CN108728048B - Ternary eutectic chloride heat transfer and storage material and preparation method and application thereof - Google Patents
Ternary eutectic chloride heat transfer and storage material and preparation method and application thereof Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 73
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 65
- 238000012546 transfer Methods 0.000 title claims abstract description 62
- 239000011232 storage material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 92
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 84
- 239000011780 sodium chloride Substances 0.000 claims abstract description 46
- 239000001103 potassium chloride Substances 0.000 claims abstract description 42
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 42
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 238000010248 power generation Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003841 chloride salts Chemical class 0.000 claims description 5
- 238000003181 co-melting Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 36
- 230000008018 melting Effects 0.000 abstract description 34
- 238000005338 heat storage Methods 0.000 abstract description 13
- 238000001816 cooling Methods 0.000 abstract description 9
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910014863 CaCl2—MgCl2 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910020949 NaCl—CaCl2 Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- RTQCAYKHUMWCEM-UHFFFAOYSA-N [Mg].ClO Chemical compound [Mg].ClO RTQCAYKHUMWCEM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- RPFLLVICGMTMIE-UHFFFAOYSA-L calcium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[Ca+2] RPFLLVICGMTMIE-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract
The invention discloses a ternary eutectic chloride heat transfer and storage material and a preparation method and application thereof, wherein the ternary eutectic chloride heat transfer and storage material is prepared by eutectic melting of sodium chloride, potassium chloride and anhydrous calcium chloride, and the mass ratio of the sodium chloride to the potassium chloride to the anhydrous calcium chloride is 20-30: 20-50: 30-50. The preparation method comprises the following steps: drying sodium chloride and potassium chloride at constant temperature; weighing the dried sodium chloride and potassium chloride according to the proportion, mixing with anhydrous calcium chloride, grinding, heating to form uniform liquid, cooling to room temperature, taking out, grinding and crushing. The ternary eutectic chloride heat-transfer and heat-storage material obtained by utilizing the advantages of high thermal stability, low steam pressure at high temperature, low price and the like and reducing the over-high melting point of the unit chloride by adopting the eutectic melting of the multiple chlorides has good heat storage and heat transfer capacities and can be used as a heat storage and heat transfer medium to be applied to a solar thermal power station.
Description
Technical Field
The invention belongs to the field of solar thermal power generation, and particularly relates to a ternary eutectic chloride heat transfer and storage material and a preparation method and application thereof.
Background
With the continuous decrease of fossil energy and the increasing demand for energy, the development of clean renewable energy has been the trend. Solar energy is regarded as inexhaustible clean energy and is increasingly paid more attention.
The concentrated solar thermal power generation technology (CSP) can combine low-cost and large-scale heat storage technologies and provide continuous, stable and high-quality electric energy, and is considered as the most promising approach for large-scale solar energy utilization in the future. Since solar energy has intermittency, a heat storage material must be used to store the absorbed heat in order to improve solar heat utilization efficiency.
Among heat storage and heat storage materials (PCM) for solar thermal power generation, molten salt is considered as the most promising candidate material. Because of its good thermal stability, high latent heat value and low vapor pressure, and in addition, it is cheap and abundant in reserves relative to heat transfer media such as conduction oil, liquid metal and the like.
Currently, in Solar thermal power generation molten salt systems, the most used is the nitrate/nitrite system, namely Solar salt (60% NaNO)3-40％KNO3Melting point of 220 ℃ and upper limit use temperature of 565 ℃ and Hitec (7% NaNO)3-53％KaNO3-40％NaNO2Melting point 142 ℃ and application temperature < 500 ℃. Nitrates are inexpensive and less corrosive, and have the disadvantage of having a limited temperature range of use and are unstable and susceptible to decomposition above 500 ℃. To further improve thermal efficiency, CSP applications require that the operating temperature of the next generation solar thermal conversion system be at least 550 ℃ to 720 ℃.
