CN113582579A - Metal manganese oxide heat storage material module and preparation method thereof - Google Patents
Metal manganese oxide heat storage material module and preparation method thereof Download PDFInfo
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- CN113582579A CN113582579A CN202011463646.5A CN202011463646A CN113582579A CN 113582579 A CN113582579 A CN 113582579A CN 202011463646 A CN202011463646 A CN 202011463646A CN 113582579 A CN113582579 A CN 113582579A
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 130
- 238000005338 heat storage Methods 0.000 title claims abstract description 126
- 239000011232 storage material Substances 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 52
- 239000011572 manganese Substances 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 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 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003980 solgel method Methods 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims 4
- 229910000896 Manganin Inorganic materials 0.000 claims 2
- 238000006722 reduction reaction Methods 0.000 abstract description 30
- 238000007254 oxidation reaction Methods 0.000 abstract description 29
- 230000003647 oxidation Effects 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- -1 oxygen ion Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- 238000010405 reoxidation reaction Methods 0.000 description 11
- 230000035939 shock Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying 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
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
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- 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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Abstract
The invention provides a manganese metal oxide heat storage material module and a preparation method thereof, wherein the manganese metal oxide heat storage material comprises the following raw materials of manganese nitrate, ferric nitrate, citric acid, ethylene glycol, deionized water, an additive and a binder. The main component of the manganese metal oxide heat storage material is (Mn)0.8Fe0.2)2O3The metal manganese oxide heat storage material has strong oxygen adsorption capacity and high oxygen ion diffusion rate, so that the oxidation/reduction reaction rate and the cyclicity of the metal manganese oxide heat storage material are improved, and the material can be ensured to be capable of efficiently and repeatedly circularly storing heat and releasing heat. The reaction temperature range of the manganese metal oxide heat storage material provided by the invention is large, and the heat storage temperature is more than 800 DEG CAnd the method has wide application prospect in the fields of improving the utilization rate of surplus energy, utilizing industrial waste heat, generating electricity by high-temperature solar heat and the like.
Description
Technical Field
The invention relates to the technical field of heat storage materials, in particular to a manganese metal oxide heat storage material module and a preparation method thereof.
Background
The energy storage technology is a key technical support for the continuous and robust development and large-scale utilization of renewable energy. The heat storage is an important component of energy storage, and is an effective means for improving the system efficiency of solar thermal power generation and carrying out power peak regulation. It is estimated that the heat storage market of China around 2025 can reach 300 billion yuan only by taking solar thermal power generation as an example. Meanwhile, the chemical energy converted from the waste electric power generated by the surplus energy in daytime or peak time can be stored and reasonably used according to the requirement, so that the energy waste caused by real-time balance, immediate use and immediate use is avoided. In addition, the overall utilization rate of waste heat resources in China is low, waste heat generated in the industrial process is usually directly discharged into the environment, the resources are wasted after the waste heat is discharged for a long time, severe thermal pollution is caused to the atmospheric environment, and the problems of dispersity, large energy level gradient and the like of the industrial waste heat can be effectively solved by recycling the high-temperature industrial waste heat through a heat storage technology.
The heat storage mainly comprises three forms of sensible heat, latent heat and chemical heat. The sensible heat storage (such as fused salt, heat transfer oil, water/steam and the like) has the widest application, the heat storage temperature is generally not more than 570 ℃, the heat storage energy density is generally 100-300kJ/kg, and the heat storage energy density is difficult to meet the next generation of high-temperature application technology (such as supercritical CO)2Brayton cycle power generation, etc.), (>700 ℃ C.), novel molten salts (such as chloride and carbonate) are still to be developed, but the problems of molten salt corrosivity and the like still exist. The latent heat storage changes along with the temperature range according to the difference of phase change materials, the heat exchange is difficult to control in the phase change process, the coating process is complex, and the cost is high. Chemical heat storage is to store and release energy by using the heat effect of reversible chemical reaction, and the optional heat storage temperature range is wider according to the difference of reaction substances. For high temperature application techniques, the oxidation/reduction reaction temperature of the metal oxide is high (>700 ℃ and a high energy density of (>400kJ/kg) has great development potential.Metal oxide systems suitable for high temperature heat storage applications mainly include: co3O4/CoO、Mn2O3/Mn3O4、 CuO/Cu2O and Fe2O3/Fe3O4And the like.
