CN113603458A - Low-cost calcium-based heat storage material and preparation method thereof - Google Patents
Low-cost calcium-based heat storage material and preparation method thereof Download PDFInfo
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- CN113603458A CN113603458A CN202110885964.9A CN202110885964A CN113603458A CN 113603458 A CN113603458 A CN 113603458A CN 202110885964 A CN202110885964 A CN 202110885964A CN 113603458 A CN113603458 A CN 113603458A
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- 239000011575 calcium Substances 0.000 title claims abstract description 59
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 44
- 238000005338 heat storage Methods 0.000 title claims abstract description 37
- 239000011232 storage material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 41
- 239000010459 dolomite Substances 0.000 claims abstract description 41
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000031700 light absorption Effects 0.000 claims abstract description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000020477 pH reduction Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
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Abstract
The invention discloses a low-cost calcium-based heat storage material and a preparation method thereof, belonging to the technical field of heat storage materials. The calcium-based raw material of the calcium-based heat storage material is natural dolomite doped with manganese nitrate Mn (NO) as a light absorption component in different proportions3)2Fe (NO), iron nitrate3)3·9H2And O. According to the invention, the storage/heat release performance of the dolomite material is enhanced through the acidification pretreatment of the calcined dolomite; the defect of poor optical absorption performance of the traditional calcium-based material is overcome by doping the light-absorbing components in different molar ratios (Ca/Mg: Mn: Fe =100:0.5:1,100:1:2,100:2: 4). The calcium-based material doped with the light absorbing component can directly interact with solar radiation photons and, therefore, can absorb more solar radiation. In the invention, the acidification method is simple, the cost of the calcium-based raw material is low, and the method is suitable forEnlarging the technical route, large-scale mass production and industrial application.
Description
Technical Field
The invention belongs to the technical field of heat storage materials, and particularly relates to a calcium-based heat storage material modified based on natural dolomite acid and doped with a light absorption component Fe/Mn and a preparation method thereof.
Background
In order to relieve the problems of energy shortage and environmental pollution, the smooth transition from fossil fuel to clean renewable energy is realized. Concentrated Solar Power (CSP) offers the possibility of large-scale Power generation and commercial expansion as one of two major technologies for Solar energy utilization. Efficient and cost competitive thermal energy storage systems play a crucial role in overcoming the limitations of solar energy utilization. Compared with the sensible heat energy storage of the first generation and the latent heat energy storage of the second generation, the thermochemical energy storage has wide application prospect due to high energy storage density and high working temperature range.
Calcium carbonate CaCO to date due to high reaction kinetics and inexpensive raw materials3Is distinguished from a plurality of thermochemical energy storage materials. The thermochemical energy storage process based on Calcium cycling (CaL Looping, CaL) is applied to CSP and proposed in the late 70 th century earliest, and is widely concerned by researchers again due to the advantages of wide sources, no toxicity, environmental protection, high energy storage density and the like.
Researchers do a lot of work on basic research of calcium-based heat storage agents and obtain a plurality of stage research results, but few researchers pay attention to the low solar radiation absorption rate of calcium carbonate materials so far, and the direct conversion efficiency of the solar heat energy of the calcium-based materials is greatly limited due to the inherent characteristics.
The prior art focuses more on the carbonation stage in the calcium cycle process, and makes a series of improvements on calcium-based materials, such as mechanochemical modification, incorporation of structural stabilizers, eutectic doping of molten salts, and addition of biological templates. However, few researchers have studied the problem of low solar radiation absorption of calcium-based materials in the solar calcination process. The optical absorption of solar radiation by calcium carbonate is weak (less than 10%), and this very weak solar energy collection makes it difficult to reach the decomposition temperature of calcium carbonate required to drive the reverse endothermic reaction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a calcium-based heat storage material modified based on natural dolomite acid and doped with Fe/Mn light absorption components and a preparation method thereof. This direct light absorption mode can effectively reduce the period of heat transfer, thereby suppressing radiant heat loss and improving heat utilization efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a calcium-based heat storage material comprises the following raw materials: a calcium-based material and a light absorbing component;
the calcium-based material is natural dolomite, and the light absorption components are manganese nitrate and ferric nitrate;
ca in the calcium-based material2+And Mg2+With Mn in manganese nitrate2+Fe in ferric nitrate3+In a molar ratio of 100:0.5:1,100:1:2,100:2:4 and 100:4: 8.
