ratio of the erythritol to the hydrophobically modified ferroferric oxide powder of 100:1,300:1,600:1 and 900:1 respectively to form mixed materials, and then weighing 10mg of the mixed materials with different mass ratios respectively and placing the mixed materials on the surface of the super-hydrophobic heating plate.
(2) And heating the heating plate to 140 ℃, melting erythritol in the mixed material and spontaneously aggregating to form balls, and adhering the hydrophobic modified ferroferric oxide powder in the mixture to the surface of the erythritol spherical melt to form the melt marble.
The melt marble prepared by this example is shown in FIG. 7.
The movable semi-encapsulated solid-liquid phase change heat storage material prepared in the above example was analyzed for structure and performance as follows:
(I) structural analysis
The images of the melt marble and the solid marble formed by phase change of the melt marble prepared in examples 1 to 9 and the preparation process thereof are collected, and the obtained photographs are shown in fig. 2 to 4, fig. 6 and fig. 7, and it can be seen from the figures that the movable semi-encapsulated solid-liquid phase change heat storage material of the invention is a melt marble formed by coating solid-liquid phase change heat storage substrate melt with sparse solid-liquid phase change heat storage substrate melt powder or a solid marble formed by cooling and phase change of the melt marble.
(II) analysis of Properties
1. Analysis of phase-change thermal storage Properties
The thermal infrared analysis was performed on the pure erythritol melt without being coated with the hydrophobically modified silica and the erythritol melt marble prepared in example 8 using the hydrophobically modified silica powder as the hydrophobic-liquid phase change thermal storage substrate melt powder and the erythritol as the phase change thermal storage substrate, and the test results are shown in fig. 5. The initial temperature of the hot plate was set at 140 ℃, but the initial temperature of the erythritol melt marbles was only 130 ℃ probably due to the presence of the surface coated hydrophobically modified silicondioxide powder, while the temperature of the pure erythritol melt was 138 ℃ higher than the initial temperature of the erythritol melt marbles. The temperatures of the pure erythritol melt and the erythritol melt marbles gradually decrease along with the temperature decrease in the cooling process, and the temperatures of the pure erythritol melt and the erythritol melt marbles are reduced to 67.3 ℃ from the initial temperature after 40 seconds, and the temperatures are basically kept stable and do not change any more. The cooling process is the release of sensible heat, the release speeds of the pure erythritol fusant and the erythritol fusant marbles are almost the same, namely the heat exchange efficiency between the erythritol fusant marbles and the erythritol fusant is almost the same, which fully shows that the encapsulation powder of the fusant marbles can realize the stable structure of the fusant, the phase-change material does not leak, and the heat exchange efficiency of the fusant is not influenced, so that the encapsulation of the phase-change material is very beneficial.
The pure erythritol melt and the erythritol melt marbles were then stimulated sequentially with a hydrophobic needle, respectively, and they underwent phase changes sequentially (see fig. 5). After the phase change occurs, the temperatures of the pure erythritol melt and the erythritol melt marbles start to rise firstly, rise from 67.3 ℃ to nearly 100 ℃, the highest temperatures of the pure erythritol melt and the erythritol melt are not greatly different, and then fall from the highest temperature to about 67.3 ℃, and the latent heat of phase change is released; all latent heat is released when the phase change temperature of the pure erythritol melt is continuously changed for 25.2s, and the latent heat is completely released when the phase change temperature of the erythritol melt marbles is continuously changed for 30.9sThe reason is that the outer surface of the erythritol fused marble is coated with the hydrophobically modified SiO 2 Powder, the time for releasing the phase change latent heat is increased, but the increase is not large. Therefore, the latent heat release of the erythritol melt marble is relatively slow compared with that of a pure erythritol melt, but the erythritol melt marble has the characteristic of fast latent heat release in the whole view.
The analysis shows that the movable semi-packaged solid-liquid phase change heat storage material provided by the invention has good heat exchange performance and can be used as a medium for photo-thermal energy storage and waste heat recovery.
2. Stability analysis
The cyclic phase change process of the solid-liquid phase change thermal storage material prepared by using the hydrophobic modified silica powder as the hydrophobic solid-liquid phase change thermal storage substrate molten liquid powder and using the erythritol as the phase change thermal storage substrate in example 8 was tested, and the collected picture is shown in fig. 6. As can be seen from FIG. 6, the erythritol melt marble was transformed into a solid marble by cooling and the erythritol solid marble was transformed into a melt marble by melting with heating during a single phase transition. Example 8 shows that the erythritol melt marble has supercooling phenomenon, the phase change occurs rapidly after the melt marble is stirred by a hydrophobic needle, and the time for converting the melt marble into a solid marble is less than 1 s. As can be seen from FIG. 6(a), the volume hardly changes during the process of converting the erythritol fused marble into the solid marble, and the calculated volume change rate is less than 5%, the contact angle is reduced from 137 degrees to 130 degrees, and the light transmittance is instantly reduced.
