CN116376519A - Sugarcane-derived porous silicon carbide ceramic-based heat storage material, preparation method and device - Google Patents
Sugarcane-derived porous silicon carbide ceramic-based heat storage material, preparation method and device Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000919 ceramic Substances 0.000 title claims abstract description 58
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 45
- 239000011232 storage material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
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Abstract
The invention discloses a sugarcane derivative porous silicon carbide ceramic-based heat storage material, a preparation method and a device, wherein the heat storage material is obtained by compounding a sugarcane derivative silicon carbide ceramic skeleton and a phase change material; the silicon carbide ceramic skeleton derived from the sugarcane is obtained by immersing the sugarcane in a phenolic resin ethanol solution, carbonizing, reacting with molten silicon under vacuum, and removing redundant silicon. And filling paraffin into the gaps of the porous silicon carbide ceramic skeleton to obtain the sugarcane-derived porous ceramic-based heat storage material. The sugarcane derivative porous ceramic skeleton provided by the invention has three-dimensional continuous honeycomb heat conduction channels, high porosity and high heat conductivity of the heat storage material can be realized at the same time, the prepared heat storage material is further used as a heat storage unit to design a stacked bed phase change heat storage device, and compared with pure paraffin which is used as the stacked bed phase change heat storage device of the heat storage unit, the heat exchange rate of the stacked bed phase change heat storage device is obviously improved, so that more possibility is provided for applying the sugarcane derivative bionic material to high-efficiency and rapid heat energy storage.
Description
Technical Field
The invention belongs to the technical field of phase-change heat storage material preparation, and particularly relates to a sugarcane-derived porous silicon carbide ceramic skeleton and paraffin composite heat storage material, a preparation method and a preparation device.
Background
With the continuous development of social economy, the energy situation is more serious. In recent years, renewable energy sources have received attention because of their advantages of cleanliness, environmental protection, recyclability, and the like. However, the fluctuation and intermittence of renewable energy sources can lead to unbalanced supply and demand of energy sources, which restricts the large-scale application of the renewable energy sources. Among the various renewable energy utilization technologies, thermal energy storage technologies are considered as one of the most promising candidate technologies because of the ability to store or release thermal energy cyclically as needed. Among them, latent heat storage technology is attracting attention due to its high energy density and almost constant operating temperature during phase change. However, conventional phase change materials typically have low thermal conductivity, resulting in slow and inefficient thermal energy storage. In addition, leakage of phase change materials is also a bottleneck to be solved by practical applications. To address these problems, highly thermally conductive fillers are often added to the phase change material to improve overall thermal conductivity. But higher thermal conductivity cannot be achieved because conventional inorganic fillers such as metal particles, carbon-based particles, etc. cannot form continuous thermal conduction channels in the phase change material. In order to effectively improve the heat conduction performance of the phase change material, a continuous metal framework and a continuous carbon framework are widely used as carriers of the composite phase change material, but the high density of the metal framework limits the high energy storage density of the composite phase change material; while the carbon skeleton is easily corroded at high temperatures.
Ceramic materials, particularly silicon carbide ceramics, have received attention for their excellent physicochemical stability and high thermal conductivity. The silicon carbide ceramic framework can effectively solve the problems of low energy storage density of the metal framework and easy corrosion of the carbon framework. However, the general silicon carbide ceramic skeleton preparation process is complex, and in order to prepare the silicon carbide skeleton with three-dimensional continuous and ordered heat conduction channels more quickly, copying the three-dimensional continuous structure of the biomass material to prepare the silicon carbide skeleton is a research direction with great potential. Meanwhile, a proper latent heat storage device is further designed to verify the thermal performance of the biomass silicon carbide skeleton and the phase change material after being compounded, and the method has very important significance for expanding the potential application of the biomass-derived ceramic skeleton in the future.
Disclosure of Invention
The invention aims to: aiming at the defects, the invention provides a sugarcane-derived porous silicon carbide ceramic-based heat storage material with high heat conductivity and high energy storage density, a preparation method and a device based on the material.
