CN117923552A - Ferromanganese composite metal oxide heat storage material and preparation method thereof - Google Patents
Ferromanganese composite metal oxide heat storage material and preparation method thereof Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 95
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000005338 heat storage Methods 0.000 title claims abstract description 84
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 73
- 239000011232 storage material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 24
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 22
- 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 description 18
- 239000000463 material Substances 0.000 description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- -1 copper-manganese metal oxide Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a ferromanganese composite metal oxide heat storage material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a manganese source, an iron source and a solvent, then adding a complexing agent and a pH regulator, and stirring to obtain a gel solution; and sequentially drying, first calcining and second calcining the gel solution to obtain the ferromanganese composite metal oxide heat storage material. The general formula of the ferromanganese composite metal oxide heat storage material is (Mn xFe1‑x)2O3, wherein x is more than or equal to 0.5 and less than or equal to 0.8. The ferromanganese composite metal oxide heat storage material prepared by the preparation method provided by the invention has the advantages of high heat storage density, high oxidation reduction rate and excellent circulating heat storage performance.
Description
Technical Field
The invention belongs to the technical field of heat storage materials, and particularly relates to a ferromanganese composite metal oxide heat storage material and a preparation method thereof.
Background
In order to cope with problems such as global warming and exhaustion of non-renewable resources, more and more countries are beginning to pay attention to the use of renewable energy sources. With the gradual increase of the duty ratio of renewable energy sources in energy consumption, the problem of mismatch of renewable energy sources such as solar energy, wind energy and the like in time and space supply and demand is increasingly highlighted, and the development of a novel energy storage technology is a key support technology for solving the problem. The thermochemical heat storage has the advantages of high energy storage density, long energy storage period and small heat loss.
The principle of thermochemical heat storage is to utilize reversible thermochemical reactions to realize the heat storage and release processes. Thermochemical is largely divided into metal hydride systems, carbonate systems, hydroxide systems, metal oxide systems, ammonia systems and organic systems. Currently, the most studied is the metal oxide system. The metal oxide heat storage system realizes energy storage and release by utilizing the mutual conversion of metal oxides between different valence states.
Researchers find that the Mn 2O3/Mn3O4 oxide system has the advantages of environmental friendliness, no toxicity, low production cost and the like, and is a very potential heat storage material. However, under the repeated high temperature condition, the single Mn 2O3/Mn3O4 heat storage material has obvious grain growth and coarsening of manganese oxide particles, so that the defects of poor redox power, poor cycle performance and the like exist, and the normal use of the material is seriously influenced.
CN113736432B discloses a metal oxide heat storage material, a metal oxide heat storage unit and a preparation method, wherein the metal oxide material is a Cu 1.5Mn1.5O4 composite metal oxide material, the Cu 1.5Mn1.5O4 composite metal oxide material is prepared by a hydrothermal method, a hydrothermal reaction product is subjected to high-temperature calcination at 800-900 ℃ in the hydrothermal method to obtain the Cu 1.5Mn1.5O4 composite metal oxide material, and the Cu 1.5Mn1.5O4 composite metal oxide material has a hollow porous structure after multiple heat storage cycles.
However, the cyclic heat storage performance of the copper-manganese metal oxide heat storage material still needs to be improved, and development of a novel manganese-based metal oxide heat storage material is needed to improve the oxidation reduction rate and the cyclic heat storage performance of the novel manganese-based metal oxide heat storage material.
Disclosure of Invention
The invention aims to provide a ferromanganese composite metal oxide heat storage material and a preparation method thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the invention provides a method for preparing a ferromanganese composite metal oxide heat storage material, which comprises the following steps:
(1) Mixing a manganese source, an iron source and a solvent, then adding a complexing agent and a pH regulator, and stirring to obtain a gel solution;
(2) And (3) sequentially drying, first calcining and second calcining the gel solution obtained in the step (1) to obtain the ferromanganese composite metal oxide heat storage material.
In the present invention, the first calcination and the second calcination are performed in a muffle furnace under an air atmosphere.
The preparation method provided by the invention comprises the steps of preparing a precursor by a sol-gel method, and then drying and calcining twice. The preparation method is simple and convenient, has high production efficiency, and is suitable for large-scale industrial production; the prepared ferromanganese composite metal oxide heat storage material has high heat storage density, high oxidation-reduction rate and excellent circulating heat storage performance.
