CN116426249A - Heat-storage energy-storage molten salt material and preparation method and application thereof - Google Patents
Heat-storage energy-storage molten salt material and preparation method and application thereof Download PDFInfo
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- CN116426249A CN116426249A CN202310669235.9A CN202310669235A CN116426249A CN 116426249 A CN116426249 A CN 116426249A CN 202310669235 A CN202310669235 A CN 202310669235A CN 116426249 A CN116426249 A CN 116426249A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000004146 energy storage Methods 0.000 title claims abstract description 61
- 238000005338 heat storage Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 134
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims abstract description 119
- 239000000429 sodium aluminium silicate Substances 0.000 claims abstract description 119
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 116
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 103
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000919 ceramic Substances 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011575 calcium Substances 0.000 claims abstract description 56
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 56
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910021389 graphene Chemical class 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 42
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 29
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 20
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 20
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 19
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 17
- 229940071870 hydroiodic acid Drugs 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 16
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000011232 storage material Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010248 power generation Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- AMKLQLYNAGNCJE-UHFFFAOYSA-N cerium(3+);lanthanum(3+);hexanitrate Chemical compound [La+3].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AMKLQLYNAGNCJE-UHFFFAOYSA-N 0.000 description 54
- 239000002245 particle Substances 0.000 description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000005056 compaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S60/00—Arrangements for storing heat collected by solar heat collectors
- F24S60/30—Arrangements for storing heat collected by solar heat collectors storing heat in liquids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a heat-storage energy-storage molten salt material, a preparation method and application thereof, wherein the heat-storage energy-storage molten salt material is formed by raw materials comprising 10-12 parts by weight of rare earth nitrate-sodium aluminosilicate composite material, 70-80 parts by weight of calcium-based modified rare earth nitrate and 8-10 parts by weight of potassium nitrate; the rare earth nitrate-sodium aluminosilicate composite material is formed by raw materials comprising sodium aluminosilicate ceramic loaded with modified rare earth nitrate and graphene oxide; the calcium-based modified rare earth nitrate is formed by calcium hydroxide and rare earth nitrate; the rare earth element in the rare earth nitrate is selected from lanthanum element and/or cerium element. The heat-storage energy-storage molten salt material has low operation temperature required by heat storage and higher energy-storage and energy-release efficiency.
Description
Technical Field
The invention relates to a heat-storage energy-storage molten salt material, and a preparation method and application thereof.
Background
Molten salt refers to liquid salt in a molten state, and molten salt used in engineering generally refers to an inorganic salt melt. The molten salt has the characteristics of high boiling point, low viscosity, low steam pressure and high volume heat, and is an excellent heat storage and heat accumulation medium. The fused salt energy storage technology is to utilize the temperature difference of fused salt in the heating and cooling processes to realize heat energy storage. In the application field, people usually use the characteristic of molten salt to combine photo-thermal power generation with molten salt heat storage energy storage technology, can realize stable and continuous power supply for 24 hours, has adjustable, more friendly to a power grid and stronger compatibility, is the most conditional new energy source serving as basic power load, and the high-temperature molten salt mainly comprises nitrate, carbonate, sulfate, fluoride, chloride, oxide and the like.
Among the heat storage materials, molten salt is one of the most studied and applied at present, can be used as a latent heat storage material and a sensible heat material to be applied to photo-thermal power generation, has the characteristics of being not possessed by other heat storage materials, and therefore, the molten salt is widely focused and studied by students at home and abroad.
CN111410938A discloses a binary molten salt and a preparation method thereof, wherein the binary molten salt is a nitrate system binary molten salt, and comprises potassium nitrate and sodium nitrate in a mass ratio of 4:6. CN107057654a discloses a mixed nitrate heat transfer and storage working medium consisting of Ca (NO 3 ) 2 、KNO 3 、NaNO 3 And LiNO 3 Composition is prepared.
