CN117143573A - Efficient and stable low-cost calcium-based heat storage particles based on solid waste utilization and preparation method and application thereof - Google Patents
Efficient and stable low-cost calcium-based heat storage particles based on solid waste utilization and preparation method and application thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 67
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011575 calcium Substances 0.000 title claims abstract description 48
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 48
- 238000005338 heat storage Methods 0.000 title claims abstract description 45
- 239000002910 solid waste Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 43
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000010902 straw Substances 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 17
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 15
- 239000010959 steel Substances 0.000 claims abstract description 15
- 239000010459 dolomite Substances 0.000 claims abstract description 14
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 14
- 239000004579 marble Substances 0.000 claims abstract description 13
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract 2
- 239000001569 carbon dioxide Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 22
- 238000004146 energy storage Methods 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 8
- 238000005563 spheronization Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 11
- 230000003595 spectral effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 43
- 239000002243 precursor Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000002131 composite material Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C09K5/16—Materials undergoing chemical reactions when used
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a high-efficiency stable low-cost calcium-based heat storage particle based on solid waste utilization, which comprises solid waste, natural ore and chloride; wherein the solid waste comprises marble tailings, steel slag and straw, the natural ore is dolomite, and the chloride salt is magnesium chloride; the preparation method comprises the following steps: (1) Mixing solid waste and natural ore, adding chloride salt solution prepared by chloride salt, and granulating; (2) Calcining the particles, and carbonating the particles in a carbon dioxide atmosphere to obtain the calcium-based heat storage particles; the calcium-based heat storage particles improve the spectral absorptivity and the circulation stability by doping steel slag powder, improve the circulation stability by doping natural ores and chloride salt, and improve the heat storage rate of calcium carbonate by doping straw and chloride salt.
Description
Technical Field
The invention relates to a calcium-based heat storage particle and a preparation method and application thereof, in particular to a high-efficiency and stable low-cost calcium-based heat storage particle based on solid waste utilization and a preparation method and application thereof.
Background
The widespread use of fossil fuels has resulted in serious greenhouse gas emissions and environmental pollution. The renewable energy sources can be developed and utilized, so that the emission of greenhouse gases can be effectively reduced, and the natural environment is protected. Compared with other renewable energy sources, solar energy has the unique advantages of abundant resources, wide distribution, no pollution and the like, and is considered to be the mostClean and develop the energy with the greatest potential. In order to solve the problems of dispersion and instability of solar energy, concentrating solar power generation technology with integrated heat storage system has become a solution with strong schedulability and significantly improved flexibility of power system. Third generation CSP power plants will operate at high temperatures to increase power generation efficiency, but molten salts cannot meet the latest technical requirements due to their limited operating temperature and strong corrosiveness. The calcium loop (CaL) process is a potential thermal energy storage technology because it uses CaCO which is cheap, easily available, nontoxic and harmless 3 Base materials have become a focus of attention. The principle of heat storage/release through CaL technology is CaCO 3 Reversible calcination and carbonation reaction between CaO. With repetition of the energy storage/release cycle, caCO 3 The rapid sintering of CaO results in a sharp drop in energy storage density, which is detrimental to subsequent energy storage. Various methods have been proposed to inhibit CaCO 3 Sintering of the material, such as acid treatment, mechanical activation and doping with inert stabilizers. Wherein the doping inert stabilizer is used for improving CaCO 3 The most common and effective method for cycle stability. In addition, black substances are doped in the calcium-based material as inert materials to improve the solar absorptivity of the calcium-based material, so that the calcium-based material can absorb solar energy under direct irradiation, and heat resistance and heat loss are reduced. Although the cycle stability and the energy storage density of the composite calcium-based materials are greatly improved, the composite calcium-based materials have high synthesis cost and complex preparation method, and are not beneficial to large-scale production. To solve the problem of high cost of calcium-based materials, we choose to use solid wastes containing calcium and natural ores, which are not only cheap but also environmentally friendly. Therefore, there is interest in large scale thermochemical energy storage using calcium-containing solid waste (steel slag, carbide slag, marble tailings) and natural ores (dolomite, marble). Despite extensive research on these materials, the problems of complex solid waste and natural ore processing processes and high processing costs remain unsolved. Extrusion spheronization is a prominent one among many synthetic methods due to its mass productivity, solving the problem of complex preparation methods. CaCO prepared by the method 3 The particles have good heat storage/release propertiesCan be used for effectively preventing elutriation-shaped powder materials in a reactor with mechanical strength. However, this preparation method exacerbates the decrease in reaction kinetics caused by the doping of inert materials. Thus, caCO is improved 3 The reaction kinetics of the particles can be studied from two angles. One is to dope some chloride salt accelerator into CaCO 3 In the granules, this has proved to be effective in improving CaCO 3 But the material is expensive and may be relatively CaCO 3 Has a negative effect on the cycle stability of (c). The other is to dope a proper amount of pore-forming agent in the particles to maintain the porous structure, but the cost of pore-forming agent such as microcrystalline cellulose (MCC) is very high. There is a need to select suitable low cost pore formers and accelerators to improve CaCO 3 Is a reaction kinetics of (2). Straw is used as one of main solid wastes, and has the potential of becoming a particle pore-forming agent after being crushed. However, there is currently no inexpensive and readily available CaCO that can be enhanced 3 An effective promoter of the circulation stability. Thus, the recovery of solid waste produces a low cost, efficient, stable CaCO 3 Heat storage pellets are a great challenge for industrialization of CaL processes.