It is worth to say that the invention adopts twice calcination treatment after obtaining the dried gel, so that the product performance is more excellent. First calcining at low temperature, removing water adsorbed on the surface and oxidizing various alkoxy groups, and then second calcining at high temperature, wherein organic groups in the gel material are removed; in addition, the gel material may continuously release various gases during the temperature rising process. Compared with the primary calcination process, the sample has more uniform grain size and better oxidation-reduction rate and cycle performance after the secondary calcination.
As a preferred embodiment of the present invention, the molar ratio of the manganese source to the iron source in the step (1) is (1-5): 1, and may be, for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or 4.5:1, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
It is worth to say that the invention can make iron oxide and manganese oxide have stronger interaction by regulating the doping proportion of Mn and Fe to form Mn-Fe composite metal oxide, mn-Fe composite metal oxide is far better than single manganese oxide or iron oxide in oxidation reduction performance, and after multiple times of circulation, high temperature sintering phenomenon is avoided, and higher heat storage density can still be maintained.
Preferably, the manganese source of step (1) comprises any one or a combination of at least two of nitrate, acetate, chloride or sulfate salts of manganese.
Preferably, the iron source of step (1) comprises any one or a combination of at least two of nitrate, acetate, chloride or sulfate salts of iron.
Preferably, the step (1) solvent comprises water.
The amount of the solvent to be added is not particularly limited in the present invention, as long as the added solvent can dissolve the manganese source and the iron source.
Preferably, the temperature of the mixing in the step (1) is 70 to 90 ℃, and for example, 72 ℃, 74 ℃,75 ℃, 77 ℃, 79 ℃, 80 ℃, 82 ℃, 84 ℃, 85 ℃, 87 ℃, 89 ℃ or the like can be used, but the above-mentioned values are not limited thereto, and other values not shown in the numerical range are applicable.
Preferably, the mixing of step (1) is performed with stirring.
As a preferred embodiment of the present invention, the complexing agent of step (1) comprises ethylenediamine tetraacetic acid (EDTA).
In the invention, the precursor is prepared by a sol-gel method, and ethylenediamine tetraacetic acid is used as a complexing agent, so that the ethylenediamine tetraacetic acid can chelate a plurality of metal ions, four carboxyl oxygen and two amino nitrogen can be used as coordination atoms, the four carboxyl oxygen and the two amino nitrogen can be used as tetradentate ligands and hexadentate ligands, the tetradentate ligands and the hexadentate ligands can be used as chelate complexes with metal ions such as manganese, iron and the like, and the EDTA can form chelate complexes with a plurality of five-membered rings when reacting with the metal ions, so that the complexing reaction has high completeness, and the EDTA can ensure that the manganese ions and the iron ions are uniformly distributed in a solution in a short time.
Preferably, the ratio of the molar amount of complexing agent to the total molar amount of manganese source and iron source in step (1) is (0.8-1.2): 1, which may be, for example, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1 or 1.15:1, etc., but is not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the pH adjuster of step (1) comprises aqueous ammonia.
Preferably, the pH regulator in step (1) regulates the pH of the system to 7-8, which may be, for example, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 or 7.9, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the stirring in the step (1) is 70 to 90 ℃, and for example, 72 ℃, 74 ℃,75 ℃, 77 ℃, 79 ℃, 80 ℃, 82 ℃, 84 ℃, 85 ℃, 87 ℃, 89 ℃ or the like can be used, but the stirring is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the stirring time in the step (1) is 2-4h, for example, 2.2h, 2.4h, 2.5h, 2.7h, 2.9h, 3h, 3.2h, 3.4h, 3.5h, 3.7h or 3.9h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In a preferred embodiment of the present invention, the drying temperature in the step (2) is 170 to 200 ℃, and for example, it may be 172 ℃, 175 ℃, 177 ℃, 179 ℃, 180 ℃, 182 ℃, 185 ℃, 187 ℃, 190 ℃, 192 ℃, 195 ℃, 197 ℃, 199 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the drying time in step (2) is 4-6h, for example, 4.2h, 4.4h, 4.5h, 4.7h, 4.9h, 5h, 5.2h, 5.4h, 5.5h, 5.7h or 5.9h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature rising rate of the first calcination in the step (2) is 3 to 7 ℃/min, and may be, for example, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, or 6.5 ℃/min, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the temperature rising end point of the first calcination in the step (2) is 350 to 450 ℃, for example, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃ or 440 ℃ and the like, but the method is not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the first calcination in step (2) has a holding time of 3-5h, for example, 3.2h, 3.4h, 3.5h, 3.7h, 3.9h, 4h, 4.2h, 4.4h, 4.5h, 4.7h or 4.9h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, after the first calcining in step (2), the second calcining is further followed by cooling to room temperature with a furnace.