Wherein Mn is2O3/Mn3O4The system has the advantages of low price, no toxicity, no harm and reaction temperature lower than 1000 ℃, so that the system is concerned about in the field of energy storage, but the reoxidation reaction rate is slow, the reoxidation can hardly occur, the whole reaction process is influenced, and the development and application of the system are severely restricted.
Based on the self chemical property of the high-temperature thermochemical heat storage material, the method has the defects of poor cyclicity of oxidation/reduction chemical reaction, slow reaction rate and the like. Therefore, it is urgently needed to develop a novel high-temperature thermochemical metal manganese oxide heat storage material, which realizes complete reoxidation of the material, and simultaneously considers the rate and the cyclicity of the oxidation/reduction reaction of the material, and ensures that the material can efficiently store and release heat in a plurality of cycles.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the metal manganese oxide heat storage material module, compared with the material prepared by the traditional technology, the crystal powder of the metal manganese oxide heat storage material module has smaller grain size and more uniform distribution, the complete reoxidation of the material is realized, the oxidation/reduction rate and the cyclicity of the material are considered, the metal manganese oxide heat storage material module can be ensured to be capable of storing and releasing heat circularly for many times with high efficiency, and the metal manganese oxide heat storage material module provides guiding significance for a large-scale energy storage system.
The invention provides a metal manganese oxide heat storage material module, which is modified by (Mn) modified by an additive1-xFex)2O3Powder is pressed, wherein (Mn)1-xFex)2O3The powder is prepared by a sol-gel method, wherein x is a constant between 0.1 and 0.4. Since the raw materials used in the sol-gel method are first dispersed in a solvent to form a low-viscosity solution, uniformity at the molecular level can be obtained in a short time, and molecular water can be kept between reactants when forming a gelMixed evenly on the flat.
Further, the invention provides (Mn) in the metal manganese oxide heat storage material module1-xFex)2O3X in (b) is a constant between 0.18 and 0.22. Within the numerical range, the ferromanganese oxide has strong oxygen adsorption capacity, and the diffusion rate of oxygen ions is improved, so that the oxidation/reduction reaction rate and the cyclicity of the metal manganese oxide heat storage material are improved, and the material can be ensured to be capable of efficiently and repeatedly circularly storing heat and releasing heat.
Preferably, the manganese metal oxide heat storage material module provided by the invention is modified by an additive (Mn)1-xFex)2O3The powder is prepared by using manganese nitrate, ferric nitrate, citric acid, glycol and an additive as raw materials. Wherein, manganese nitrate and ferric nitrate are used as main materials; citric acid acts as a complexing agent, helping to form metal ion complexes; in the sol-gel method, the glycol not only can be used as a solvent, but also has the function of providing hydroxyl.
Preferably, the additive used in the metal manganese oxide heat storage material module in the preferred embodiment of the present invention can be, but is not limited to, silicon dioxide, aluminum oxide or zirconium dioxide. The material used as the additive has higher melting point and boiling point and good thermal shock resistance, is suitable for being used as the additive in the heat storage material used in a high-temperature environment, has relatively lower thermal expansion coefficient, namely the thermal stress generated along with the temperature change is smaller, and has smaller requirement on the strength of the material when the same thermal shock is borne.
Further, in the preferred technical scheme of the invention, the mass of the additive does not exceed 30% of the mass of the metal manganese oxide heat storage material module. Experimental results show that the admixture with the mass ratio not more than 30% can be fully fused into the manganese metal oxide heat storage material, the oxidation/reduction performance of the manganese metal oxide heat storage material module is ensured, and meanwhile, the thermal shock resistance of the manganese metal oxide heat storage material module is improved, so that the pressed manganese metal oxide heat storage material module is more stable and firmer and is not easy to deform. And the additive with the mass ratio of more than 30 percent can reduce the thermal shock resistance of the metal manganese oxide heat storage material module, and is easy to deform and even crack in the using process.
Preferably, the binder used in the metal manganese oxide heat storage material module in the preferred embodiment of the present invention is polyvinyl alcohol (PVA), and the mass percentage concentration of the PVA is 5-20%. The polyvinyl alcohol has good dissolution stability and strong caking property, can be mixed with a plurality of materials, and is an efficient caking agent preparation material.
