CN111205827A - Method for preventing loss of molten salt phase change heat storage material by using activated carbon - Google Patents
Method for preventing loss of molten salt phase change heat storage material by using activated carbon Download PDFInfo
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Abstract
The invention discloses a method for preventing loss of a molten salt phase change heat storage material by using activated carbon, and belongs to the field of phase change heat storage materials. The method comprises the following steps: (1) preparing molten salt particles; (2) adsorbing a molten salt phase change material by using activated carbon; (3) and (5) carrying out mixed pressing and sintering on the sample. According to the invention, the activated carbon is adopted to adsorb the molten salt phase change material, based on the preparation method of the stable phase change heat storage material, the pressing and granulation method is utilized to prepare the molten salt large particles, the activated carbon is adopted to adsorb the molten salt large particles, and finally, the activated carbon powder adsorbing the molten salt phase change material is mixed with the binder to be pressed and sintered, so that the composite phase change heat storage body is obtained. The preparation method is simple, low in cost and suitable for large-scale production, not only solves the problem that the fused salt phase-change material is easy to run off in the using process, but also has long service cycle and excellent mechanical property, and has important significance for expanding the use of the phase-change heat storage material.
Description
Technical Field
The invention belongs to the field of phase-change heat storage materials, and particularly relates to a method for preventing loss of a molten salt phase-change heat storage material by using activated carbon.
Background
The energy storage technology is an important component in energy conversion and utilization technology as a strategic emerging industry of China, and the selection of a proper energy storage technology route has important significance for improving the utilization efficiency of renewable energy, enhancing the peak regulation capability of thermal power generation and relieving power grid dispatching, and the large-scale application of the energy storage technology has great influence on energy transformation, power grid pattern and power supply structure. The heat storage material is the core and key of the heat storage technology, excess energy which is not used temporarily in a period or a certain space is collected and stored in a certain way, and is released again in the peak period of energy demand, and the excellent heat storage material has the advantages of high heat storage density, large heat conductivity coefficient, good stability and the like. The phase-change heat storage material is mainly used for storing or releasing a large amount of heat energy through two-phase conversion, so that peak clipping and valley filling in electric heating are realized, and electric energy is fully utilized.
The fused salt phase-change material has high heat storage density and low cost, and is a hotspot of research in the field of energy storage materials, but at present, fused salt still has many problems in a heat storage system as the phase-change heat storage material, such as fused salt loss in the use process, insufficient mechanical properties of a heat storage body and the like. These problems seriously affect the application period and the application range of the heat storage body, and need to be solved urgently.
Researchers at home and abroad mainly adopt an integral packaging method to solve the problem, Ryo Fukahori (FukahoriR, Nomura T, Zhu C, Sheng N, Okinaka N, Akiyama T, macro-encapsulation of metallic phase change materials using a cylindrical-type ceramic contacts for thermal energy storage [ J]Appl Energy 2016; 170:324-8) adopting a ceramic cup to package the molten salt, placing the molten salt into the ceramic cup body, and covering and packaging the outer layer, wherein the method can isolate the humidity environment and provide a supporting structure, and the space of the cup body can reserve an expansion space for the molten salt, so that the problem of large expansion coefficient of the molten salt is solved, but the method is complicated to prepare and has high cost; the adhesion between the ceramic cup and the cup cover can generate the phenomenon of falling and aging along with the increase of the cycle times; pau Gimenez (Gimenez P, Ferres S. glass encapsulated phase) changematerials for high temperature thermal energy storage[J]Renewable Energy,2017,107: 497-one 507.) adopted NaNO3The glass spheres are injected to play roles of packaging and supporting, although the method can completely solve the problem of hygroscopicity of the molten salt in an integrated mode and provide a supporting structure in a normal temperature environment, the process is difficult, the glass has a softening phenomenon at high temperature, and the softened glass cannot bear the weight of the molten salt to further cause the problem of leakage of the molten salt from the bottom, so that the structural supporting effect cannot be achieved, and the whole material fails; TEAP and EPS Ltd (Pendyala S. macroencapsis of Phase Change Materials for thermal energy Storage [ J)].Dissertations&Theses-Gradworks, 2012) respectively utilize polymer and metal materials to encapsulate molten salt into a sphere, which can isolate the molten salt from the external humidity