The preparation method of the calcium-based heat storage material comprises the following steps:
step 1, pretreating natural dolomite to prepare a dolomite solution;
step 3, drying the mixed solution obtained in the step 2;
and 4, calcining the dried substance obtained in the step 3 to obtain the calcium-based heat storage material.
Further, the pretreatment in step 1 is to dissolve calcined dolomite in a propionic acid solution to prepare a dolomite solution.
Further, the calcining condition is 900 ℃ and 1 h; the concentration of the propionic acid solution is 50 Vol.%, the solid-to-liquid ratio is 1:15, and the dissolution conditions are 50 ℃.
Further, in the step 2, the complexing agent is citric acid.
Further, the drying conditions in step 3 were 110 ℃ for 48 hours.
Further, the calcination conditions in step 4 are: the heating rate is 5 ℃/min, the temperature is increased to 800 ℃, and the constant temperature is kept for 120 min.
Compared with the prior art, the method has the following beneficial effects:
1. the natural calcareous mineral dolomite is used, so that the cost is further reduced, and the acidification method is simple and easy to operate, and is suitable for enlarging a technical route and realizing large-scale mass production.
2. By doping the calcium-based material with the light-absorbing component manganese nitrate Mn (NO)3)2And iron nitrate Fe (NO)3)3·9H2And O, the capability of the calcium-based material for directly capturing photons from solar radiation is improved, and a direct solar radiation absorption mode is realized.
3. The invention does not need harsh conditions such as high temperature or sealing, has simple preparation method and no toxic waste in the production process, and is suitable for large-scale production.
Drawings
FIG. 1 shows the heat storage density per unit mass of the samples of comparative example and examples 1 to 5.
FIG. 2 is the spectral absorptance of examples 1-5.
Detailed Description
The purpose, technical scheme and advantages of the invention are more clearly understood through the accompanying drawings and the detailed description. It should be understood that the following examples are illustrative of the present invention only and are not to be construed as limiting the present invention. The examples do not show the concrete conditions or conditions, and the techniques or conditions described in the literature in the field are performed according to the instructions. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Preparation of Ca/Mg100 calcium-based heat storage material
The dolomite-based calcium-based heat storage material is prepared based on a sol-gel method, and specifically comprises the following steps:
step 1, preparing 90mL of propionic acid solution with the concentration of 50 Vol.%, and calcining dolomite with the particle size of 75-150 mu m in a muffle furnace at 900 ℃ for 1 h.
And 2, weighing 6g of calcined dolomite sample, pouring the weighed sample into 50 Vol.% propionic acid solution, and stirring the mixed solution for 30min in a constant-temperature heating stirrer at 50 ℃ until the dolomite is completely dissolved.
And 3, placing the mixed solution in an oven, and drying for 24 hours at 110 ℃.
And 4, putting the dried sample into a muffle furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the constant temperature for 120min to obtain the Ca/Mg100 modified calcium-based heat storage material based on dolomite acid.
Example 2
Preparation of Ca/Mg100-Mn0.5-Fe1 calcium-based heat storage material
The Ca/Mg: Mn: Fe ═ 100:0.5:1 calcium-based heat storage material was prepared based on a sol-gel method. The method specifically comprises the following steps:
step 1, preparing 90mL of propionic acid solution with the concentration of 50 Vol.%; calcining dolomite with the grain diameter of 75-150 mu m for 1h at 900 ℃ in a muffle furnace.
And 2, weighing 6g of calcined dolomite sample, pouring the weighed sample into 50 Vol.% propionic acid solution, and stirring the mixed solution for 30min in a constant-temperature heating stirrer at 50 ℃ until the dolomite is completely dissolved.
Step 3, heating the stirrer to 80 ℃ at constant temperature, adding 25.88g of complexing agent citric acid C into the mixed solution in sequence6H8O7·H2O, 141. mu.L of light-absorbing component manganese nitrate Mn (NO)3)2And 0.49g of iron nitrate Fe (NO)3)3·9H2O。
And 4, placing the filtrate in an oven, and drying for 24 hours at the temperature of 110 ℃.