In a preferred embodiment of the present invention, the temperature rising rate of the second calcination in the step (2) is 3 to 7 ℃/min, and may be, for example, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, or 6.5 ℃/min, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the second calcination in step (2) has a temperature rise end point of 750 to 850 ℃, for example 760 ℃, 770 ℃, 780 ℃, 790 ℃,800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the second calcination in step (2) has a holding time of 3-5h, for example, 3.2h, 3.4h, 3.5h, 3.7h, 3.9h, 4h, 4.2h, 4.4h, 4.5h, 4.7h or 4.9h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferable technical scheme of the invention, the second calcination in the step (2) further comprises cooling to room temperature along with the furnace.
In the present invention, the second calcination is cooled to room temperature and then further comprises grinding.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing a manganese source, an iron source and a solvent at 70-90 ℃, then adding a complexing agent and a pH regulator, and stirring for 2-4 hours at 70-90 ℃ to obtain a gel solution;
The molar ratio of the manganese source to the iron source is (1-5): 1;
The complexing agent comprises ethylenediamine tetraacetic acid; the ratio of the molar amount of the complexing agent to the total molar amount of the manganese source and the iron source is (0.8-1.2): 1;
the pH regulator comprises ammonia water; the pH regulator regulates the pH of the system to 7-8;
(2) Drying the gel solution obtained in the step (1) at 170-200 ℃ for 4-6 hours, then heating to 350-450 ℃ at the heating rate of 3-7 ℃/min for first calcination and heat preservation for 3-5 hours, then cooling to room temperature along with a furnace, heating to 750-850 ℃ at the heating rate of 3-7 ℃/min for second calcination and heat preservation for 3-5 hours, and then cooling to room temperature along with the furnace to obtain the ferromanganese composite metal oxide heat storage material.
In a second aspect, the invention provides a ferromanganese composite metal oxide heat storage material, which is prepared by the preparation method in the first aspect.
In a preferred embodiment of the present invention, the general formula of the ferromanganese composite metal oxide heat storage material is (Mn xFe1-x)2O3, wherein 0.5.ltoreq.x.ltoreq.0.8, and for example, 0.52, 0.55, 0.57, 0.6, 0.62, 0.65, 0.67, 0.7, 0.72, 0.75, 0.77, or 0.79, etc., but not limited to the values listed, other values not listed in the numerical range are equally applicable.
According to the invention, the sintering agglomeration phenomenon of manganese oxide is effectively improved by adding iron ions, and the oxidation-reduction rate of the ferromanganese composite metal oxide heat storage material is high, and the cycle performance is greatly improved.
It is worth to say that the regulation and control of the manganese ion content in the composite metal oxide is particularly important, and when the manganese ion ratio is too small, the composite metal oxide only undergoes a reduction reaction and does not undergo an oxidation reaction in the oxidation-reduction process. When the manganese ion ratio is too large, the composite metal oxide hardly changes in mass during oxidation-reduction, and it is considered that the composite metal oxide does not participate in the reaction. The composite metal oxide heat storage material has good cycle performance and heat storage/release performance only when the manganese ion proportion is controlled within the range of 0.5-0.8.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method provided by the invention prepares the precursor through sol-gel method, and then prepares the ferromanganese composite metal oxide heat storage material after drying and twice calcining, and the preparation method is simple and convenient, has high production efficiency and is suitable for large-scale industrial production;
(2) The ferromanganese composite metal oxide heat storage material provided by the invention effectively improves the sintering agglomeration phenomenon of single manganese oxide, and the obtained ferromanganese composite metal oxide heat storage material has the advantages of high heat storage density, high oxidation-reduction rate and excellent circulating heat storage performance.