CN115558470a discloses a nitrate modified calcium-based thermochemical energy storage material, which is obtained by mixing calcium hydroxide and metal nitrate by a wet method. The operation temperature required by heat accumulation of the material is reduced. CN115746798A discloses a molten salt material with high energy storage density and a preparation method thereof, comprising the following steps: preparing modified ceramic powder; dehydrated KNO 3 Powder, dehydrated NaNO 2 Powder, dehydrated KNO 2 Mixing, stirring and heating the powder and the modified ceramic powder, and statically melting to obtain a molten nitrate salt mixed system; mixing, kneading, carbonizing and purifying graphite, graphene oxide, a phenolic resin binder and mesophase carbon microspheres to obtain a purified graphite mixture; mixing the purified graphite mixture, nano silver and hydrotalcite powder to obtain a graphite mixture; static pressure preparation of the graphite mixture to obtain graphite blocks; and (3) impregnating the graphite blocks with a molten nitrate salt mixed system to obtain the molten salt material.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a heat-storing and energy-storing molten salt material, which has a low operation temperature required for heat storage and further has a high energy-storing and energy-releasing efficiency. Furthermore, the natural distribution of lanthanum cerium nitrate can be adopted, so that the cost can be reduced according to local conditions. The invention further aims at providing a preparation method of the heat-storage energy-storage molten salt material. The invention further aims at providing an application of the heat-storage energy-storage molten salt material.
In one aspect, the invention provides a heat-storage and energy-storage molten salt material, which is formed by raw materials comprising 10-12 parts by weight of rare earth nitrate-sodium aluminosilicate composite material, 70-80 parts by weight of calcium-based modified rare earth nitrate and 8-10 parts by weight of potassium nitrate;
the rare earth nitrate-sodium aluminosilicate composite material is formed by raw materials comprising sodium aluminosilicate ceramic loaded with modified rare earth nitrate and graphene oxide; wherein, the mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is 4-5:11-15;
the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is formed by raw materials comprising sodium aluminosilicate ceramic and modified rare earth nitrate; wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7; the modified rare earth nitrate is calcium-based modified rare earth nitrate;
the calcium-based modified rare earth nitrate is formed by calcium hydroxide and rare earth nitrate, wherein the mass ratio of the calcium hydroxide to the rare earth nitrate is 0.8-1.2:3-3.5;
wherein the rare earth element in the rare earth nitrate is selected from lanthanum element and/or cerium element.
According to the heat-storage and energy-storage molten salt material, preferably, the heat-storage and energy-storage molten salt material is formed by only 10-12 parts by weight of rare earth nitrate-sodium aluminosilicate composite material, 70-80 parts by weight of calcium-based modified rare earth nitrate and 8-10 parts by weight of potassium nitrate.
On the other hand, the invention also provides a preparation method of the heat-storage energy-storage molten salt material, which comprises the following steps:
1) Forming the calcium-based modified rare earth nitrate;
2) Forming the rare earth nitrate-sodium aluminosilicate composite material;
3) And mixing the rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate, melting, cooling, solidifying and grinding to form the heat-storage energy-storage molten salt material.
According to the preparation method of the present invention, preferably, the step 1) includes the following specific steps:
mixing calcium hydroxide and rare earth nitrate, drying, roasting at 400-600 ℃, and grinding to obtain calcium-based modified rare earth nitrate; wherein the mass ratio of the calcium hydroxide to the rare earth nitrate is 0.8-1.2:3-3.5.
According to the preparation method of the present invention, preferably, the step 2) includes the following specific steps:
(a) Mixing sodium aluminosilicate with calcium oxide, compacting, drying, sintering at 1000-1200 deg.C for 4-8 h to obtain sodium aluminosilicate ceramic; wherein, the mass ratio of the sodium aluminosilicate to the calcium oxide is 7-8:9-12;
(b) Respectively placing sodium aluminosilicate ceramic and modified rare earth nitrate in two crucibles, roasting at 260-300 ℃ for 15-30 min, cooling, transferring sodium aluminosilicate ceramic into modified rare earth nitrate powder, and mixing to obtain a material A; continuously heating the material A at 260-300 ℃ for 40-80 min, cooling, and polishing the surface of the mixture to obtain sodium aluminosilicate ceramic loaded with modified rare earth nitrate; wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7; the modified rare earth nitrate is calcium-based modified rare earth nitrate;
(c) Adding sodium aluminosilicate ceramic loaded with modified rare earth nitrate into an acidic graphene oxide aqueous solution, mixing, heating for 2-5 hours at 120-130 ℃, and then filtering, washing and drying to obtain a rare earth nitrate-sodium aluminosilicate composite material; wherein, the mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is 4-5:11-15; in the acidic graphene oxide aqueous solution, the concentration of graphene oxide is 0.4-0.6 mg/mL.