The technical scheme is as follows: in order to solve the problems, the invention provides a sugarcane derivative porous silicon carbide ceramic-based heat storage material, which is prepared by compounding a sugarcane derivative porous silicon carbide ceramic skeleton and paraffin; the porosity of the sugarcane derivative porous silicon carbide ceramic skeleton is 80% -90%; the mass ratio of the sugarcane-derived porous silicon carbide ceramic skeleton to paraffin is 40:57 to 63.
Further, the porosity of the sugarcane-derived porous silicon carbide ceramic skeleton is 85%, and the mass ratio of the sugarcane-derived porous silicon carbide ceramic skeleton to paraffin is 39.7:60.3.
the invention also provides a technical scheme of the preparation method of the sugarcane-derived porous silicon carbide ceramic-based heat storage material, which comprises the following steps:
(1) After the sugarcane is initially cut, putting the sugarcane into a freeze dryer for drying; putting the frozen and dried sugarcane into a phenolic resin solution, and standing for 1-2 days;
(2) Carbonizing sugarcane impregnated with phenolic resin solution in a tube furnace, heating to 900 ℃ in an inert atmosphere, and preserving heat for 2 hours to obtain carbonized sugarcane; the carbonized sugarcane and silicon powder are mixed according to the mass ratio of 1:3.5 to 4, heating to 1450 to 1600 ℃ in a high-temperature furnace, preserving heat for 1.5 to 2 hours, and reacting to generate a silicon carbide-silicon mixture; removing redundant silicon at 1750-1850 ℃ for 2-4 hours to obtain a sugarcane derivative porous silicon carbide ceramic skeleton;
(3) Mixing the sugarcane derivative porous silicon carbide ceramic skeleton with paraffin, and coating the porous silicon carbide skeleton in the paraffin by adopting a vacuum impregnation method to obtain the sugarcane derivative porous silicon carbide ceramic-based heat storage material.
Further, in the step (1), the freeze-drying process is as follows: the sugarcane is frozen for 4 to 8 hours at the temperature of minus 40 ℃ in a freeze dryer, and then dried in vacuum for 1 to 2 days at the temperature of minus 10 ℃.
Further, in the step (1), the phenolic resin solution is prepared from phenolic resin powder and ethanol according to the mass ratio of 15-25: 85-75% of the raw materials.
Further, the reaction temperature of the carbonized sugarcane and the silicon powder in the step (2) in a high-temperature furnace is 1600 ℃, and the silicon removal temperature in the silicon carbide-silicon mixture silicon removal process in the high-temperature furnace is 1800 ℃.
Further, the vacuum impregnation method in the step (3) is specifically operated as follows: the silicon carbide skeleton is buried in excess paraffin, placed in a vacuum oven, and kept at 70 ℃ for 12 hours.
The beneficial effects are that: compared with the prior art, the invention has the remarkable advantages that:
(1) The sugarcane derivative porous silicon carbide ceramic skeleton has a three-dimensional continuous honeycomb structure, forms continuous and orderly high-heat-conduction channels, and effectively improves the heat conductivity of the phase change material after loading the phase change material;
(2) The heat storage material prepared by the invention has adjustable and very high porosity, and can balance high energy storage density and high thermal conductivity after the phase change material is loaded.
(3) The heat storage material prepared by the invention has good leakage resistance and good circulation stability. The porosity of the sugarcane-derived porous silicon carbide ceramic skeleton prepared by the method is up to 80-90%, after paraffin is loaded, the thermal conductivity of the composite material is improved to 10.34W/(m.K), the energy storage density reaches 151.20kJ/kg, the retention rate of the phase change material reaches 60.3%, and the unification of high energy storage density and high thermal conductivity is achieved.
The invention also provides a stacked bed phase change heat storage device which comprises a plurality of heat storage units, wherein the heat storage units are prepared from the sugarcane-derived porous silicon carbide ceramic-based heat storage material.