Drawings
FIG. 1 is a graph showing the thermogravimetric curve of the heat storage material of ferromanganese composite metal oxide prepared in example 1 compared with commercially available pure manganese oxide;
FIG. 2 is a TG-DSC graph of the heat storage material of ferromanganese composite metal oxide prepared in example 1;
FIG. 3 is an X-ray diffraction chart of the ferromanganese composite metal oxide heat storage material prepared in example 1;
FIG. 4 is a graph showing the thermogravimetric profile of the ferromanganese composite metal oxide heat storage material prepared in example 1 after different cycle times.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a ferromanganese composite metal oxide heat storage material, which comprises the following steps:
(1) Mixing manganese nitrate, ferric nitrate and water at 80 ℃, then adding ethylenediamine tetraacetic acid and ammonia water, and stirring for 3 hours at 80 ℃ to obtain a gel solution;
The molar ratio of the manganese nitrate to the ferric nitrate is 4:1;
the ratio of the molar quantity of the ethylenediamine tetraacetic acid to the total molar quantity of the manganese nitrate and the ferric nitrate is 1:1;
The ammonia water adjusts the pH of the system to 7.5;
(2) Drying the gel solution obtained in the step (1) at 180 ℃ for 5 hours, then heating to 400 ℃ at a heating rate of 5 ℃/min for first calcination and heat preservation for 4 hours, then cooling to room temperature along with a furnace, then heating to 800 ℃ at a heating rate of 5 ℃/min for second calcination and heat preservation for 4 hours, then cooling to room temperature along with the furnace, and finally grinding for 15 minutes to obtain the ferromanganese composite metal oxide heat storage material.
The ferromanganese composite metal oxide heat storage material prepared in the embodiment is subjected to material performance characterization:
(1) The measurement and analysis of thermogravimetry and reaction enthalpy were carried out using a synchronous thermal analyzer model STA-449F3 manufactured by the company of che, germany, the test procedure was to heat up from room temperature to 1050 ℃, keep the temperature for 5 minutes, then cool down to 700 ℃ for the first time to remove impurities and interference factors, the air flow was set to 50mL/min, the nitrogen gas was a shielding gas, the nitrogen flow was set to 20mL/min, and then one cycle was repeated for data recording.
(2) The X-ray diffraction analysis was performed using an X-ray diffractometer Rigaku SmartLab of japan corporation, and the step size was set to 0.01 °.
Fig. 1 is a graph comparing the thermal weight curves of the ferromanganese composite metal oxide heat storage material prepared in this example and commercially available pure manganese oxide, and as can be seen from fig. 1, the commercially available manganese oxide particles only undergo a reduction reaction after undergoing a first high temperature, and lose the oxidizing ability. The ferromanganese composite metal oxide prepared by the embodiment has good oxidation-reduction cycle capability, normal sample weight loss and weight gain in the oxidation-reduction process, low sample loss rate when heating is stopped, and excellent heat storage/release performance.
Fig. 2 is a TG-DSC graph of the heat storage material of the ferromanganese composite metal oxide prepared in this example, and as can be seen from fig. 2, the reduction enthalpy of the ferromanganese composite metal oxide is 261.8J/g, and the oxidation enthalpy is 262.6J/g. The reduction temperature of the ferromanganese composite metal oxide is 998 ℃ and the oxidation temperature is 819 ℃. This shows that: the ferromanganese composite metal oxide prepared by the preparation method provided by the invention has large oxidation enthalpy value and large heat storage density.
Fig. 3 is an X-ray diffraction diagram of the heat storage material of the ferromanganese composite metal oxide prepared in this example, and as can be seen from fig. 3, manganese nitrate and ferric nitrate raw materials form a new crystal phase from two crystal phases, and the prepared ferromanganese composite oxide is a main substance participating in the oxidation-reduction process.
Fig. 4 is a graph of thermal gravimetric curves of the heat storage material of the ferromanganese composite metal oxide prepared in this example after different cycle times, and as can be seen from fig. 4, the redox capability of the ferromanganese composite metal oxide was tested after the ferromanganese composite metal oxide underwent 50, 100, 150 and 200 redox cycles in the tube furnace. The ferromanganese composite metal oxide can still maintain good oxidation-reduction capability after 200 cycles, and the weight loss rate and the weight gain rate are in normal ranges without obvious weight loss or weight gain. This shows that: the ferromanganese composite metal oxide prepared by the preparation method provided by the invention has better oxidation-reduction capability.