According to the preparation method of the invention, preferably, the acidic graphene oxide aqueous solution is obtained by adding an auxiliary agent and an inorganic acid to the graphene oxide aqueous solution; wherein the auxiliary agent is selected from one of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid and hydroiodic acid; based on the mass of graphene oxide, the using amount of the auxiliary agent is 10-12 wt% and the using amount of the inorganic acid is 3-5 wt%.
According to the preparation method of the invention, preferably, the auxiliary agent is sodium dodecyl sulfonate.
According to the production method of the present invention, preferably, the inorganic acid is hydroiodic acid or hydrobromic acid.
According to the preparation method of the present invention, preferably, the step 3) includes the following specific steps:
mixing the dried rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate, pre-melting for 2-3 hours at 80-90 ℃, then melting for 25-40 minutes at 100-120 ℃, cooling, solidifying, crushing and grinding into 100-200 mesh powder, thus obtaining the heat-storage energy-storage molten salt material.
In still another aspect, the invention further provides an application of the heat-storage energy-storage molten salt material as described above in photo-thermal power generation.
The invention mainly utilizes rare earth lanthanum cerium nitrate and modifies the rare earth lanthanum cerium nitrate, and the obtained heat storage and energy storage molten salt material has lower operation temperature required for heat storage and higher energy storage and energy release efficiency. Furthermore, the natural distribution of lanthanum cerium nitrate can be adopted, so that local abundant rare earth lanthanum cerium resources can be utilized according to local conditions, and the cost is reduced. In addition, the invention can change the distribution by adding lanthanum nitrate or cerium nitrate on the basis of natural distribution of lanthanum nitrate cerium, and adjust the working temperature of molten salt in a certain range, thereby better adapting to the requirements of different use processes.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited thereto.
The heat-storage energy-storage molten salt material has lower operation temperature required by heat storage, utilizes the locally rich rare earth lanthanum cerium resources, reduces the cost and further has higher energy-storage and energy-release efficiency.
Heat-accumulating energy-storing molten salt material
The heat-storage energy-storage molten salt material is formed by raw materials comprising 10-12 parts by weight of rare earth nitrate-sodium aluminosilicate composite material, 70-80 parts by weight of calcium-based modified rare earth nitrate and 8-10 parts by weight of potassium nitrate. The heat-storage energy-storage molten salt material formed by the raw materials in the proportion has low operation temperature required by heat storage and higher energy storage and release efficiency.
The rare earth element in the present invention is preferably lanthanum element and/or cerium element. In the present invention, the rare earth nitrate may be one or more of lanthanum nitrate, cerium nitrate, or lanthanum cerium nitrate.
In certain embodiments, the heat and energy storing molten salt material of the present invention is formed only from 10 to 12 parts by weight of a rare earth nitrate-sodium aluminosilicate composite, 70 to 80 parts by weight of a calcium-based modified rare earth nitrate, and 8 to 10 parts by weight of potassium nitrate.
In the present invention, the calcium-based modified rare earth nitrate may be 70 to 80 parts by weight, preferably 75 to 80 parts by weight, more preferably 78 to 80 parts by weight. The rare earth nitrate-sodium aluminosilicate composite material may be 10 to 12 parts by weight, preferably 10 to 11.5 parts by weight, more preferably 10.5 to 11 parts by weight. The potassium nitrate may be 8 to 10 parts by weight, preferably 9 to 10 parts by weight, more preferably 9.5 to 10 parts by weight.
In the invention, the rare earth nitrate-sodium aluminosilicate composite material is formed from raw materials including graphene oxide and sodium aluminosilicate ceramic loaded with modified rare earth nitrate. The mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate can be 4-5:11-15, preferably 4.5-5:12-15, and more preferably 4.5-4.8:13-14.5.
In the invention, the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is formed by raw materials comprising sodium aluminosilicate ceramic and modified rare earth nitrate. Wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7, preferably 3-4:5-6, more preferably 3-3.5:5-5.5. The modified rare earth nitrate in the step is calcium-based modified rare earth nitrate.
In the present invention, the sodium aluminosilicate ceramic is formed from a feedstock comprising sodium aluminosilicate and calcium oxide. In certain specific embodiments, the sodium aluminosilicate ceramic is formed solely from sodium aluminosilicate and calcium oxide. Wherein, the mass ratio of the sodium aluminosilicate to the calcium oxide can be 7-8:9-12, preferably 7-8:10-12, more preferably 7.5-7.8:11-11.5.