Further, the heat storage units are divided into two arrangements of concentric axes and different axes.
Further, the heat storage unit comprises a plurality of layers of cylinder assemblies, and four heat storage units are arranged in each layer of cylinder assemblies, and five layers are all arranged.
The beneficial effects are that: compared with the pure paraffin heat storage unit, the bulk bed phase change heat storage device has the advantages that the melting time is obviously reduced, and the heat exchange rate of the bulk bed phase change heat storage device is obviously improved.
Drawings
FIG. 1 is a schematic diagram of a preparation flow of a storage material and a schematic diagram of different arrangements of heat storage units of a stacked bed phase change heat storage device;
FIG. 2 is an SEM image of sugarcane after carbonization in example 1;
FIG. 3 is an SEM image of a porous silicon carbide ceramic prepared in example 1;
FIG. 4 is the latent heat of phase change of DSC of the composite phase change material of example 1;
FIG. 5 is a graph of thermal conductivity after silicon carbide and phase change material are combined at different porosities;
FIG. 6 is an SEM image of a porous silicon carbide ceramic prepared in comparative example 1 without impregnating with an ethanol solution of a phenolic resin;
fig. 7 is a comparison of melting times of the prepared composite phase change material and pure paraffin wax as a heat storage unit in different arrangements obtained from experiments and simulations in example 1.
Detailed Description
Example 1
(1) Washing sugarcane with deionized water, and drying in a freeze dryer to remove crystal water in sugarcane. The procedure for setting up the freeze dryer was: firstly, freezing for 4-8 hours at the temperature of minus 40 ℃, and then vacuum drying for 1-2 days at the temperature of minus 10 ℃. The phenolic resin powder and ethanol are mixed according to the mass ratio of 20:80 preparing phenolic resin ethanol solution, and mechanically stirring uniformly. And (3) putting the frozen and dried sugarcane into a phenolic resin ethanol solution, and standing for 1-2 days.
(2) And (3) placing the sugarcane immersed with the phenolic resin ethanol solution into a tube furnace for carbonization, heating to 900 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, and then preserving heat for 2 hours to obtain carbonized sugarcane. The carbonized sugar cane was cut into cylindrical samples with a diameter of 13mm and a thickness of 3mm as carbon precursors. Mixing the cut carbon precursor with silicon powder according to a mass ratio of 1: 3.5-4, and placing the mixture into a high-temperature furnace for silicon melting reaction. And in a vacuum environment, heating to 1600 ℃ at a heating rate of 15 ℃/min, and preserving heat for 1-2 hours to enable the carbon precursor and the silicon powder to fully react to obtain the silicon carbide-silicon mixture. Finally, the silicon carbide-silicon mixture was placed in a high temperature furnace and heated to 1800 ℃ to remove excess silicon. In order to maintain the structural strength of the silicon carbide skeleton and completely remove the redundant silicon, the heat preservation time is controlled within 1-2 hours, and the state of the silicon carbide skeleton is observed when the high-temperature furnace is cooled after the silicon removal is completed each time. Repeating the silicon removing process for 2-3 times to completely remove the redundant silicon, thereby obtaining the sugarcane-derived porous silicon carbide ceramic skeleton with the porosity of 85%.
(3) Embedding the silicon carbide skeleton obtained in the first step into excessive paraffin, placing the paraffin into a vacuum oven, and preserving the heat for 12 hours at 70 ℃ to obtain the sugarcane-derived porous silicon carbide ceramic-based heat storage material.