environment and provide a stable structural shape, but this method not only increases the preparation cost and complicates the process, but also the low use temperature range of the polymer and the high conductivity of the metal material severely limit the application environment in electric heating; bhardwaj (Bhardwaj A. metallic encapsulation for High Temperature) (>500℃)Thermal Energy Storage Applications[J]2015.) carbon steel and nickel are adopted to package and granulate NaCl-KCl eutectic salt, a carbon steel cylinder is coated with nickel, and molten salt is placed in the carbon steel cylinder, the material prepared by the method has good thermal conductivity and thermal stability, can withstand 1700 times of thermal cycles at 580-680 ℃, and is simple in manufacturing process, but the preparation cost of the mould is high in the method, the carbon steel is easy to rust in a humidity environment, although the moisture absorption of the molten salt is prevented, the container still rust to cause failure, the carbon steel and the nickel also have electrical conductivity, and short circuit is easy to cause in an electric heating environment; noeii Arconada (Arconada N, Arribas L, LucioB, et al, macroencapsulation of sodium chloride as phase change materials for thermal energy storage [ J]Solar Energy,2018,167: 1-9.) using TiO2With SiO2As an encapsulating material, a NaCl fused salt cylinder is coated by a sol-gel method to prepare microcapsule particles, the method can isolate fused salt from the external environment in a humidity environment to avoid the problem of moisture absorption, but the method can not only prevent the generation of moisture absorption, but also prevent the generation of moisture absorptionThe method has the advantages of complex preparation process, high cost and difficult realization of industrial production, and the SiO is2The heat conduction is poor, so the moisture absorption problem is solved, but the heat storage performance is reduced; li et al (Li J, Lu W, Luo Z, et al. Synthesis and thermal properties of novelsodium nitrate microcapsules for high-temperature thermal energy storage [ J].Solar Energy Materials&Solar Cells,2017,159:440-3The method can prepare relatively uniform particles by microcapsule encapsulation, and the melting point and the heat storage capacity are not obviously changed, but not only the preparation process is complex, but also the melting point of the packaging material polysilazane is low, so that the packaging material is not suitable for a medium-high temperature molten salt phase change heat storage material; leng G et al (Leng G, Qiao G, Jiang Z, et al. micro encapsulated&form-stable phase change materials for high temperature thermal energystorage[J]Applied Energy,2018,217: 212-.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preventing loss of a molten salt phase change heat storage material by using activated carbon.
Aiming at the problem that the fused salt phase change heat storage material (nitrate, carbonate and multi-eutectic salt) is lost in the heat storage process, the invention utilizes the activated carbon to adsorb the fused salt particles, and then the fused salt particles are mixed and sintered with the binder (water glass and kaolin). In the heating adsorption stage, the molten salt is changed from a solid powder body into a liquid flowing body to flow into the pores of the activated carbon, and the activated carbon is cooled to realize the adsorption of the molten salt particles. The phase change process of the molten salt in the sintering process is carried out in the pores of the activated carbon, and the combination of the activated carbon powder and the binder is not influenced to a great extent to form a stable sintered body. Namely, the problem of large loss of molten salt can not occur in the use process of the molten salt composite heat storage material, and the problem of insufficient mechanical property of the heat storage body in the use process can be solved because the structure of a sintered body can not change too much relatively. In addition, the activated carbon has better heat conductivity coefficient and lower influence on heat storage performance, and finally the composite phase change heat storage body with difficult loss of the phase change material and excellent mechanical property can be prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preventing loss of a molten salt phase change heat storage material by using active carbon, which comprises the following steps:
(1) mixing and grinding the activated carbon powder and the molten salt phase-change material to obtain a uniform mixture;
(2) heating the mixture prepared in the step (1) to a fused salt melting temperature or above to convert the fused salt from a solid powder body into a liquid fluid, then preserving heat for a certain time to enable the liquid fused salt to flow into the activated carbon, and then cooling to prepare the activated carbon powder carrying the fused salt;
(3) and (3) mixing the activated carbon powder prepared in the step (2) with a binder, pressing and forming, and sintering at a certain temperature to form blocks, thus obtaining the phase change heat storage body of which the phase change material is not easy to run off in the use process.
Further, the step (2) is carried out by melting the molten salt phase change material in the step (1), immersing activated carbon into the molten salt phase change material, allowing the molten salt to enter the activated carbon, and cooling to obtain the activated carbon powder carrying the molten salt.