The patent application No. 201310092911.7 provides a method for the preparation and use of binary eutectic sodium chloride-calcium chloride, which, although having a higher use temperature than the nitrate system, has a low latent heat value and no analysis of its thermal properties. The application No. 201510134557.9 patent provides a preparation method and application of a high thermal conductivity metal-chloride molten salt material, which has good thermal conductivity, and the thermal conductivity coefficient of the system is high at high temperature, but the melting point is too high, so that the material is not suitable for solar thermal power stations.
NaCl-KCl-MgCl present at present2And NaCl-CaCl2-MgCl2Iso system, anhydrous MgCl2Has strong water absorption, only 4 water molecules can be removed when the water is dehydrated in the air, and serious side reaction can not occur. If the remaining 2 molecules of water are removed, the magnesium chloride will be significantly hydrolyzed to produce magnesium hydroxychloride, magnesium oxide, hydrogen chloride, and the like. Pure substance anhydrous MgCl2Very poor melting effect, obvious endothermic peaks for removing free water and crystal water, and MgCl containing two water molecules which cannot be removed2Influencing the subsequent eutectic phenomenon of continuous temperature rise. At the same time due to MgCl2The strength of the inter-particle bonds in the crystal lattice is smaller than the strength of the ionic bonds in NaCl and KCl, and MgCl is shown at the same temperature2The vapor pressure of (a) is higher than that of other chlorine salts. Due to MgCl2Has strong water absorption, is volatile in molten state, and is not suitable for the sunThe field of thermal power generation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a ternary eutectic chloride heat transfer and storage material which is high in latent heat value, low in melting point and good in specific heat capacity and takes sodium chloride, potassium chloride and calcium chloride as raw materials, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a ternary eutectic chloride heat transfer and storage material is prepared by eutectic melting of sodium chloride, potassium chloride and anhydrous calcium chloride, wherein the mass ratio of the sodium chloride to the potassium chloride to the anhydrous calcium chloride is 20-30: 20-50: 30-50.
In order to have better heat storage capacity and heat conduction efficiency, improve the heat storage efficiency and avoid local overheating of the device, the ternary eutectic chloride heat transfer and storage material preferably comprises 20: 50: 30 of sodium chloride, potassium chloride and anhydrous calcium chloride in a mass ratio.
The ternary eutectic chloride heat transfer and storage material preferably comprises, by mass, 30: 40: 30 of sodium chloride, potassium chloride and anhydrous calcium chloride.
As a general inventive concept, the invention also provides a preparation method of the ternary eutectic chloride heat transfer and storage material, which comprises the following steps:
weighing anhydrous calcium chloride, dried sodium chloride and dried potassium chloride according to the mass ratio, mixing, and grinding; heating the ground mixture to form a homogeneous liquid; and taking out the obtained liquid after the obtained liquid is cooled to room temperature, and grinding and crushing the liquid to obtain the ternary eutectic chloride heat transfer and storage material.
In the preparation method of the ternary eutectic chloride heat transfer and storage material, the heating temperature is preferably 700-900 ℃.
In the preparation method of the ternary eutectic chloride heat transfer and storage material, the heating time is preferably 3-5 h.
In the preparation method of the ternary eutectic chloride heat transfer and storage material, preferably, the drying is constant-temperature drying.
In the preparation method of the ternary eutectic chloride heat transfer and storage material, the constant-temperature drying temperature is preferably 120-150 ℃.
In the preparation method of the ternary eutectic chloride heat transfer and storage material, the constant-temperature drying time is preferably 24-48 h.
As a general inventive concept, the invention also provides an application of the ternary eutectic chloride heat transfer and storage material or the ternary eutectic chloride heat transfer and storage material prepared by the preparation method in solar thermal power generation.
Compared with the prior art, the invention has the advantages that:
(1) the ternary eutectic chloride heat transfer and storage material prepared by the invention has good heat storage and transfer performance, the latent heat value can reach more than 156J/g, the melting point is as low as about 531 ℃, the average specific heat capacity at 600-900 ℃ can reach 2.1J/Kg, and the ternary eutectic chloride heat transfer and storage material can be applied to the fields of tower type solar supercritical power generation and light-gathering solar thermochemistry utilization.