Preferably, in the preferred embodiment of the present invention, (Mn) modified by adding an additive1-xFex)2O3The metal manganese oxide heat storage material module directly pressed by powder is in a cube or cylinder with a porous structure. The metal manganese oxide heat storage material module prepared by the direct pressing method can effectively improve (Mn)1-xFex)2O3The proportion of the material in the metal manganese oxide heat storage material module, and the design of the porous structure can increase the reaction area of the oxidation/reduction chemical reaction of the metal manganese oxide heat storage material and accelerate the oxidation/reduction reaction rate, thereby further improving the heat storage/release rate of the metal manganese oxide heat storage material.
The invention also provides a preparation method of the metal manganese oxide heat storage material module, which comprises the following steps:
step S1, providing a molar ratio of 4: 1, manganese nitrate and ferric nitrate as main raw materials;
step S2, mixing the main raw materials, ethylene glycol and citric acid according to the molar ratio of 3:10:15, adding deionized water, and preparing the metal manganese oxide heat storage material (Mn) by a sol-gel method0.8Fe0.2)2O3；
Step S3, adding an additive into the metal manganese oxide heat storage material, and calcining to obtain the additive modified (Mn)0.8Fe0.2)2O3And mixing the powder with a binder, and pressing to form the metal manganese oxide heat storage material module. Preferably, the heat storage of the manganese metal oxide is preparedThe material comprises the following main raw materials in a molar ratio of manganese nitrate to ferric nitrate of 4: 1, and realizes uniform doping of ferromanganese element in the material on a molecular level. The experiment result shows that the molar ratio is 4: 1, the manganese nitrate and the ferric nitrate are prepared into the manganese metal oxide heat storage material which has good oxidation/reduction performance, and the reduced material can be oxidized in a high proportion.
Compared with the prior art, the preparation method of the metal manganese oxide heat storage material module overcomes the defects that the oxidation reaction rate of manganese oxide is slow, the manganese oxide can not be oxidized any more and the like, and the module is more beneficial to large-scale processing and utilization. The preparation method can uniformly and quantitatively dope the trace iron element and realize uniform doping on the molecular level, and (Mn) is generated by adding a proper amount of the iron element1-xFex)2O3The oxygen adsorption capacity of the metal manganese oxide heat storage material is enhanced, the oxygen ion diffusion rate is improved, an approximately linear weight loss/weight gain curve is formed at a continuous lifting temperature, the reaction rate is high, and good cycle characteristics are still maintained after multiple cycles. In addition, the additive is added and then the mixture is pressed into a porous structure through an independently designed mold, so that the thermal shock resistance of the module is obviously improved, and the reaction activity is still high after multiple cycles.
Further, in a preferred technical scheme of the invention, the purity of the manganese nitrate, ferric nitrate, citric acid, glycol, an additive and other chemical reagents in the manganese metal oxide heat storage material is of analytical pure grade, namely the purity is over 99.7%, and interference impurities are few.
Drawings
FIG. 1 shows a manganese metal oxide (Mn) heat storage material according to one embodiment of the present invention1-xFex)2O3The x value in (1) is a thermogravimetric curve comparison graph at different values;
FIG. 2 is a schematic thermal gravimetric curve diagram of a manganese metal oxide thermal storage material module for multiple oxidation/reduction reactions in the embodiment of FIG. 1;
FIG. 3 is a manganese metal oxide heat storage material (Mn) provided in the embodiment of FIG. 11-xFex)2O3X-ray diffraction analysis (XRD) pattern of (a);
FIG. 4 is a manganese metal oxide heat storage material (Mn) provided in the embodiment of FIG. 11-xFex)2O3Scanning Electron Microscope (SEM) images of (a);
FIG. 5 is a schematic view of a manganese metal oxide heat storage material module provided in the embodiment of FIG. 1;
FIG. 6 is a graph comparing the effect of different types and amounts of additives on a manganese metal oxide heat storage material module provided in the embodiment of FIG. 1;
fig. 7 is a schematic view of a method for manufacturing a manganese metal oxide heat storage material module according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, fall within the scope of the present invention.