Further, the molten salt includes nitrate NaNO3、KNO3、LiNO3、Na2CO3、K2CO3、BaCO3、CaCO3、Li2CO3、NaNO3-KNO3、Na2CO3-K2CO3、NaNO3-LiNO3、Na2CO3-Li2CO3At least one of (1).
Further, the binder comprises at least one of phenolic resin, water glass and kaolin.
Further, the mass ratio of the activated carbon to the molten salt particles in the step (1) is 2: 3.
further, in the step (2), the infiltration temperature is higher than the phase transition point of the molten salt by more than 50 ℃, so that the molten salt can be fully infiltrated into the matrix structure.
Further, the mass ratio of the activated carbon powder to the binder in the step (3) is 1: 1.
further, the sintering process in the step (3) is as follows: putting the block material into a muffle furnace, setting the sintering temperature within the range of +/-5 ℃ of the phase transition point of the molten salt, preserving the heat for 3 hours, and cooling along with the furnace.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the activated carbon is adopted to adsorb the molten salt particles, based on the stable molten salt phase-change material preparation method, the activated carbon is utilized to adsorb the molten salt powder, then the activated carbon adsorbing the molten salt and the binder are mixed and sintered, and the phase-change heat storage material liquefied in the using process can be loaded and certain mechanical property can be provided through the adsorption of the activated carbon to the molten salt and the sufficient formability provided by the binder. The preparation method is simple, has low cost, can be used for large-scale production, solves the problem that the fused salt phase-change material is easy to run off in the using process, can prepare the phase-change heat storage body with long service cycle and excellent mechanical property, and has important significance for expanding the use of the phase-change heat storage material.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a schematic structural diagram of the molten salt phase-change heat storage body prepared by the invention.
Detailed Description
Comparative example 1
The comparative example was carried out according to the methods specified in the prior art, comprising the following steps:
1. pressing and sintering the phase-change material
(1) MgO powder and solar salt particles are mixed according to the mass ratio of MgO: solar salt 55: 45 grinding and mixing to ensure that the two components are uniformly distributed; solar salt is prepared from 60 wt% NaNO3And 40% wt KNO3And (3) mixing eutectic composition.
(2) Mixing the mixed powder in the step (1) with phenolic resin according to the mass ratio: phenol resin ═ 9: 1 grinding and mixing to mix them evenly.
(3) And (3) putting the mixed particle powder into a mould, applying 14000N pressure, maintaining the pressure for 60s, and demoulding to prepare the block material.
(4) And (3) putting the block material into a muffle furnace, setting the sintering temperature at 200 ℃, setting the heating rate at 5 ℃/min, preserving the heat for 360 minutes, and then cooling along with the furnace.
2. The obtained samples were subjected to a performance test
The sample compression strength is 40.6MPa through a sample compression test, the sample latent heat storage is 34.624J/g through a DSC test, however, 30.982J/g of latent heat storage is left after five times of circulation, namely, the phase change material is seriously lost and leaked in the use process of the heat storage material, and if the heat storage material is used in practical application, the problem of short service life of the heat storage material is solved, and the problem of corrosion to the surrounding environment caused by the loss of the molten salt phase change material is solved.
Example 1
The method for preventing loss of the molten salt phase change heat storage material by using the activated carbon comprises the following steps:
1. activated carbon adsorbs molten salt particles
(1) Taking the prepared activated carbon and the solar salt particles as the activated carbon according to the mass ratio: grinding and mixing the solar salt 2:3 to ensure that the two components are uniformly distributed; wherein the solar salt is composed of 60 wt% NaNO3And 40% wt KNO3And (3) mixing eutectic composition.
(2) And (3) putting the mixed powder into a tube furnace, preserving heat for 3 hours at the temperature of 250 ℃, completely melting solar salt, enabling the solar salt to flow into the active carbon holes, and cooling to room temperature to obtain the active carbon powder for bearing the molten salt phase change material.
2. Pressing and sintering a molten salt phase-change material sample
(1) Taking activated carbon powder bearing the molten salt phase change material and phenolic resin as activated carbon powder according to the mass ratio: phenol resin 2:3 grinding and mixing to obtain uniformly mixed particle powder.
(2) And putting the granular powder into a mold, applying 14000N pressure, maintaining the pressure for 60s, and demolding to prepare the block material.