As can be seen from fig. 6(b), in the process of heating the erythritol solid marble from the solid phase to the liquid phase, the solid is gradually converted into the melt from the bottom of the solid marble because the heating plate is at the bottom of the solid marble, but it is observed that the hydrophobic modified silica powder on the surface is kept substantially still at the beginning of heating, mainly because the hydrophobic modified silica powder on the surface forms a complete shell layer, contacts and supports each other, and is adhered to the melt without moving; with the rise of temperature, the packaging shell layer on the surface part of the marble is cracked due to local uneven stress and volume expansion in the solid-liquid conversion process of erythritol; along with the continuous increase of the temperature, the crack is gradually increased until the erythritol is completely in a molten state, and the packaging powder moves in the process and is rearranged and moved, but is always positioned on the surface of the melt marble to form a compact or loose packaging shell layer to bind the phase change heat storage material, so that the leakage is prevented; in the process of converting from a solid phase to a liquid phase, the light transmittance of the marble is gradually enhanced, and the contact angle of the marble on a heating plate is gradually increased. Example 8 shows that the morphology and stability (including volume, light transmittance, contact angle, etc.) of the melt marble are basically kept unchanged with the increase of the phase change times, and the melt marble can still exist stably after being subjected to phase change for 10 times.
It can be seen from the above analysis that the mobile semi-encapsulated solid-liquid phase change thermal storage material prepared in example 8 by using hydrophobically modified silica powder as the hydrophobic solid-liquid phase change thermal storage base material molten powder and erythritol as the solid-liquid phase change thermal storage base material has stability of cyclic phase change, and can realize a stable heat absorption-heat release cyclic process. Therefore, the movable semi-packaged solid-liquid phase change heat storage material provided by the invention has good phase change stability and can be used as a medium for photo-thermal energy storage and waste heat recovery.
3. Analysis of Mass transfer Properties
The erythritol solid beads obtained in step (3) of example 8 were subjected to mass transfer performance analysis, and the test results are shown in fig. 8. As can be seen from FIG. 8, the mass of the erythritol solid marble bead gradually increased from the initial 0.402g as water vapor was introduced, mainly due to the absorption of water molecules by the erythritol inside the marble bead through the surface packing material. The time for introducing the water vapor is prolonged, the water content absorbed by the erythritol solid marble is gradually increased until the mass is gradually gentle after 500s, the mass of the finally absorbed erythritol solid marble is increased to 0.421g, and the transparency of the absorbed erythritol solid marble is increased. The water-absorbed erythritol solid marble was then placed in a drying oven and heated at 80 ℃ (no phase change occurred due to the fact that the mass of the erythritol solid marble was lower than the melting point of erythritol), and it was found that the mass of the erythritol solid marble dropped very quickly within 30s, and was directly decreased from 0.402g to 0.398g, and then the mass decreasing speed of the erythritol solid marble was gradually decreased, but still decreased until the mass of the erythritol solid marble dropped to 0.394g, the transparency of the dried erythritol solid marble decreased to appear white, and the mass of the dried erythritol solid marble was smaller than the initial weighed mass of the erythritol solid marble.
According to the analysis, in example 8, the movable semi-encapsulated solid-liquid phase change thermal storage material prepared by using the hydrophobic modified silica powder as the hydrophobic solid-liquid phase change thermal storage substrate molten liquid powder and using the erythritol as the phase change thermal storage substrate has the characteristic of mass transfer, and gas in the external environment can permeate the encapsulating material of the solid marble to absorb and release the gas.
Therefore, the movable semi-packaged solid-liquid phase change heat storage material provided by the invention has good material transfer characteristics, can be used as a medium for recovering waste heat of flue gas, and can be used as an absorbent for absorbing moisture, hydrogen sulfide, carbon dioxide, gas oxides of sulfur, gas oxides of nitrogen, volatile organic matters and other gases in the flue gas, so that the waste heat of the flue gas is recovered and gas purification is realized.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. A movable semi-packaged solid-liquid phase change heat storage material is characterized in that the phase change heat storage material is a solid-liquid phase change heat storage substrate melt marble formed by coating sparse solid-liquid phase change heat storage substrate molten liquid powder on the surface of solid-liquid phase change heat storage substrate melt or a solid marble formed by phase change of the melt marble.