(2) The ternary eutectic chloride heat transfer and storage material overcomes the defect that a nitrate system cannot be applied to the field of solar high-temperature heat utilization due to low upper limit use temperature.
(3) The ternary eutectic chloride heat transfer and storage material prepared by the invention avoids MgCl2The chlorinated salt of the system has the defects of strong water absorption and high vapor pressure at high temperature, and provides a new choice for the application of the molten salt in the field of solar thermal power generation.
(4) The eutectic chloride heat transfer and storage material not only keeps a series of advantages of good thermal stability and chemical stability of chloride, low saturated steam pressure, large specific heat capacity and the like, but also avoids the defect of overhigh melting point of chloride, thereby being widely applied in industry.
Drawings
FIG. 1 is a graph of the heat flow curves from 500 deg.C to 900 deg.C for sample No. 4, sapphire and blank controls of example 4 of the present invention.
FIG. 2 is a graph showing specific heat capacity curves of sample No. 1 of example 1 and sample No. 4 of example 4 of the present invention.
Detailed Description
The invention is described in more detail below with reference to examples and the accompanying drawings, but the invention is not limited thereto.
The materials and equipment used in the following examples are commercially available.
Example 1
The ternary eutectic chloride heat transfer and heat storage material is prepared by eutectic melting of sodium chloride, potassium chloride and anhydrous calcium chloride, wherein the contents of the sodium chloride, the potassium chloride and the anhydrous calcium chloride are respectively 30 wt.%, 40 wt.% and 30 wt.%.
The invention relates to a ternary eutectic chloride heat transfer and storage material, which is prepared by the following steps:
drying sodium chloride and potassium chloride at 120 deg.C for 24 hr to remove water; mixing the dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 30 wt.%, 40 wt.% and 30 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride heat transfer and storage material.
The ternary eutectic chloride heat transfer and storage material prepared in the present example was subjected to melting point and latent heat value tests using a differential scanning calorimeter, the test results are shown in table 1, and the sample number is sample No. 1.
The ternary eutectic chloride heat transfer and storage material in the embodiment has the melting point of 537.75 ℃ and the latent heat value of 150.8J/g, and can be applied to the fields of tower type solar supercritical power generation and light-gathering solar thermochemistry utilization.
Example 2
The invention relates to a ternary eutectic chloride heat transfer and storage material, which is prepared by the following steps:
drying sodium chloride and potassium chloride at 120 deg.C for 24 hr to remove water; mixing dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 30 wt.%, 30 wt.% and 40 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride heat transfer and storage material.
The test method is the same as that of example 1, and the test results of the melting point and the latent heat value of the ternary eutectic chloride heat transfer and storage material prepared in the example are shown in table 1, and the label is sample No. 2.
The melting point of the ternary eutectic chloride heat transfer and storage material in the embodiment is 554.82 ℃, the latent heat value is 153.6J/g, and the ternary eutectic chloride heat transfer and storage material can be applied to the fields of tower type solar supercritical power generation and light-gathering solar thermochemistry utilization.
Example 3
The invention relates to a ternary eutectic chloride heat transfer and storage material, which is prepared by the following steps:
drying sodium chloride and potassium chloride at 120 deg.C for 24 hr to remove water; mixing dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 30 wt.%, 20 wt.% and 50 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride heat transfer and storage material.
The test method is the same as that of example 1, and the test results of the melting point and the latent heat value of the ternary eutectic chloride heat transfer and storage material prepared in this example are shown in table 1, and the label is sample No. 3.
The ternary eutectic chloride heat transfer and storage material in the embodiment has the melting point of 554.60 ℃ and the latent heat value of 156.2J/g, and can be applied to the fields of tower type solar supercritical power generation and light-gathering solar thermochemistry utilization.
Example 4
The ternary eutectic chloride heat transfer and heat storage material is prepared by eutectic melting of sodium chloride, potassium chloride and anhydrous calcium chloride, wherein the contents of the sodium chloride, the potassium chloride and the anhydrous calcium chloride are 20 wt.%, 50 wt.% and 30 wt.%, respectively.