(3) And (3) putting the block material into a muffle furnace, setting the sintering temperature at 200 ℃, setting the heating rate at 5 ℃/min, preserving the heat for 360 minutes, and then cooling along with the furnace.
3. The obtained samples were subjected to a performance test
The compression strength of the sample is 27.9MPa through a compression test of the sample, the latent heat storage of the sample is 34.562J/g through a DSC test, and the latent heat storage is 34.531J/g after five cycles.
Example 2
The method for preventing loss of the molten salt phase change heat storage material by using the activated carbon comprises the following steps:
1. activated carbon adsorbs molten salt particles
(1) Taking the prepared activated carbon and the solar salt particles as the activated carbon according to the mass ratio: grinding and mixing the solar salt 2:3 to ensure that the two components are uniformly distributed; wherein the solar salt is composed of 60 wt% NaNO3And 40% wt KNO3And (3) mixing eutectic composition.
(2) And (3) putting the mixed powder into a tube furnace, preserving heat for 3 hours at the temperature of 250 ℃, completely melting solar salt, enabling the solar salt to flow into the active carbon holes, and cooling to room temperature to obtain the active carbon powder for bearing the molten salt phase change material.
2. Pressing and sintering a molten salt phase-change material sample
(1) Taking activated carbon powder bearing the molten salt phase change material and phenolic resin as activated carbon powder according to the mass ratio: phenol resin 1: 1, grinding and mixing to obtain uniformly mixed particle powder.
(2) And putting the granular powder into a mold, applying 14000N pressure, maintaining the pressure for 60s, and demolding to prepare the block material.
(3) And (3) putting the block material into a muffle furnace, setting the sintering temperature at 200 ℃, setting the heating rate at 5 ℃/min, preserving the heat for 360 minutes, and then cooling along with the furnace.
3. The obtained samples were subjected to a performance test
The sample compressive strength is 21.5MPa through a compressive test on the sample, the sample latent heat storage is 50.354J/g through a DSC test, and the latent heat storage is 50.352J/g after five cycles.
Two examples prove that the invention can ensure that the phase-change material is not greatly lost in the use process and further ensure that the heat storage material can be recycled for a long time on the basis of ensuring the heat storage performance and the mechanical performance.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. A method for preventing loss of a molten salt phase change heat storage material by using activated carbon is characterized in that the preparation steps of the molten salt phase change heat storage material are as follows:
(1) mixing and grinding the activated carbon powder and the molten salt phase-change material to obtain a uniform mixture;
(2) heating the mixture prepared in the step (1) to a fused salt melting temperature or above to convert the fused salt from a solid powder body into a liquid fluid, then preserving heat for a certain time to enable the liquid fused salt to flow into the activated carbon, and then cooling to prepare the activated carbon powder carrying the fused salt;
(3) and (3) mixing the activated carbon powder prepared in the step (2) with a binder, pressing and forming, and sintering at a certain temperature to form blocks, thus obtaining the phase change heat storage material which is not easy to run off in the use process.
2. The method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon according to claim 1, wherein the step (2) is carried out by immersing the activated carbon after the molten salt phase change material in the step (1) is melted, so that the liquid molten salt enters the activated carbon, and then cooling to prepare the activated carbon powder carrying the molten salt.
3. The method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the molten salt comprises nitrate NaNO3、KNO3、LiNO3、Na2CO3、K2CO3、BaCO3、CaCO3、Li2CO3、NaNO3-KNO3、Na2CO3-K2CO3、NaNO3-LiNO3、Na2CO3-Li2CO3At least one of (1).
4. The method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the binder comprises at least one of phenolic resin, water glass and kaolin.
5. The method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the mass ratio of the activated carbon to the molten salt particles in the step (1) is about 2: 3.
6. the method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the molten salt can be fully impregnated into the matrix structure by the step (2) that the infiltration temperature is 50 ℃ or more higher than the phase change point of the molten salt.
7. The method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the mass ratio of the activated carbon powder to the binder in the step (3) is 1: 1.
8. the method for preventing the loss of the molten salt phase change heat storage material by using the activated carbon as claimed in claim 1 or 2, wherein the sintering process in the step (3) is as follows: putting the block material into a muffle furnace, setting the sintering temperature within the range of +/-5 ℃ of the phase transition point of the molten salt, preserving the heat for 3 hours, and cooling along with the furnace.
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Application publication date: 20200529 |