In the invention, the calcium-based modified rare earth nitrate is formed by calcium hydroxide and rare earth nitrate, wherein the mass ratio of the calcium hydroxide to the rare earth nitrate can be 0.8-1.2:3-3.5, preferably 1.0-1.2:3.2-3.5, and more preferably 1.1-1.15:3.3-3.4. The rare earth nitrate is preferably lanthanum cerium nitrate.
The source of the lanthanum cerium nitrate is not particularly limited, and the lanthanum cerium nitrate can be naturally-distributed lanthanum cerium nitrate with purity more than 99%, wherein the content of the lanthanum nitrate can be 34-36 wt% and the content of the cerium nitrate is 64-66 wt%.
Preparation method
The invention also provides a preparation method of the heat-storage energy-storage molten salt material, which comprises the following steps: 1) Preparing calcium-based modified rare earth nitrate; 2) Preparing a rare earth nitrate-sodium aluminosilicate composite material; 3) And (3) preparing the heat-storage energy-storage molten salt material. Optionally, the method further comprises a step of forming an acidic graphene oxide aqueous solution.
Preparation of calcium-based modified rare earth nitrate
The calcium-based modified rare earth nitrate is prepared by the following steps: mixing calcium hydroxide and rare earth nitrate, drying, roasting and grinding to obtain the calcium-based modified rare earth nitrate. Therefore, the calcium oxide obtained under high-temperature decomposition can be uniformly dispersed in the rare earth nitrate system in situ, so that the performance of the obtained calcium-based modified rare earth nitrate is more uniform. Compared with the calcium-based modified rare earth nitrate obtained by a wet method, the calcium-based modified rare earth nitrate obtained in situ can help to improve the energy storage and release efficiency of the finally obtained heat storage and energy storage molten salt material.
Wherein, the mass ratio of the calcium hydroxide to the rare earth nitrate can be 0.8-1.2:3-3.5, preferably 1.0-1.2:3.2-3.5, more preferably 1.1-1.15:3.3-3.4.
The drying in this step is preferably vacuum drying, and the drying temperature may be 80 to 110 ℃, preferably 90 to 105 ℃, more preferably 95 to 100 ℃. The drying time may be 18 to 36 hours, preferably 20 to 32 hours, more preferably 24 to 28 hours.
The firing temperature in this step may be 400 to 600 ℃, preferably 450 to 550 ℃, more preferably 500 to 550 ℃. The calcination time may be 1 to 3 hours, preferably 1 to 2 hours, more preferably 1 to 1.5 hours.
According to one embodiment of the invention, calcium hydroxide and lanthanum cerium nitrate are mixed, dried in vacuum at 100 ℃ for 24 hours, roasted at 400-600 ℃ and ground to obtain calcium-based modified lanthanum cerium nitrate; wherein the mass ratio of the calcium hydroxide to the lanthanum cerium nitrate is 0.8-1.2:3-3.5.
Preparation of rare earth nitrate-sodium aluminosilicate composite material
The rare earth nitrate-sodium aluminosilicate composite material is prepared by the following steps: (a) forming a sodium aluminosilicate ceramic; (b) Forming sodium aluminosilicate ceramic loaded with modified rare earth nitrate; (c) forming a rare earth nitrate-sodium aluminosilicate composite material. The composite material is compositely modified with the calcium-based modified rare earth nitrate formed in situ, which is more beneficial to improving the performance of the finally obtained heat-storage energy-storage molten salt material, in particular the energy-storage energy-release efficiency. For details see description below.
In the step (a) of the process,
mixing sodium aluminosilicate with calcium oxide, compacting, drying and sintering to obtain sodium aluminosilicate ceramic. The mass ratio of sodium aluminosilicate to calcium oxide may be 7-8:9-12, preferably 7-8:10-12, more preferably 7.5-7.8:11-11.5. The compaction can be performed by adopting 8-15 MPa of hydraulic power in real time, and preferably 10-12 MPa of hydraulic power is adopted for compaction. The drying temperature may be 100 to 120 ℃, preferably 100 to 115 ℃, more preferably 105 to 110 ℃. The drying time may be 10 to 16 hours, preferably 12 to 14 hours, more preferably 12 to 13 hours. The sintering temperature may be 1000 to 1200 ℃, preferably 1050 to 1150 ℃, more preferably 1050 to 1100 ℃. The sintering time may be 4 to 8 hours, preferably 5 to 8 hours, more preferably 6 to 7 hours.