From the above characterization results, it is known that the ferromanganese composite metal oxide heat storage material prepared by the embodiment has high heat storage density, high oxidation-reduction rate and excellent cycle heat storage performance; meanwhile, the product has higher purity, better crystallinity and uniform particle size.
Example 2
The embodiment provides a preparation method of a ferromanganese composite metal oxide heat storage material, which comprises the following steps:
(1) Mixing manganese chloride, ferric chloride and water at 70 ℃, then adding ethylenediamine tetraacetic acid and ammonia water, and stirring for 4 hours at 70 ℃ to obtain a gel solution;
the molar ratio of the manganese chloride to the ferric chloride is 1:1;
The ratio of the molar amount of the ethylenediamine tetraacetic acid to the total molar amount of the manganese chloride and the ferric chloride is 0.8:1;
The ammonia water adjusts the pH of the system to 7;
(2) Drying the gel solution obtained in the step (1) at 170 ℃ for 6 hours, then heating to 350 ℃ at a heating rate of 3 ℃/min for first calcination and heat preservation for 5 hours, cooling to room temperature along with a furnace, heating to 750 ℃ at a heating rate of 3 ℃/min for second calcination and heat preservation for 5 hours, cooling to room temperature along with the furnace, and finally grinding for 15 minutes to obtain the ferromanganese composite metal oxide heat storage material.
Example 3
The embodiment provides a preparation method of a ferromanganese composite metal oxide heat storage material, which comprises the following steps:
(1) Mixing manganese nitrate, ferric nitrate and water at 90 ℃, then adding ethylenediamine tetraacetic acid and ammonia water, and stirring for 2 hours at 90 ℃ to obtain a gel solution;
The molar ratio of the manganese nitrate to the ferric nitrate is 5:1;
The ratio of the molar quantity of the ethylenediamine tetraacetic acid to the total molar quantity of the manganese nitrate and the ferric nitrate is 1.2:1;
the ammonia water adjusts the pH value of the system to 8;
(2) Drying the gel solution obtained in the step (1) at the temperature of 200 ℃ for 4 hours, then heating to 450 ℃ at the heating rate of 7 ℃/min for first calcination and heat preservation for 3 hours, then cooling to room temperature along with a furnace, then heating to 850 ℃ at the heating rate of 7 ℃/min for second calcination and heat preservation for 3 hours, then cooling to room temperature along with the furnace, and finally grinding for 15 minutes to obtain the ferromanganese composite metal oxide heat storage material.
Example 4
The present embodiment provides a method for preparing a manganese-iron composite metal oxide heat storage material, and the conditions are the same as those of embodiment 1 except that the molar ratio of manganese nitrate to iron nitrate in step (1) is 0.5:1.
Example 5
The present embodiment provides a method for preparing a manganese-iron composite metal oxide heat storage material, and the conditions are the same as those in embodiment 1 except that the molar ratio of manganese nitrate to iron nitrate in step (1) is 6:1.
Example 6
The present example provides a method for preparing a ferromanganese composite metal oxide heat storage material, and the conditions are the same as those in example 1 except that the ratio of the molar amount of ethylenediamine tetraacetic acid to the total molar amount of manganese nitrate and ferric nitrate in step (1) is 0.5:1.
Example 7
The present embodiment provides a method for preparing a ferromanganese composite metal oxide heat storage material, wherein the conditions are the same as those in embodiment 1 except that the ratio of the molar amount of ethylenediamine tetraacetic acid to the total molar amount of manganese nitrate and ferric nitrate in step (1) is 2:1.
Example 8
The present example provides a method for preparing a ferromanganese composite metal oxide heat storage material, and the conditions are the same as those of example 1 except that "ethylenediamine tetraacetic acid" in step (1) is replaced with "citric acid".
Example 9
The present example provided a method for preparing a ferromanganese composite metal oxide heat storage material, and the conditions were the same as in example 1 except that "add ethylenediamine tetraacetic acid and ammonia" in step (1) were adjusted to "add citric acid and ethylene glycol".