The preparation method of the ternary eutectic chloride heat transfer and storage material comprises the following steps:
drying sodium chloride and potassium chloride at 120 deg.C for 24 hr to remove water; weighing the dried sodium chloride and potassium chloride according to the proportion, mixing with anhydrous calcium chloride, and grinding uniformly; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride heat transfer and storage material.
The test method is the same as that of example 1, and the test results of the melting point and the latent heat value of the ternary eutectic chloride heat transfer and storage material prepared in the example are shown in table 1, and the label is sample No. 4.
The ternary eutectic chloride heat transfer and storage material in the embodiment has the melting point of 531.86 ℃ and the latent heat value of 154.3J/g, and can be applied to the fields of tower type solar supercritical power generation and light-gathering solar thermochemistry utilization.
Comparative example 1
A ternary eutectic chloride material is prepared by the following steps:
drying sodium chloride and potassium chloride in a forced air drying oven at 120 deg.C for 24 hr to remove water; mixing dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 40 wt.%, 30 wt.% and 30 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride material.
The results of the melting point and latent heat value tests for the ternary eutectic chloride salt material prepared in this comparative example are shown in table 1 and are labeled sample No. 5, as in example 1.
Comparative example 2
A ternary eutectic chloride material is prepared by the following steps:
drying sodium chloride and potassium chloride in a forced air drying oven at 120 deg.C for 24 hr to remove water; mixing dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 40 wt.%, 20 wt.% and 40 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride material.
The results of the melting point and latent heat value tests for the ternary eutectic chloride salt material prepared in this comparative example are shown in table 1 and are labeled sample No. 6, as in example 1.
Comparative example 3
A ternary eutectic chloride material is prepared by the following steps:
drying sodium chloride and potassium chloride at 120 deg.C for 24 hr to remove water; mixing dried sodium chloride and potassium chloride with anhydrous calcium chloride, and uniformly grinding, wherein the content of the dried sodium chloride, the content of the dried potassium chloride and the content of the anhydrous calcium chloride are respectively 30 wt.%, 50 wt.% and 20 wt.%; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powdery particles, and sealing and storing the powdery particles to obtain the ternary eutectic chloride material.
The results of the melting point and latent heat value tests for the ternary eutectic chloride salt material prepared in this comparative example are shown in table 1 and are labeled sample No. 7, as in example 1.
Comparative example 4
A binary eutectic chloride heat transfer and heat storage material is prepared from sodium chloride and anhydrous calcium chloride, and the optimal proportion is selected in the comparative example, wherein the contents of the sodium chloride and the anhydrous calcium chloride are respectively 32 wt.% and 68 wt.%.
The preparation method of the binary eutectic chloride heat transfer and storage material comprises the following steps:
drying sodium chloride at 120 deg.C for 24 hr to remove water; mixing the dried sodium chloride and anhydrous calcium chloride according to the proportion, and uniformly grinding; heating the ground mixture to 900 ℃ by a static melting method, and keeping the temperature for 3 hours to form uniform liquid; and taking out the obtained liquid after natural cooling, grinding and crushing the liquid into powder particles, and sealing and storing the powder particles to obtain the binary eutectic chloride heat transfer and storage material.
The test method is the same as that of example 1, and the test results of the melting point and the potential heat value of the binary eutectic chloride heat transfer and storage material prepared in the above example are shown in table 1 and are marked as sample No. 8.
TABLE 1
As can be seen from Table 1, when NaCl, KCl and CaCl are used2When the mass ratio of the components is 20-30: 20-50: 30-50, the latent heat value of the molten salt system is very high and far higher than 100J/g and more than 150J/g, and the latent heat value is far higher than that of binary NaCl-CaCl2When NaCl, KCl and CaCl are added2When the mass ratio of (A) is out of this range, the latent heat values are all less than 100J/g. Examples 1 and 4 (sample No. 1 and sample No. 4, respectively) having lower melting points among the four examples all had melting points around 530 ℃. Sample No. 1 and sample No. 4, which have lower melting points, were selected for specific heat capacity calculation. The formula is as follows:
in the formula, mcalM is the molar mass of the standard samplespThe molar mass of the sample is,
the specific heat of the sample is used as the sample specific heat,
is the specific heat of the standard sample, PspecimenIs the heat flow of the sample, PblankFor blank heat flow, PcalibrationIs the standard sample heat flow. Wherein,
and
has the unit of J/K.g, mcalAnd mspHas a molar mass of g/mol, Pspecimen、PblankAnd PcalibrationUnit of (d) is MW.