SEM images of sugarcane carbonized and SEM images of silicon carbide frameworks obtained after removing excessive silicon through silicon melting reaction are shown in fig. 2 and 3. The microscopic morphology of the silicon carbide ceramic presents a continuous honeycomb structure, is consistent with the morphology of the carbon precursor, and shows that the silicon carbide ceramic inherits the excellent three-dimensional continuous structure of the sugarcane. Meanwhile, the enlarged SEM image shows that the grains of the silicon carbide ceramic are closely packed, and the closely packed grains help to reduce interface thermal resistance, thereby improving thermal conductivity. In addition, no redundant silicon is found in the silicon carbide pores, which indicates that the purity of the prepared silicon carbide ceramic structure is higher. The prepared heat storage material also has good leakage resistance, and leakage of the phase change material caused by volume expansion in the melting process can be well prevented due to capillary force generated by small pores and an ordered honeycomb structure.
The sugarcane derivative porous silicon carbide ceramic-based heat storage material prepared in the embodiment has the following performance parameters: the thermal conductivity of the composite phase-change material measured by a laser thermal conductivity meter is 10.34W/(m.K), the enthalpy value of the composite material measured by DSC is 151.20kJ/kg, and the ratio of the enthalpy value of the composite phase-change material to the enthalpy value of the pure phase-change material is generally defined as the retention rate of the composite phase-change material, so that the retention rate of the composite phase-change material is 60.3%.
Example 2
The specific preparation method is the same as in example 1, except that the concentration of the ethanol solution of the lyophilized sugarcane-impregnated phenolic resin is different.
The phenolic resin and ethanol are mixed according to the mass ratio of 15:85, 25:75 preparing phenolic resin ethanol solution, removing redundant silicon after carbonization and molten silicon reaction, wherein the porosity of the porous silicon carbide ceramic framework is 88% and 82%, the corresponding thermal conductivity of the composite phase change material is 7.26W/(m.K) and 11.10W/(m.K), and the thermal conductivity of the silicon carbide framework with different porosities after being compounded with paraffin is shown in figure 5. As the concentration of the phenolic resin ethanol solution increases, the porosity of the prepared silicon carbide skeleton decreases and the thermal conductivity increases, on the one hand, because more phenolic resin is converted into carbon during carbonization and adheres to the pyrolyzed carbon skeleton of sugarcane, resulting in a decrease in porosity; on the other hand, more carbon adheres to the carbon skeleton, and more densely packed grains are formed during high-temperature sintering. The porosity of the prepared porous silicon carbide ceramic skeleton can be adjusted to a certain extent by adjusting the concentration of the phenolic resin ethanol solution.
Comparative example 1
The SEM of the obtained silicon carbide ceramic is shown in figure 6, and the porosity of the obtained silicon carbide ceramic is 90 percent, but the high porosity leads to the easy destruction of a framework structure and poor mechanical properties, so the silicon carbide ceramic is not suitable for preparing the composite phase change material by compounding with paraffin.
Comparative example 2
The sugar cane is dried by oven drying rather than freeze drying. As the oven drying mode can not remove crystal water on the basis of maintaining the original structure of the sugarcane like freeze drying, the sugarcane structure can be rapidly contracted in the actual drying process, the original three-dimensional continuous ordered structure can not be maintained, and the method is not suitable for being further used as a carbon precursor.
Example 3
The embodiment provides a stacked bed phase change heat storage device.
The sugarcane-derived porous silicon carbide ceramic-based heat storage material obtained in example 1 was used as a heat storage unit of a packed bed phase change heat storage device, the prepared heat storage material was cut into cylinders with a diameter of 20mm and a height of 10mm, and arranged in a concentric and a different axis, and experimental and simulated comparison was performed to compare the heat storage material with pure paraffin at an inlet air flow of 5.8m 3 And/h, the influence on the heat exchange rate of the packed bed at 60 ℃. The result shows that compared with pure paraffin serving as a heat storage unit, the melting time is reduced by 21.6% under the coaxial arrangement by adopting the heat storage material as the heat storage unit; further adopting the off-axis arrangement, the melting time is reduced by 44.3% compared with the pure paraffin heat storage unit in the on-axis arrangement, as shown in fig. 7. Therefore, the heat exchange rate of the heat storage units arranged in different axes is obviously better than that of the heat storage units arranged in the same axes; meanwhile, compared with the pure paraffin serving as the heat storage unit, the heat exchange rate of the packed bed phase change heat storage device can be remarkably improved by adopting the heat storage material serving as the heat storage unit.