Example 10
The present embodiment provides a method for preparing a ferromanganese composite metal oxide heat storage material, wherein the conditions are the same as those of embodiment 1 except that the temperature rising end point of the first calcination in the step (2) is 300 ℃.
Example 11
The present embodiment provides a method for preparing a ferromanganese composite metal oxide heat storage material, wherein the conditions are the same as those of embodiment 1 except that the temperature rising end point of the first calcination in the step (2) is 550 ℃.
Example 12
The present embodiment provides a method for preparing a ferromanganese composite metal oxide heat storage material, wherein the conditions are the same as those of embodiment 1 except that the temperature rising end point of the second calcination in the step (2) is 700 ℃.
Example 13
The present embodiment provides a method for preparing a ferromanganese composite metal oxide heat storage material, wherein the conditions are the same as those of embodiment 1 except that the temperature rising end point of the second calcination in the step (2) is 950 ℃.
Comparative example 1
This comparative example provides a method for preparing a ferromanganese composite metal oxide heat storage material, under the same conditions as in example 1 except that the second calcination in step (2) is not performed.
The ferromanganese composite metal oxide heat storage materials prepared in the above examples and comparative examples were subjected to a cyclic heat storage performance test in which the temperature was raised from room temperature to 1050 ℃, the temperature was maintained for 5 minutes, then the temperature was lowered to 700 ℃ to remove impurities and interference factors, the air flow rate was set to 50mL/min, nitrogen was a shielding gas, the nitrogen flow rate was set to 20mL/min, and then the cycle was repeated 50 times. The test results are shown in Table 1.
TABLE 1
As can be seen from table 1:
(1) The ferromanganese composite metal oxide heat storage material prepared by the preparation method provided by the invention has the characteristics of high oxidation-reduction rate, excellent circulating heat storage performance and the like; wherein, the reduction conversion rate is more than or equal to 3.4 percent, and the reoxidation rate is more than or equal to 3.2 percent;
(2) As can be seen from comparison of examples 1 and examples 4 to 5, when the manganese nitrate content in the metal raw material is too small, the resultant contains a small portion of ferromanganese composite metal oxide, most of the ferromanganese composite metal oxide is ferric oxide, and the oxidation-reduction temperature of the ferric oxide is higher than that of the ferromanganese composite metal oxide, so that only a part of the ferromanganese composite oxide undergoes oxidation-reduction reaction; when the proportion of manganese nitrate in the metal raw material is excessive, only a small amount of ferromanganese composite metal oxide in the product simultaneously has a large amount of manganese oxide, and only a small amount of ferromanganese composite metal oxide in the product participates in the reaction because the oxidation-reduction capability of the manganese oxide is weak;
(3) As is clear from the comparison between the examples 1 and 6-7, when the amount of ethylenediamine tetraacetic acid added is too small, the complex metal oxide is not formed because part of metal ions are not coordinated, so that the redox performance of the obtained ferromanganese complex metal oxide is poor; when the adding amount of the ethylenediamine tetraacetic acid is excessive, more ammonia water is needed to neutralize, the effect on the result is small, but the cost is increased, and the subsequent treatment is complicated; as can be seen from comparison of the comprehensive examples 1 and examples 8-9, when citric acid is adopted to replace ethylenediamine tetraacetic acid, the complexing effect of ethylenediamine tetraacetic acid is better than that of citric acid, so that the prepared ferromanganese composite metal oxide has better specific surface area, better particle size uniformity and better oxidation-reduction performance;
(4) As can be seen from comparison of the examples 1 and 10-11, when the temperature of the first calcination is too low or too high, the organic impurities cannot volatilize, so that the polymerization of the material in the next high temperature is affected, and the oxidation-reduction performance of the prepared ferromanganese composite metal oxide is poor; as can be seen from comparison of examples 1 and examples 12 to 13, when the second calcination temperature is too low, the oxidation-reduction performance of the obtained ferromanganese composite metal oxide is poor because the material is not polymerized and sintered at high temperature; when the temperature of the second calcination is too high, the material is sintered in a large range, so that the oxygen inlet and outlet of the material in the oxidation-reduction process are influenced, and the oxidation-reduction performance of the prepared ferromanganese composite metal oxide is poor;
(5) As can be seen from the comparison between the example 1 and the comparative example 1, when the second calcination is not performed, the material is only subjected to the lower temperature heat treatment from the dried gel, and the material does not undergo complete condensation-polymerization, sintering and other processes, so that the prepared ferromanganese composite metal oxide contains more impurities, the quality loss occurs in the low temperature stage during the heating process, and the substances participating in the oxidation-reduction process are reduced in the high temperature stage.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the ferromanganese composite metal oxide heat storage material is characterized by comprising the following steps of:
(1) Mixing a manganese source, an iron source and a solvent, then adding a complexing agent and a pH regulator, and stirring to obtain a gel solution;
(2) And (3) sequentially drying, first calcining and second calcining the gel solution obtained in the step (1) to obtain the ferromanganese composite metal oxide heat storage material.