2. The transportable semi-encapsulated solid-liquid phase change thermal storage material according to claim 1, wherein the solid-liquid phase change thermal storage base material is at least one of a crystalline hydrate, a molten salt, a eutectic salt, a urea, sulfur, paraffin, and an alcohol.
3. The transportable semi-encapsulated solid-liquid phase change thermal storage material according to claim 2, wherein the crystalline hydrate comprises iron nitrate nonahydrate, sodium silicate pentahydrate, iron trichloride hexahydrate, or sodium acetate trihydrate; the molten salt comprises sodium nitrate, potassium nitrate or lithium nitrate; the eutectic salt comprises 50% of lithium chloride-50% of aluminum trichloride, sodium nitrate-erythritol, solar salt or potassium iodide-lithium iodide; the ureas include thiourea or urea phosphate; the alcohol comprises erythritol, polyethylene glycol, erythritol or sorbitol.
4. The mobile semi-encapsulated solid-liquid phase change thermal storage material according to any one of claims 1 to 3, wherein the powder of the solvophobic-liquid phase change thermal storage substrate melt is at least one of a metal powder, a metal oxide powder and an inorganic non-metal powder modified from the solvophobic-liquid phase change thermal storage substrate melt, and an organic polymer powder of the solvophobic-liquid phase change thermal storage substrate melt.
5. The transportable semi-encapsulated solid-liquid phase change thermal storage material according to claim 4, wherein the metal powder comprises iron powder, copper powder or gold powder; the metal oxide powder comprises ferroferric oxide powder, copper oxide powder or titanium dioxide powder; the inorganic non-metal powder comprises silicon dioxide powder, talcum powder, graphene powder or carbon nano tubes; the organic polymer powder of the solid-liquid phase change heat storage substrate molten liquid comprises polypropylene powder, polytetrafluoroethylene powder or polystyrene powder.
6. The mobile semi-encapsulated solid-liquid phase change thermal storage material according to any one of claims 1 to 3, wherein the size of the solid-liquid phase change thermal storage base material melt powder is in the order of nanometers, micrometers or millimeters.
7. The method for preparing a mobile semi-encapsulated solid-liquid phase change thermal storage material according to any one of claims 1 to 6, wherein the solid-liquid phase change thermal storage matrix powder and the solidphobic-liquid phase change thermal storage matrix melt powder are used as raw materials, the solid-liquid phase change thermal storage matrix powder and the solidphobic-liquid phase change thermal storage matrix melt powder are measured according to the mass ratio of (1-1000):1, and the melt marbles are prepared by a melt coating or pre-mixing melting process;
the melting and coating process comprises the following steps: heating and melting solid-liquid phase change heat storage substrate powder on a solid-liquid phase change heat storage substrate melting liquid heating plate which is higher than a solid-liquid phase change heat storage substrate melting point and lower than a solid-liquid phase change heat storage substrate decomposition temperature to obtain solid-liquid phase change heat storage substrate melt, and then rolling the solid-liquid phase change heat storage substrate melt on the solid-liquid phase change heat storage substrate melting liquid powder arranged on the super-solid-liquid phase change heat storage substrate melting liquid heating plate to enable the solid-liquid phase change heat storage substrate melting liquid powder to be coated on the surface of the solid-liquid phase change heat storage substrate melt to form a melt marble;
the premixing and melting process comprises the following steps: the solid-liquid phase change heat storage base material powder and the dispersed solid-liquid phase change heat storage base material molten liquid powder are uniformly mixed to form a mixture, the mixture is placed on a dispersed solid-liquid phase change heat storage base material molten liquid heating plate which is higher than the solid-liquid phase change heat storage base material melting point and lower than the solid-liquid phase change heat storage base material decomposition temperature, the mixture is heated and melted, the solid-liquid phase change heat storage base material powder in the mixture is melted and aggregated into a solid-liquid phase change heat storage base material melt, and then the dispersed solid-liquid phase change heat storage base material molten liquid powder is coated on the surface of the solid-liquid phase change heat storage base material melt to form a melt marble.
8. The method of claim 7, wherein the loose-liquid phase-change heat-storage substrate melt heating plate is one of a loose-liquid phase-change heat-storage substrate melt modified metal plate, an alloy plate, and an inorganic non-metal plate.
9. Use of the mobile semi-encapsulated solid-liquid phase change thermal storage material of any one of claims 1 to 6 for energy storage and release, and mass transfer.
10. Use according to claim 9, characterized in that the substance in the substance transfer comprises water, hydrogen sulphide, carbon dioxide, gaseous oxides of sulphur, gaseous oxides of nitrogen or volatile organic compounds.
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