Disclosure of Invention
The invention aims to: the invention aims to provide a high-efficiency and stable low-cost calcium-based heat storage particle based on solid waste utilization and a preparation method thereof.
The technical scheme is as follows: the low-cost calcium-based heat storage particles based on the utilization of solid wastes are efficient and stable, and the raw materials comprise solid wastes, natural ores and chloride; the solid waste comprises marble tailings, straw and steel slag.
Further, the natural ore is dolomite and the chloride salt is magnesium chloride.
Further, the solid waste and the natural ore are in the form of powder.
Further, the mass ratio of the marble powder Dan Wei, the dolomite powder, the steel slag powder, the straw powder and the magnesium chloride in the precursor is 90:30:30:10:10-15.
The composite calcium-based particlesMixing solid waste and natural ore, adding chloride salt solution prepared by chloride salt to prepare a precursor, adjusting the humidity of the precursor, preparing the precursor mixture into particles by an extrusion-spheronization method, calcining the particles in an air atmosphere, and then placing the particles in CO 2 Carbonating in the atmosphere to obtain the composite calcium-based particles.
Further, the condition of calcining the spherical particles in an air atmosphere is 600-1000 ℃ for several hours.
Further, in CO 2 The carbonating condition in the atmosphere is 600-900 ℃ for several hours.
The application of the composite calcium-based particles in solar thermochemical energy storage.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the spectral absorptivity and the cyclic stability are improved by doping the slag powder, dolomite powder and magnesium chloride, and the heat storage rate of the calcium carbonate is improved by doping the magnesium chloride and the straw powder. In addition, the composite calcium carbonate particles prepared by adopting the extrusion-spheronization method can directly absorb solar energy, and can reduce heat loss to realize high-efficiency energy conversion. The composite calcium carbonate particles have better reaction characteristics, i.e., lower reaction temperature and faster reaction rate, in addition to excellent cycle stability, than other calcium carbonate particles.
Drawings
FIG. 1 is a schematic illustration of a process for preparing calcium-based heat storage particles;
FIG. 2 is an SEM image of the surface and interior of the calcium-based heat storage particles prepared in example 1;
FIG. 3 is an XRD pattern of the calcium-based heat storage particles prepared in example 1 and comparative examples 1 and 7;
FIG. 4 is a schematic illustration of a calcium-based heat storage particle heat storage/release process;
FIGS. 5 and 6 are the cyclic stability at 750℃of the calcium-based heat storage particles prepared in examples and comparative examples;
FIGS. 7 and 8 are the cycling stability at 800℃of the calcium-based heat storage particles prepared in examples and comparative examples;
FIG. 9 is a spectral absorption diagram of the calcium-based heat storage particles prepared in example 1 and comparative examples 1, 2, 4 and 7;
FIG. 10 is a graph comparing the decomposition rates at 750℃for examples and comparative examples;
fig. 11 is a graph showing the mechanical strength of the examples and comparative examples.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
The invention adopts an extrusion-spheronization method to prepare composite calcium-based heat storage particles as shown in figure 1. The method comprises the following specific steps:
step 1, uniformly stirring marble Dan Wei mineral powder, dolomite powder, straw powder and steel slag powder in a beaker to obtain precursor powder;
step 2, adding a precursor solution into precursor powder, wherein the mass ratio of marble Dan Wei mineral powder, dolomite powder, steel slag powder, straw powder and magnesium chloride is 90:30:30:10:10, dissolving anhydrous magnesium chloride into tap water to prepare the precursor solution, fully stirring other powder until the precursor solution is completely uniform, pouring the precursor solution into the precursor powder, and uniformly mixing to obtain a precursor mixture;
step 3, airing the precursor mixture to a proper humidity (the moisture accounts for 10-60 wt% of the mixture), and granulating the precursor mixture by an extrusion-spheronization machine;
step 4, placing the particles into a muffle furnace, and calcining for 3 hours in an air atmosphere at 700 ℃ to obtain composite CaO particles; the temperature rise rate was 10℃per minute to 700 ℃.