2. The method according to claim 1, wherein the molar ratio of the manganese source to the iron source in step (1) is (1-5): 1;
preferably, the manganese source of step (1) comprises any one or a combination of at least two of nitrate, acetate, chloride or sulfate salts of manganese;
Preferably, the iron source of step (1) comprises any one or a combination of at least two of nitrate, acetate, chloride or sulfate of iron;
preferably, the step (1) solvent comprises water;
Preferably, the temperature of the mixing in step (1) is 70-90 ℃;
Preferably, the mixing of step (1) is performed with stirring.
3. The method of claim 1 or 2, wherein the complexing agent of step (1) comprises ethylenediamine tetraacetic acid;
Preferably, the ratio of the molar amount of complexing agent to the total molar amount of manganese source and iron source of step (1) is (0.8-1.2): 1;
preferably, the pH adjuster of step (1) comprises aqueous ammonia;
preferably, the pH regulator in step (1) regulates the pH of the system to 7-8;
preferably, the temperature of the stirring in the step (1) is 70-90 ℃;
preferably, the stirring time in the step (1) is 2-4h.
4. A method of preparation according to any one of claims 1 to 3, wherein the drying temperature in step (2) is 170 to 200 ℃;
preferably, the drying time of step (2) is 4-6 hours.
5. The method according to any one of claims 1 to 4, wherein the first calcination in step (2) has a temperature rise rate of 3 to 7 ℃/min;
Preferably, the temperature rising end point of the first calcination in the step (2) is 350-450 ℃;
preferably, the first calcination in step (2) has a holding time of 3-5 hours;
preferably, after the first calcining in step (2), the second calcining is further followed by cooling to room temperature with a furnace.
6. The method of any one of claims 1-5, wherein the second calcination in step (2) has a ramp rate of 3-7 ℃/min;
preferably, the temperature rising end point of the second calcination in the step (2) is 750-850 ℃;
Preferably, the incubation time of the second calcination of step (2) is 3-5h.
7. The method of any one of claims 1-6, wherein the second calcining of step (2) further comprises furnace cooling to room temperature.
8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
(1) Mixing a manganese source, an iron source and a solvent at 70-90 ℃, then adding a complexing agent and a pH regulator, and stirring for 2-4 hours at 70-90 ℃ to obtain a gel solution;
The molar ratio of the manganese source to the iron source is (1-5): 1;
The complexing agent comprises ethylenediamine tetraacetic acid; the ratio of the molar amount of the complexing agent to the total molar amount of the manganese source and the iron source is (0.8-1.2): 1;
the pH regulator comprises ammonia water; the pH regulator regulates the pH of the system to 7-8;
(2) Drying the gel solution obtained in the step (1) at 170-200 ℃ for 4-6 hours, then heating to 350-450 ℃ at the heating rate of 3-7 ℃/min for first calcination and heat preservation for 3-5 hours, then cooling to room temperature along with a furnace, heating to 750-850 ℃ at the heating rate of 3-7 ℃/min for second calcination and heat preservation for 3-5 hours, and then cooling to room temperature along with the furnace to obtain the ferromanganese composite metal oxide heat storage material.
9. The ferromanganese composite metal oxide heat storage material is characterized in that the ferromanganese composite metal oxide heat storage material is prepared by the preparation method of any one of claims 1-8.
10. The ferromanganese composite metal oxide heat storage material according to claim 9, wherein the ferromanganese composite metal oxide heat storage material has a general formula of (Mn xFe1-x)2O3, wherein 0.5-0.8.
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