In this embodiment, a manganese metal oxide heat storage material module is provided, which is modified with (Mn) additives1- xFex)2O3Powder is pressed, wherein (Mn)1-xFex)2O3The powder is prepared by a sol-gel method. Since the raw materials used in the sol-gel method are first dispersed in a solvent to form a low viscosity solution, uniformity at a molecular level can be obtained in a short time, and reactants can be uniformly mixed at a molecular level when forming a gel.
Further, the invention provides (Mn) in the metal manganese oxide heat storage material module1-xFex)2O3X in the (1) is a constant of 0.18-0.22, and the metal manganese oxide heat storage material (Mn)1-xFex)2O3In the case of different values of xThe line contrast graph is shown in fig. 1. Wherein the experimental temperature change is represented by the solid broken line. When the metal manganese oxide heat storage material is not doped with iron element, namely (Mn)1-xFex)2O3When the value of x in (b) is 0, the weight loss rate after the reduction reaction is about 3.3%, the degree of reoxidation is extremely low, complete reoxidation cannot be achieved until the initial weight is reached, and the reaction curve is shown by a short dotted line marked as 0. When (Mn)1- xFex)2O3When the value of x in (1) is 0.1, the reoxidation rate is slow, and it takes more than 6000s to complete the reoxidation process, and the reaction curve is shown by a dot-dash line marked as 0.1. The data can judge that when the metal manganese oxide heat storage material is not doped with iron element or has less iron element, the reoxidation reaction rate is slow, and the mass fraction oxidation proportion is not ideal. When (Mn)1-xFex)2O3The value of x in (1) is 0.3, the time for the oxidation/reduction reaction is short, but complete reoxidation is not yet achieved, and the reaction curve is shown by the dotted line labeled 0.3. When (Mn)1-xFex)2O3The value of x in (1) is 0.4, the time of oxidation/reduction reaction is very short, but after the oxidation reaction, the initial mass is not reached in a completely reversible manner, and the mass fraction decreases by about 0.3% compared with that before the reduction reaction, and the reaction curve is shown by the dotted line marked 0.4. According to the data, the oxidation/reduction reaction rate is improved when the manganese metal oxide heat storage material is doped with more iron elements, but the mass fraction has certain loss compared with that before the reduction reaction. When (Mn)1-xFex)2O3When the value of x in the formula (I) is 0.2, the time of oxidation/reduction reaction is short, and after the oxidation/reduction reaction, the data are basically equal to the data before the reduction reaction, so that the initial quality can be achieved, and complete reoxidation can be realized. And as can be seen from FIG. 2, when (Mn)1-xFex)2O3When the value of x in (1) is 0.2, i.e., (Mn)0.8Fe0.2)2O3After multiple oxidation/reduction reactions, the mass change rate is kept stable, the weight loss rate is not reduced along with the increase of the reaction times, and the product is recycledThe sample was able to recover to the original mass.
(Mn) modified with an additive in the metal manganese oxide heat storage material module of the present embodiment0.8Fe0.2)2O3The powder is prepared by using manganese nitrate, ferric nitrate, citric acid, glycol and an additive as raw materials. Wherein manganese nitrate and ferric nitrate are used for preparation (Mn)0.8Fe0.2)2O3The main raw materials of the method, citric acid and glycol, are common preparation materials of a sol-gel method. Wherein citric acid acts as a complexing agent, helping to form metal ion complexes; in the sol-gel method, the glycol not only can be used as a solvent, but also has the function of providing hydroxyl. (Mn) obtained by the above Process0.8Fe0.2)2O3The X-ray diffraction analysis diagram is shown in FIG. 3, in which several independent peaks are observed, the diffraction peak is strong, the peak width is narrow, and the description shows (Mn)0.8Fe0.2)2O3The crystal has high crystalline phase content and good crystallization condition. And FIG. 4 is (Mn)0.8Fe0.2)2O3The length of the scale of the image of the crystal under the scanning electron microscope is 5um, and the (Mn) can be seen0.8Fe0.2)2O3The crystal has smaller grain diameter, more uniform distribution, fine gap and good crystal structure.