And 5, putting the dried sample into a muffle furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the constant temperature for 120min to obtain the Ca/Mg100-Mn0.5-Fe1 calcium-based heat storage material.
Example 3
Preparation of Ca/Mg100-Mn1-Fe2 calcium-based heat storage material
The Ca/Mg: Mn: Fe: 100:1:2 calcium-based heat storage material is prepared based on a sol-gel method. The method specifically comprises the following steps:
step 1, preparing 90mL of propionic acid solution with the concentration of 50 Vol.%; calcining dolomite with the grain diameter of 75-150 mu m for 1h at 900 ℃ in a muffle furnace.
And 2, weighing 6g of calcined dolomite sample, pouring the weighed sample into 50 Vol.% propionic acid solution, and stirring the mixed solution for 30min in a constant-temperature heating stirrer at 50 ℃ until the dolomite is completely dissolved.
Step 3, heating the stirrer to 80 ℃ at constant temperature, and sequentially adding 26.27g of complexing agent citric acid C into the mixed solution6H8O7·H2O, 282 μ L of manganese nitrate Mn (NO) as light-absorbing component3)2And 0.98g of iron nitrate Fe (NO)3)3·9H2O。
And 4, placing the filtrate in an oven, and drying for 24 hours at the temperature of 110 ℃.
And 5, putting the dried sample into a muffle furnace, heating to 800 ℃ g at the heating rate of 5 ℃/min, and keeping the constant temperature for 120min to obtain the Ca/Mg100-Mn1-Fe2 calcium-based heat storage material.
Example 4
Preparation of Ca/Mg100-Mn2-Fe4 calcium-based heat storage material
The Ca/Mg: Mn: Fe: 100:2:4 calcium-based heat storage material is prepared based on a sol-gel method. The method specifically comprises the following steps:
step 1, preparing 90mL of propionic acid solution with the concentration of 50 Vol.%; calcining dolomite with the grain diameter of 75-150 mu m for 1h at 900 ℃ in a muffle furnace.
And 2, weighing 6g of calcined dolomite sample, pouring the weighed sample into 50 Vol.% propionic acid solution, and stirring the mixed solution for 30min in a constant-temperature heating stirrer at 50 ℃ until the dolomite is completely dissolved.
Step 3, heating the stirrer to 80 ℃ at constant temperature, and adding 27.03g of complexing agent citric acid C into the mixed solution in sequence6H8O7·H2O, 564. mu.L of light-absorbing component manganese nitrate Mn (NO)3)2And 1.96g of iron nitrate Fe (NO)3)3·9H2O。
And 4, placing the filtrate in an oven, and drying for 24 hours at the temperature of 110 ℃.
And 5, putting the dried sample into a muffle furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the constant temperature for 120min to obtain the Ca/Mg100-Mn2-Fe4 calcium-based heat storage material.
Example 5
Preparation of Ca/Mg100-Mn4-Fe8 calcium-based heat storage material
The Ca/Mg: Mn: Fe: 100:4:8 calcium-based heat storage material is prepared based on a sol-gel method. The method specifically comprises the following steps:
step 1, preparing 90mL of propionic acid solution with the concentration of 50 Vol.%; calcining dolomite with the grain diameter of 75-150 mu m for 1h at 900 ℃ in a muffle furnace.
And 2, weighing 6g of calcined dolomite sample, pouring the weighed sample into 50 Vol.% propionic acid solution, and stirring the mixed solution for 30min in a constant-temperature heating stirrer at 50 ℃ until the dolomite is completely dissolved.
Step 3, heating the stirrer to 80 ℃ at constant temperature, and adding 28.56g of complexing agent citric acid C into the mixed solution in sequence6H8O7·H2O, 1.13mL of manganese nitrate Mn (NO) as a light-absorbing component3)2And 3.92g of iron nitrate Fe (NO)3)3·9H2O。
And 4, placing the filtrate in an oven, and drying for 24 hours at the temperature of 110 ℃.
And 5, putting the dried sample into a muffle furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the constant temperature for 120min to obtain the Ca/Mg100-Mn4-Fe8 calcium-based heat storage material.
Comparative example 1
Dolomite with particle size of 75-150 μm without any treatment.