Claims (10)
1. The sugarcane derivative porous silicon carbide ceramic-based heat storage material is characterized by being prepared by compounding a sugarcane derivative porous silicon carbide ceramic skeleton and paraffin; the porosity of the sugarcane derivative porous silicon carbide ceramic skeleton is 80% -90%; the mass ratio of the sugarcane-derived porous silicon carbide ceramic skeleton to paraffin is 40:57 to 63.
2. The sugarcane derivative porous silicon carbide ceramic-based heat storage material according to claim 1, wherein the sugarcane derivative porous silicon carbide ceramic skeleton has a porosity of 85%, and the mass ratio of the sugarcane derivative porous silicon carbide ceramic skeleton to paraffin wax is 39.7:60.3.
3. a method of preparing a sugarcane derivative porous silicon carbide ceramic-based heat storage material according to claim 1, comprising the steps of:
(1) After the sugarcane is initially cut, putting the sugarcane into a freeze dryer for drying; putting the frozen and dried sugarcane into a phenolic resin solution, and standing for 1-2 days;
(2) Carbonizing sugarcane impregnated with phenolic resin solution in a tube furnace, heating to 900 ℃ in an inert atmosphere, and preserving heat for 2 hours to obtain carbonized sugarcane; the carbonized sugarcane and silicon powder are mixed according to the mass ratio of 1:3.5 to 4, heating to 1450 to 1600 ℃ in a high-temperature furnace, preserving heat for 1.5 to 2 hours, and reacting to generate a silicon carbide-silicon mixture; removing redundant silicon at 1750-1850 ℃ for 2-4 hours to obtain a sugarcane derivative porous silicon carbide ceramic skeleton;
(3) Mixing the sugarcane derivative porous silicon carbide ceramic skeleton with paraffin, and coating the porous silicon carbide skeleton in the paraffin by adopting a vacuum impregnation method to obtain the sugarcane derivative porous silicon carbide ceramic-based heat storage material.
4. The method for preparing a sugarcane derivative porous silicon carbide ceramic-based heat storage material according to claim 3, wherein in the step (1), the freeze-drying process is as follows: the sugarcane is frozen for 4 to 8 hours at the temperature of minus 40 ℃ in a freeze dryer, and then dried in vacuum for 1 to 2 days at the temperature of minus 10 ℃.
5. The method for preparing the sugarcane derivative porous silicon carbide ceramic-based heat storage material according to claim 3, wherein the phenolic resin solution in the step (1) comprises the following components in mass ratio of phenolic resin powder to ethanol of 15-25: 85-75% of the raw materials.
6. The method for preparing a porous silicon carbide ceramic-based heat storage material derived from sugar cane according to claim 3, wherein the reaction temperature of the carbonized sugar cane in the step (2) and silicon powder in a high temperature furnace is 1600 ℃; in the silicon carbide-silicon mixture silicon removal process in the high-temperature furnace, the silicon removal temperature is 1800 ℃.
7. The method for preparing a sugarcane derivative porous silicon carbide ceramic-based heat storage material according to claim 3, wherein the vacuum impregnation method in the step (3) is specifically operated as: the silicon carbide skeleton is buried in excess paraffin, placed in a vacuum oven, and kept at 70 ℃ for 12 hours.
8. A stacked bed phase change heat storage device comprising a plurality of heat storage units prepared from the sugarcane-derived porous silicon carbide ceramic-based heat storage material of claim 1 or 2.
9. The packed bed phase change heat storage device according to claim 8, wherein the heat storage units are arranged in two ways of concentric axis and different axis.
10. The packed bed phase change heat storage device according to claim 8, wherein the heat storage units comprise a plurality of layers of cylinder assemblies, four heat storage units are placed in each layer of cylinder assemblies, and five layers are total.
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