Since sapphire has a stable specific heat capacity at high temperatures, it is commonly used as a standard sample to calculate the specific heat capacity of a sample. Fig. 1 is a heat flow curve of 500 to 900 ℃ for sample No. 4, sapphire and blank control, and the heat flow data of sample No. 4, sapphire and blank disc measured therein are substituted into the above formula to obtain the specific heat capacity of sample No. 4, and similarly, for example 1, the same method is also used to measure heat flow and calculate the specific heat capacity of the sample, and finally the specific heat capacity curves representing sample No. 1 and sample No. 4 as shown in fig. 2 are obtained.
In fig. 2, when the sample is in the temperature range of 500 ℃ to 600 ℃, the molten salt is in the phase change process, and the specific heat cannot be continuously measured, because not all heat is used for heating, and part of heat is used for generating a higher energy state of the substance, so that the specific heat measured by DSC is only suitable for the process without phase change. As can be seen from fig. 2, the specific heat capacity of the molten salt increases with an increase in temperature after higher than 600 ℃, because the crystal lattice is disturbed after the molten salt is melted, and the crystal lattice energy is a main cause of the increase in specific heat capacity.
It can also be seen from FIG. 2 that the increase in specific heat capacity of sample No. 4 above 700 ℃ is greater than that of sample No. 1, while the average specific heat capacity of sample No. 1 is 1.94J/K.g and the average specific heat capacity of sample No. 4 is 2.1J/K.g between 600 ℃ and 900 ℃. In summary, sample No. 4 can be selected as the final preferred sample.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.
Claims (9)
1. The ternary co-molten chloride heat transfer and storage material is characterized by being prepared by co-melting sodium chloride, potassium chloride and anhydrous calcium chloride, wherein the mass percentages of the sodium chloride, the potassium chloride and the anhydrous calcium chloride are 20-30%, 20-50% and 30-50%, respectively.
2. The ternary eutectic chloride heat transfer and storage material of claim 1, wherein the mass percentage of the sodium chloride, the potassium chloride and the anhydrous calcium chloride is 20% to 50% to 30%.
3. The ternary eutectic chloride heat transfer and storage material of claim 1, wherein the mass percentage of the sodium chloride, the potassium chloride and the anhydrous calcium chloride is 30% to 40% to 30%.
4. A method for preparing the ternary eutectic chloride heat transfer and storage material according to any one of claims 1 to 3, which comprises the following steps:
weighing anhydrous calcium chloride, dried sodium chloride and dried potassium chloride according to the mass percentage, mixing and grinding; heating the ground mixture to form a homogeneous liquid; taking out the obtained liquid after the obtained liquid is cooled to room temperature, grinding and crushing to obtain the ternary eutectic chloride heat transfer and storage material;
the heating temperature is 700-900 ℃.
5. The method for preparing the ternary eutectic chloride heat transfer and storage material of claim 4, wherein the heating time is 3-5 h.
6. The method for preparing the ternary eutectic chloride heat transfer and storage material of claim 4, wherein the drying is constant temperature drying.
7. The method for preparing the ternary eutectic chloride heat transfer and storage material according to claim 6, wherein the constant-temperature drying temperature is 120-150 ℃.
8. The preparation method of the ternary eutectic chloride heat transfer and storage material of claim 6, wherein the constant temperature drying time is 24-48 h.
9. The application of the ternary eutectic chloride salt heat transfer and storage material as claimed in any one of claims 1 to 3 or the ternary eutectic chloride salt heat transfer and storage material prepared by the preparation method as claimed in any one of claims 4 to 8 in solar thermal power generation.
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