Test example 1
The samples of examples 1-5 and comparative examples were subjected to cyclic energy storage/release experiments using a Netzsch thermogravimetric analyzer (STA 449F5 Jupiter).
Approximately 10mg of the sample was placed in an alumina crucible and then a cyclic heat storage/release experiment was performed under alternating atmospheres. Pure N of the sample at 850 DEG C2Calcining for 5 minutes in an atmosphere of pure CO2Carbonation was carried out for 6 minutes in the atmosphere and a cyclic storage/release test was carried out. By switching the temperature and the gas simultaneously, a complete heating is achievedEnabling a storage/release cycling process. The heat storage/release process is repeated for 30 times, so that the heat storage/release performance of the sample can be studied in depth. CO per unit mass of sample2Absorption Capacity (C)n,g CO2Per g calcined sample, g/g) energy storage density per unit mass (D)m,nGJ/t) was used to evaluate the energy storage/release properties of the samples.
Wherein n is the cycle number; m iscar,nAnd mcal,nRespectively representing the quality of the sample to be measured after n times of carbonation and calcination;
is the molar reaction enthalpy, 178 kJ/mol.
Heat storage Density per Mass D of acid-modified Dolomite examples 1-5 with different Fe/Mn doping ratiosm,nAs shown in fig. 1, all of the examples exhibited relatively stable thermal energy storage/release capabilities. The main reason is that the existence of inert MgO in the dolomite and the synergistic effect of propionic acid modification lead the Fe/Mn to be doped, and the acid modified dolomite has a good stable structure. However, as the doping ratio of the Fe/Mn absorbing component increases, the heat storage density per unit mass of the sample gradually decreases. Example 1 the highest heat storage density per unit mass, D, after 30 cyclesm,nIt was 1.08GJ/t, which was about 1.4 times that of example 5. 30 nd times of examples 2 to 4m,nThe values are relatively close and are distributed between 0.95 and 0.99 GJ/t.
Test example 2
The optical absorption characteristics of the samples of examples 1-5 were investigated using an integrating sphere UV-visible-near infrared spectrometer (Carry 5000Agilent Technologies) at the wavelength range of 300-.
Approximately 100mg of the powder sample was placed between two quartz glass moldsThe reflectance was measured by uv-vis-nir spectroscopy. In order to quantitatively compare the solar absorptance of different powder samples, an average solar absorptance is introduced, which is calculated from the weighted integral of the sample absorptance with the standard solar spectrum am1.5d. A. theaveIs expressed as
Wherein A (λ) is the solar light absorption, λ is the wavelength, I (λ)AM1.5DThe spectrum of sunlight under the condition of AM1.5D.
The spectral absorbances of the acid-modified dolomite samples doped at different Fe/Mn ratios are shown in FIG. 2. The background shaded portion is the standard am1.5d solar spectrum corresponding to the right Y-axis. The spectral irradiance of AM1.5D was found to be concentrated mainly in the wavelength range of 300-1350 nm. In the range of 300-1350nm, the average solar absorptivity of example 1 is the lowest, and is 29.5%, which indicates that the capability of absorbing sunlight is poor. The solar light absorption capacity of the acid modified dolomite sample is gradually enhanced along with the increase of the doping proportion of Fe, Mn and Mn elements. The average solar absorptance arrangements are, in order, example 5> example 4> example 3> example 2> example 1. The overall trend of the average solar absorption rate is consistent with the darker color, wherein the maximum absorption rate of example 5 is 81.2%, which is more than 2.75 times that of example 1. In contrast, examples 2-4 have limited average solar absorptance due to the lower doping ratio of Fe-Fe and Mn-Mn.
Claims (7)
1. A calcium-based heat storage material characterized by: the raw materials comprise: a calcium-based material and a light absorbing component;
the calcium-based material is natural dolomite, and the light absorption components are manganese nitrate and ferric nitrate;
ca in the calcium-based material2+And Mg2+With Mn in manganese nitrate2+Fe in ferric nitrate3+In a molar ratio of 100:0.5:1,100:1:2 or 100:2: 4.
2. A method of preparing a calcium-based heat storage material as claimed in claim 1, characterized in that: the method comprises the following steps:
step 1, pretreating natural dolomite to prepare a dolomite solution;
step 2, adding a complexing agent and a light absorption component into the dolomite solution;
step 3, drying the mixed solution obtained in the step 2;
and 4, calcining the dried substance obtained in the step 3 to obtain the calcium-based heat storage material.