Step 5, caO particles are put into a tube furnace to be treated in pure CO 2 Carbonating for 5 hours in the atmosphere, setting the temperature to 700 ℃, and heating the mixture at a speed of 10 ℃/min to obtain the composite CaCO 3 Particles;
step 6, finally, compound CaCO is obtained through a standard sieve 3 The particles are divided into different particle size ranges, such as 900-1200 μm.
Example 2
The comparative example is different from example 1 in that the mass ratio of marble Dan Wei mineral powder, dolomite powder, steel slag powder, straw powder and magnesium chloride is 90:30:30:10:15.
Comparative example 1
This comparative example differs from example 1 in that no magnesium chloride was added.
Comparative example 2
This comparative example is different from example 1 in that no steel slag powder and no magnesium chloride were added.
Comparative example 3
The difference between this comparative example and comparative example 2 is that the straw powder content is 3 times that of comparative example 2.
Comparative example 4
The present comparative example is different from comparative example 1 in that no straw powder and magnesium chloride were added.
Comparative example 5
The difference between this comparative example and comparative example 1 is that the precursor powder is pure dolomite powder.
Comparative example 6
The present comparative example is different from comparative example 1 in that the precursor powder is pure marble powder.
Comparative example 7
The present comparative example is different from comparative example 1 in that no steel slag powder, straw powder, and magnesium chloride were added.
Structural characterization
As shown in FIG. 2, the calcium-based heat storage particles prepared in example 1 have relatively rich pore structures on the inner and outer surfaces thereof, which are produced by decomposing straw powder and can be CO 2 Diffusion provides channels, thereby improving the performance of the material.
As shown in FIG. 3, the components in the calcium-based heat storage particles remove CaCO 3 In addition to CaTiO 3 、SiO 2 And Fe (Fe) 3 O 4 The inert materials effectively inhibit the sintering deactivation of calcium carbonate/calcium oxide and serve as spectral absorption enhancing substances to improve the solar spectral absorption capacity of the particles.
Performance testing
As shown in FIG. 4, the heat storage process is carried out in a bulk absorption reactor, sunlight directly irradiates the surface of particles, the particles absorb solar radiation energy, the temperature rises, and the particles are decomposed into CaO and CO 2 And respectively enterThe respective storage tanks are stored to complete the energy storage process, and CaO and CO are used for releasing energy when the energy is needed 2 The reaction is carried out in the acidification reactor, heat is released, and the energy output of the target temperature can be obtained by controlling the flow of reactants, the reaction atmosphere, the temperature and the flow of working medium.
The energy storage density testing method comprises the following steps: 12mg of calcium-based heat storage particles are taken and put into a synchronous thermal analyzer, and a test program is set: raising the temperature to 750 ℃ at a heating rate of 10 ℃/min under nitrogen atmosphere, maintaining for 15min for decomposition, and switching to 50% CO 2 The atmosphere was kept for 20min for acidification, and this procedure was repeated several times to obtain a TG curve. The energy storage density is calculated by the formulaWherein n is the number of cycles +.>And m CaO,n Is the whole compound CaCO after the nth carbonation under the constant temperature condition 3 Mass of the granules and weight of the whole composite CaO granules after the nth calcination, +.>Is CO 2 ΔH is the enthalpy of carbonation per mole of calcium oxide (178 kJ/mol).
The storage densities and the cycle stabilities before and after the cycle at 750℃are shown in Table 1.
TABLE 1
The storage densities and the cycle stabilities before and after the cycling at 800℃are shown in Table 2.
TABLE 2
From tables 1 and 2, it can be seen that dolomite powder, steel slag powder and magnesium chloride can significantly improve the circulation stability of calcium carbonate, and straw powder can improve the circulation stability, but also can reduce the energy storage density. The calcium-based heat storage particles prepared in example 1 and comparative examples 1 to 7 were subjected to stability test at a high temperature of 750 ℃ and the test results are shown in fig. 5 and 6. The calcium-based heat storage particles prepared in example 1 and comparative examples 5, 6 and 7 were cycled under more severe conditions (800 ℃) several tens of times, and the test results are shown in fig. 7 and 8. After 50 cycles, the energy storage density of the calcium-based heat storage particles prepared in example 1 is still as high as 1191kJ/kg, confirming good cycling stability of the particles.