In the metal manganese oxide heat storage material module provided in this embodiment, the added additive is zirconium dioxide. The melting point of the zirconium dioxide is 2680 ℃, the boiling point of the zirconium dioxide is 4300 ℃, and the zirconium dioxide is not easy to generate chemical reaction in a high-temperature environment. And the thermal expansion coefficient of the zirconium dioxide is relatively small, namely the thermal stress generated by the zirconium dioxide along with the temperature change is small, and the requirement on the strength of the material is small when the zirconium dioxide bears the same thermal shock. In an environment with large temperature change, when the manganese metal oxide heat storage material module is heated or cooled, the zirconium dioxide admixture can enable stress generated among crystals of the manganese metal oxide heat storage material module to be small, and therefore the crystal structure of the manganese metal oxide heat storage material module is enabled to be more stable. Further, in the present embodiment, zirconium dioxide and (Mn) are added as additives0.8Fe0.2)2O3The mass fraction ratio of (1) is 20% to 80%. Experimental results prove that the zirconium dioxide additive in the proportion can be fully fused into the manganese metal oxide heat storage material, and on the premise of ensuring the oxidation/reduction performance of the manganese metal oxide heat storage material, the thermal shock resistance of the manganese metal oxide heat storage material module is improved, so that the pressed manganese metal oxide heat storage material module is more stable and firmer and is not easy to deform.
The shape of the mn oxide heat storage material module provided in this embodiment is shown in fig. 5, and is a cube or a cylinder with a porous structure. The reaction area of the oxidation/reduction reaction of the metal manganese oxide heat storage material module can be increased by the design of the porous structure, and the reaction rate is further accelerated.
In addition, the additive added in the metal manganese oxide heat storage material module can also be aluminum oxide or silicon dioxide. The two also have the advantages of stable chemical properties, high melting point and boiling point and the like, and are not easy to react in a high-temperature environment. Additives recommended for use with (Mn) when alumina or silica is used as the additive0.8Fe0.2)2O3The mass fraction ratio is 10 percent to 90 percent. Referring to fig. 6, (a) is the thermal storage material module of manganese metal oxide after oxidation/reduction reaction for 45 times without additive, the thermal storage material module of manganese metal oxide has undergone large deformation, obvious crack appears, and the module is nearly broken; (b) the metal manganese oxide heat storage material module is formed by adding 10% of additive silicon dioxide by mass percentage and performing oxidation/reduction reaction for 250 times, and the shape is basically not changed; (c) the shape of the metal manganese oxide heat storage material module is slightly changed after adding 30% of zirconium dioxide serving as an additive by mass percent and performing oxidation/reduction reaction for 250 times. Therefore, the thermal shock resistance of the module is obviously improved after the additive is added, and the mass fraction of the additive is not more than 30% so as not to influence the cyclic reaction performance of the metal manganese oxide heat storage material module. The formulator can choose the type and proportion of the additive according to the specific properties and quantity of the heat storage material of the metal manganese oxide, and does not need to be bound more.
In the metal manganese oxide heat storage material module provided in this embodiment, the added binder is polyvinyl alcohol (PVA), and the mass percentage concentration of the PVA is 20%. The polyvinyl alcohol has good dissolution stability and strong cohesiveness, and can ensure that the metal manganese oxide heat storage material module is pressed into a specified shape more stably, so that the metal manganese oxide heat storage material module is suitable for different places to be used more conveniently. In the embodiment, in the manganese metal oxide heat storage material module, the purity of the chemical reagents such as manganese nitrate, ferric nitrate, citric acid, ethylene glycol, and the additive is of analytical grade, that is, the purity is all over 99.7%, and the interfering impurities are few. To a great extent, the interference influence of impurities on the oxidation/reduction reaction of the metal manganese oxide heat storage material module is eliminated, and the oxidation/reduction reaction rate of the metal manganese oxide heat storage material module is further improved.
In this embodiment, a method for preparing a manganese metal oxide heat storage material module is also provided, and the prepared raw materials include manganese nitrate, ferric nitrate, ethylene glycol, citric acid, an additive and a binder.