3. The method of claim 2, wherein: in the step 1, the pretreatment is to dissolve calcined dolomite in a propionic acid solution to prepare a dolomite solution.
4. The production method according to claim 3, characterized in that: the calcining condition is 900 ℃ and 1 h; the concentration of the propionic acid solution is 50 Vol.%, the solid-to-liquid ratio is 1:15, and the dissolution conditions are 50 ℃.
5. The method of claim 2, wherein: in the step 2, the complexing agent is citric acid, and the temperature is 80 ℃.
6. The method of claim 2, wherein: the drying condition in the step 3 is 110 ℃ and 48 hours.
7. The method of claim 2, wherein: the calcination conditions in step 4 are as follows: the heating rate is 5 ℃/min, the temperature is increased to 800 ℃, and the constant temperature is kept for 120 min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316921A (en) * | 2022-01-05 | 2022-04-12 | 中国科学院工程热物理研究所 | Calcium-based energy storage material, preparation method and application thereof |
| CN115784287A (en) * | 2022-12-01 | 2023-03-14 | 福州大学 | Double-template preparation method and application of sintering-resistant nano calcium-based energy storage material |
| CN116004198A (en) * | 2022-11-22 | 2023-04-25 | 南京航空航天大学 | Grade-doped calcium-based particles, and preparation method and application thereof |
| CN116162446A (en) * | 2023-02-03 | 2023-05-26 | 南京航空航天大学 | High-power-density low-cost calcium-based heat storage particles based on solid waste utilization and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658010A (en) * | 2012-05-17 | 2012-09-12 | 东南大学 | Preparation method of carbon dioxide composite calcium-base absorbent |
| CN110724500A (en) * | 2019-11-07 | 2020-01-24 | 中国矿业大学 | Magnesium-modified globular calcium-based thermochemical energy storage material and preparation method thereof |
| CN112920781A (en) * | 2021-01-25 | 2021-06-08 | 山东大学 | Heat-storage composite calcium-based heat storage spherical particle and preparation method and application thereof |
-
2021
- 2021-08-03 CN CN202110885964.9A patent/CN113603458A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658010A (en) * | 2012-05-17 | 2012-09-12 | 东南大学 | Preparation method of carbon dioxide composite calcium-base absorbent |
| CN110724500A (en) * | 2019-11-07 | 2020-01-24 | 中国矿业大学 | Magnesium-modified globular calcium-based thermochemical energy storage material and preparation method thereof |
| CN112920781A (en) * | 2021-01-25 | 2021-06-08 | 山东大学 | Heat-storage composite calcium-based heat storage spherical particle and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| KE WANG: "Porous MgO-stabilized CaO-based powders/pellets via a citric acid-based carbon template for thermochemical energy storage in concentrated solar power plants", 《CHEMICAL ENGINEERING JOURNAL》 * |
| YUN DA: "Calcium-based composites for direct solar-thermal conversion and thermochemical energy storage", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 刘爱文: "用毛蛤壳制备柠檬酸钙、丙酸钙的研究", 《应用科技》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316921A (en) * | 2022-01-05 | 2022-04-12 | 中国科学院工程热物理研究所 | Calcium-based energy storage material, preparation method and application thereof |
| CN114316921B (en) * | 2022-01-05 | 2024-04-26 | 中国科学院工程热物理研究所 | Calcium-based energy storage material, preparation method and application thereof |
| CN116004198A (en) * | 2022-11-22 | 2023-04-25 | 南京航空航天大学 | Grade-doped calcium-based particles, and preparation method and application thereof |
| CN115784287A (en) * | 2022-12-01 | 2023-03-14 | 福州大学 | Double-template preparation method and application of sintering-resistant nano calcium-based energy storage material |
| CN116162446A (en) * | 2023-02-03 | 2023-05-26 | 南京航空航天大学 | High-power-density low-cost calcium-based heat storage particles based on solid waste utilization and preparation method thereof |
| CN116162446B (en) * | 2023-02-03 | 2023-12-01 | 南京航空航天大学 | High-power-density low-cost calcium-based heat storage particles based on solid waste utilization and preparation method thereof |
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