The method is characterized in that the cyclic stability test of the calcium-based particles with the size of 1000-1200 mu m is carried out by placing composite calcium carbonate particles with the size of 1000-1200 mu m into a sample cell of an ultraviolet-visible spectrophotometer for compaction, and the reflectivity R (lambda) of a test sample is measured, wherein the data interval is 5nm, and the test range is 200-2500 nm. The absorption is obtained by a (λ) =1-R (λ). The spectral absorptivity and the radiant energy distribution of AM1.5 solar energy to the ground are then integrated to give the total energy absorbed by the particles, which is divided by the total energy of solar radiation to give the average absorptivity. The solar energy is used as an incident light source to directly provide energy for the composite energy storage particles, and in the AM1.5 spectrum range of 200-2500 nm, as shown in figure 9, the average absorptivity of the composite particles of the example 1 is 70.64%, and the composite marble and dolomite particles prepared by the same method are only 13.4%.
It can be seen from fig. 10 that the decomposition rate of example 1 is significantly faster than the other two calcium carbonate particles at 750 c, and that the decomposition rate of example 1 is 1.71 times that of comparative example 1 and 1.90 times that of comparative example 7. The decomposition rate of example 1 was also significantly faster than the other two calcium carbonate particles at 800 ℃, the decomposition rate of example 1 was 1.63 times that of comparative example 1 and 2.04 times that of comparative example 7, and the heat storage rate of example 1 was not reduced even after 30 cycles, significantly faster than the other two calcium carbonate particles. Therefore, in the heat storage process, the calcium-based heat storage particles in embodiment 1 greatly improve the solar energy utilization rate of the CSP system and improve the system efficiency.
As can be seen from FIG. 11, the average compressive strength of comparative example 6, which was synthesized with pure marble, was 3.84N, which is much higher than that of comparative example 5 (1.36N), which was synthesized with pure dolomite. The average compressive strength of comparative example 7 was between comparative example 5 and comparative example 6 and was 2.73N, and the mechanical strengths of comparative example 2 and comparative example 3 obtained were 1.05N and 0.17N, respectively. This shows that the straw powder significantly reduces CaCO 3 The mechanical strength of the granules and this effect becomes more pronounced as the straw powder content increases. When the steel slag powder was added in comparative example 7, the mechanical strength of comparative example 4 was reduced to 1.77N, indicating that the steel slag powder also reduced CaCO 3 Mechanical strength of the pellets. The mechanical strength of comparative example 1 was only 0.31N. However, the average compressive strength of example 1 increased significantly to 2.98N, which is significantly higher than the minimum (1N) required for practical use of the reactor.
Claims (10)
1. The high-efficiency stable low-cost calcium-based heat storage particle based on solid waste utilization is characterized in that raw materials comprise solid waste, natural ore and chloride, wherein the solid waste comprises marble tailings, straw and steel slag.
2. The high-efficiency stable low-cost calcium-based heat storage granule based on solid waste utilization according to claim 1, wherein the natural ore is dolomite.
3. The high-efficiency stable low-cost calcium-based heat storage granule based on solid waste utilization according to claim 2, wherein the chloride salt is magnesium chloride.
4. The efficient and stable low-cost calcium-based heat storage granule based on solid waste utilization according to claim 1, wherein the solid waste and natural ore are in powder form.
5. The high-efficiency stable low-cost calcium-based heat storage granule based on solid waste utilization according to claim 3, wherein the mass ratio of marble tailings, dolomite, steel slag, straw and magnesium chloride is 90:30:30:10:10 to 15.
6. A method for preparing the low-cost calcium-based heat storage particles of any one of claims 1 to 5, which is efficient and stable based on solid waste utilization, comprising the steps of:
(1) Mixing solid waste with natural ore, adding chloride salt solution prepared by chloride salt, and granulating;
(2) Calcining the particles, and carbonating the particles in a carbon dioxide atmosphere to obtain the calcium-based heat storage particles.
7. The method for preparing the low-cost calcium-based heat storage particles based on the high efficiency and stability of solid waste utilization according to claim 6, wherein in the step (2), the calcining temperature is 600-1000 ℃.
8. The method for preparing the low-cost calcium-based heat storage particles with high efficiency and stability based on solid waste utilization according to claim 6, wherein in the step (2), the carbonation temperature is 600-900 ℃.
9. The method for preparing the low-cost calcium-based heat storage particles based on the high efficiency and stability of solid waste utilization, which is disclosed in claim 6, is characterized in that the extrusion-spheronization method is adopted for preparing the particles.
10. Use of the high-efficiency stable low-cost calcium-based heat storage particles according to claims 1-5 for solar thermochemical energy storage based on solid waste utilization.
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