Referring to fig. 7, the preparation method mainly includes the steps of:
step S1, providing a molar ratio of 4: 1, manganese nitrate and ferric nitrate as main raw materials;
step S2, mixing the main raw materials, ethylene glycol and citric acid according to the molar ratio of 3:10:15, adding deionized water, and preparing the metal manganese oxide heat storage material (Mn) by a sol-gel method0.8Fe0.2)2O3；
Step S3, adding an additive into the metal manganese oxide heat storage material, and calcining to obtain the additive modified (Mn)0.8Fe0.2)2O3And mixing the powder with a binder, and pressing to form the metal manganese oxide heat storage material module.
In step S1, when preparing the main raw materials, manganese nitrate and iron nitrate were mixed in a ratio of 4: 1, so that the ferromanganese element is uniformly doped on a molecular level for subsequent reaction.
In step S2, (Mn)0.8Fe0.2)2O3In this case, a sol-gel method is used. The basic principle is as follows: dissolving ester compound or metal salt in organic solvent to form homogeneous solution, adding other components, reacting at certain temperature to form gel, and drying to obtain the product. Sol-gel processes have many unique advantages over other processes: since the raw materials used in the sol-gel method are first dispersed in a solvent to form a low viscosity solution, uniformity at a molecular level can be obtained in a short time, and reactants can be uniformly mixed at a molecular level when forming a gel. Due to the solution reaction step, some trace elements can be easily and uniformly and quantitatively doped, and uniform doping on a molecular level is realized. Chemical reactions are easier to perform and require lower synthesis temperatures than solid phase reactions, which are believed to be easier to perform and lower temperatures because the diffusion of components in sol gel systems is in the nanometer range, while the diffusion of components in the micrometer range is the case in solid phase reactions.
Specifically, in this embodiment, the main raw materials (manganese nitrate, iron nitrate in a molar ratio of 4: 1), ethylene glycol, and citric acid were first weighed in a molar ratio of 3:10:15, respectively, and then manganese nitrate, iron nitrate, citric acid, and an appropriate amount of deionized water were added to a beaker, stirred with a magnetic stirrer at a constant temperature of 70 ℃ for 3 hours, and then the previously weighed ethylene glycol was added, and stirring was continued with a magnetic stirrer at a constant temperature of 90 ℃ for 2 hours. And taking out the raw materials after the stirring is finished twice, and placing the raw materials in a forced air drying oven, wherein the temperature of the drying oven is set to be 200 ℃, and the drying time is 3 hours. After drying, the raw materials are placed in a tubular furnace with the heating rate of 10 ℃/min, the temperature is firstly maintained at 450 ℃, the calcination is carried out for 4 hours, and then the temperature is maintained at 800 ℃, and the calcination is carried out for 4 hours. Finally, after cooling to room temperature, taking out the powder and grinding the powder to obtain the metal manganese oxide heat storage material (Mn)0.8Fe0.2)2O3。
In step S3, the manganese metal oxide obtained in step S2 is storedThermal material (Mn)0.8Fe0.2)2O3Preparing the metal manganese oxide heat storage material module. Firstly, the metal manganese oxide heat storage material (Mn)0.8Fe0.2)2O3And the additive zirconium dioxide by mass fraction ratio of 80%: 20 percent of the mixture is uniformly mixed, and then the mixture is placed in a tube furnace and calcined for 4 hours at the high temperature of 800 ℃ to obtain the additive modified (Mn)0.8Fe0.2)2O3And (3) powder. In addition, the additive can be, but is not limited to, zirconium dioxide, aluminum oxide or silicon dioxide, and can also be used as the additive. And when the aluminum oxide or the silicon dioxide is used as the additive, the recommended mass fraction ratio of the metal manganese oxide heat storage material to the additive is 90%: 10 percent. The formulator can also adjust the variety and the use amount of the additive according to the self property of the prepared manganese metal oxide heat storage material, but the mass fraction ratio of the additive is not more than 30 percent.