In the step (b) of the process,
respectively placing sodium aluminosilicate ceramic and modified rare earth nitrate in two crucibles, roasting at 260-300 ℃ for 15-30 min, cooling, transferring sodium aluminosilicate ceramic into modified rare earth nitrate powder, and mixing to obtain a material A; continuously heating the material A at 260-300 ℃ for 40-80 min, cooling, and polishing the surface of the mixture to obtain sodium aluminosilicate ceramic loaded with modified rare earth nitrate; wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7; the modified rare earth nitrate is calcium-based modified rare earth nitrate. The calcium-based modified rare earth nitrate is prepared by the method.
The firing temperature may be 260 to 300 ℃, preferably 270 to 290 ℃, more preferably 280 to 290 ℃. The calcination time may be 15 to 30 minutes, preferably 20 to 30 minutes, more preferably 20 to 25 minutes. The mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is preferably 3-4:5-6, more preferably 3-3.5:5-5.5. The duration of the heating is preferably 60 to 80 minutes, more preferably 60 to 70 minutes. The surface of the mixture was polished to substantial flatness.
In the step (c) of the process,
adding sodium aluminosilicate ceramic loaded with modified rare earth nitrate into acidic graphene oxide aqueous solution, mixing, heating for 2-5 h at 120-130 ℃, filtering, washing and drying to obtain rare earth nitrate-sodium aluminosilicate composite material.
The acidic graphene oxide aqueous solution is obtained by adding an auxiliary agent and inorganic acid into the graphene oxide aqueous solution; wherein the auxiliary agent is selected from one of sodium dodecyl sulfonate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, preferably from sodium dodecyl sulfonate or sodium dodecyl sulfate, more preferably sodium dodecyl sulfonate. The inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid and hydroiodic acid, preferably hydroiodic acid or hydrobromic acid, and more preferably hydroiodic acid. The amount of the auxiliary agent is 9 to 12wt%, preferably 10 to 12wt%, more preferably 11 to 11.5wt%, based on the mass of the graphene oxide. The amount of the inorganic acid to be used is 3 to 5wt%, preferably 4 to 5wt%, more preferably 4 to 4.5wt%, based on the mass of the graphene oxide. The concentration of the hydroiodic acid is 25 to 45wt%, preferably 30 to 45wt%. In the present invention, the source of the aqueous graphene oxide solution is not particularly limited and is commercially available.
In the acidic graphene oxide aqueous solution, the concentration of graphene oxide is 0.4-0.6 mg/mL, preferably 0.5-0.6 mg/mL.
The mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate can be 4-5:11-15, preferably 4.5-5:12-15, and more preferably 4.5-4.8:13-14.5.
Preparation steps of heat-storage energy-storage molten salt material
Mixing the dried rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate, premelting at 80-90 ℃, melting at 100-120 ℃, cooling, solidifying, crushing and grinding to obtain the heat-storage energy-storage molten salt material.
The weight parts of the rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate are as described above, and are not described in detail herein.
According to one specific embodiment of the invention, the dried lanthanum cerium nitrate-sodium aluminosilicate composite material, the calcium-based modified lanthanum cerium nitrate and the potassium nitrate are mixed, pre-melted for 2-3 hours at 80-90 ℃, then melted for 25-40 minutes at 100-120 ℃, cooled, solidified, crushed and ground into 100-200 mesh powder, and the heat-storage energy-storage molten salt material is obtained.
The pre-melting temperature may be 80 to 90 ℃, preferably 80 to 85 ℃. The melting temperature may be from 100 to 120 ℃, preferably from 100 to 115 ℃, more preferably from 110 to 115 ℃.
According to a preferred embodiment of the invention, before mixing, the lanthanum cerium nitrate-sodium aluminosilicate composite material and the calcium-based modified lanthanum cerium nitrate are respectively ground into 100-200 mesh particles, then pre-dried for 8-12 hours at 100-115 ℃, then heated to 190-215 ℃ and continuously dried for 8-12 hours, and then put into a drying box for standby.
In the invention, before mixing, potassium nitrate can be ground according to the need, and dried for later use after grinding.
Application of
The invention also provides application of the heat-storage energy-storage molten salt material as a heat-storage energy-storage material in photo-thermal power generation.
The test methods and materials of the examples and comparative examples are described below:
energy storage and release efficiency: performance testing was performed according to the GB/T36376-2018 standard.