In step S3, additive modified (Mn) is obtained0.8Fe0.2)2O3Adding a binder which is polyvinyl alcohol (PVA) with the mass percentage concentration of 20% into the powder, and then performing module pressing by using a flat vulcanizing machine, wherein the pressing pressure is set to be 20 MPa. The above direct pressing method enables (Mn)0.8Fe0.2)2O3The ratio of the powder in the manganite heat storage material module is maximized, namely the effective material ratio for carrying out the oxidation/reduction reaction can be maximized. In the present embodiment, the shape of the mold used for pressing the module is a cube and a cylinder of a porous structure. The design of the porous structure can increase the reaction area of the oxidation/reduction reaction of the metal manganese oxide heat storage material, and further accelerate the reaction rate. The shape of the pressing module can also be designed according to the use requirement, and is not limited herein. After pressing, the module is placed in a tubular furnace, and is firstly maintained at 200 ℃ and calcined for 0.5 hour; then keeping the temperature at 400 ℃ and calcining for 0.5 hour; finally, the mixture is maintained at 800 ℃ and calcined for 8 hours. High-temperature calcination and drying can completely volatilize organic substances in the binder, and remove impurities in the metal manganese oxide heat storage material module to the maximum extentFinally, a firm metal manganese oxide heat storage material module is formed.
The embodiment provides a thermal storage unit using the metal manganese oxide thermal storage material module as a thermochemical thermal storage device with an electric heater arranged inside, and the thermal storage unit is used for improving the utilization rate of excess energy. The manganese metal oxide heat storage module is used as a heat storage unit in a thermochemical heat storage device, and an electric heater is arranged in the thermochemical heat storage device and can store heat energy generated by the electric heater; the electric heater supplies power to the electric heater by using waste electric power generated by excess energy sources such as a fan or photovoltaic equipment in daytime or peak time, or supplies power to the electric heater by using commercial power when the overall load of a power grid is reduced, and can coordinate with the utilization time of the waste wind and the waste light to make up the problem of heat supply stability when the wind power and the photovoltaic power generation amount are insufficient, so that the power consumption capacity is enhanced. The manganese metal oxide heat storage material module has good heat storage/release rate, so the process can be completed in a short time, the temperature of the thermochemical heat storage device can be adjusted according to output requirements to release heat in a specific time, and the output heat energy can be used for building heating, industrial heating and the like.
So far, the technical scheme of the invention has been described with reference to the attached drawings. However, it is to be understood by those skilled in the art that the scope of the present invention is not limited to the above embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (10)
1. The metal manganese oxide heat storage material module is characterized in that the metal manganese oxide heat storage material module is modified by (Mn) modified by an additive1-xFex)2O3Powder of (Mn) to form1-xFex)2O3The powder is prepared by a sol-gel method, wherein x is a constant between 0.1 and 0.4.
2. The manganous oxide heat storage material module of claim 1, wherein x is a constant between 0.18 and 0.22.
3. The manganous oxide heat storage material module of claim 1, wherein the additive modified (Mn)1-xFex)2O3The powder is prepared by using manganese nitrate, ferric nitrate, citric acid, glycol and an additive as raw materials.
4. The metal manganese oxide heat storage material module of claim 3, wherein said additive is silicon dioxide, aluminum oxide or zirconium dioxide.
5. The manganous oxide heat storage material module of claim 4, wherein the mass of the additive is not more than 30% of the mass of the manganous oxide heat storage material.
6. The manganin heat storage material module of claim 1, wherein the manganin heat storage material module is modified with the additive (Mn)1-xFex)2O3The powder is mixed with a binder and then pressed to form the powder, wherein the binder is polyvinyl alcohol, and the mass percentage concentration of the binder is 5-20%.
7. The metal manganese oxide heat storage material module of claim 1, wherein said metal manganese oxide heat storage material module is a porous structure.
8. A method for preparing a module of a manganese metal oxide heat storage material as claimed in any one of claims 1 to 7, comprising the steps of:
step S1, providing a molar ratio of 4: 1, manganese nitrate and ferric nitrate as main raw materials;
step S2, according to the molar ratioExample 3:10:15 mixing the main raw materials, ethylene glycol, citric acid, and deionized water, preparing manganese metal oxide heat storage material (Mn) by sol-gel method0.8Fe0.2)2O3；
Step S3, adding an additive into the metal manganese oxide heat storage material, and calcining to obtain the additive modified (Mn)0.8Fe0.2)2O3And mixing the powder with a binder, and pressing to form the metal manganese oxide heat storage material module.
9. The method of claim 8, wherein the mass of the additive is not more than 30% of the mass of the thermal storage material.
10. The method of claim 8, wherein the binder is polyvinyl alcohol, and the mass percentage concentration of the polyvinyl alcohol is 5-20%.
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