The lanthanum cerium nitrate is naturally-distributed lanthanum cerium nitrate, wherein the content of lanthanum nitrate is 34wt% and the content of cerium nitrate is 66wt%.
Preparation example 1-preparation of calcium-based modified lanthanum cerium nitrate
Mixing 0.8 part by weight of calcium hydroxide with 3 parts by weight of lanthanum cerium nitrate to obtain a mixture, vacuum drying the mixture at 100 ℃ for 24 hours, grinding, then heating and roasting at 400 ℃ for 1 hour, cooling and grinding again to obtain the calcium-based modified lanthanum cerium nitrate.
PREPARATION EXAMPLE 2 lanthanum cerium nitrate sodium aluminosilicate composite Material
Mixing sodium aluminosilicate particles subjected to 120 μm screening with calcium oxide powder, carrying out hydraulic compaction under 10MPa, maintaining for 1min, drying at 100 ℃ for 12h, and sintering at 1100 ℃ for 6h to obtain sodium aluminosilicate ceramic; wherein, the mass ratio of the sodium aluminosilicate particles to the calcium oxide powder is 7:9.
Respectively placing sodium aluminosilicate ceramic and modified lanthanum cerium nitrate in two crucibles, roasting at 280 ℃ for 20min, cooling, transferring the sodium aluminosilicate ceramic into modified lanthanum cerium nitrate powder, and mixing to obtain a material A; continuously heating the material A at 280 ℃ for 60min, cooling, and polishing the surface of the mixture by using sand paper to obtain sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate; wherein the mass ratio of the sodium aluminosilicate ceramic to the modified lanthanum cerium nitrate is 3:5; the modified lanthanum cerium nitrate is calcium-based modified lanthanum cerium nitrate; the crucible is an alumina crucible.
Adding sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate into an acidic graphene oxide aqueous solution (the concentration of graphene oxide is 0.5 mg/mL), uniformly mixing, heating at 120 ℃ for 3 hours, and then filtering, washing and drying to obtain a lanthanum cerium nitrate-sodium aluminosilicate composite material; wherein the mass ratio of graphene oxide to the sodium aluminosilicate ceramic loaded with the modified lanthanum cerium nitrate is 5:12. Wherein the acidic graphene oxide aqueous solution is formed by adding sodium dodecyl sulfonate and hydroiodic acid into a graphene oxide aqueous solution, and the mass ratio of the graphene oxide to the sodium dodecyl sulfonate to the hydroiodic acid is 1:0.11:0.04; the concentration of hydroiodic acid was 45wt%.
Example 1-Heat accumulating energy storing molten salt Material
The lanthanum cerium nitrate-sodium aluminosilicate composite material obtained in preparation example 2 and the calcium-based modified lanthanum cerium nitrate obtained in preparation example 1 were respectively ground to obtain particles of about 100 mesh. Drying the particles at 100 ℃ for 10 hours, and then heating to 200 ℃ for continuous drying for 10 hours for later use;
uniformly mixing 10 parts by weight of particles of the lanthanum cerium nitrate-sodium aluminosilicate composite material, 80 parts by weight of particles of calcium-based modified lanthanum cerium nitrate and 10 parts by weight of potassium nitrate, pre-melting the mixture at 80 ℃ for 2 hours, heating to 100 ℃, continuously melting for 30 minutes, cooling, and grinding into 100-200 meshes of powder to obtain the heat-storage energy-storage molten salt material. The energy storage and release efficiency of the obtained heat storage and energy storage molten salt material is 67.2%.
Preparation example 3-preparation of calcium-based modified lanthanum cerium nitrate
Mixing 1.0 weight part of calcium hydroxide with 3.2 weight parts of lanthanum cerium nitrate to obtain a mixture, vacuum drying the mixture at 100 ℃ for 24 hours, grinding, then heating and roasting at 500 ℃ for 1 hour, cooling and grinding again to obtain the calcium-based modified lanthanum cerium nitrate.
PREPARATION EXAMPLE 4 lanthanum cerium nitrate sodium aluminosilicate composite Material
Mixing sodium aluminosilicate particles subjected to 120 μm screening with calcium oxide powder, carrying out hydraulic compaction under 10MPa, maintaining for 1min, drying at 100 ℃ for 12h, and sintering at 1100 ℃ for 6h to obtain sodium aluminosilicate ceramic; wherein the mass ratio of the sodium aluminosilicate particles to the calcium oxide powder is 7.5:10.
Respectively placing sodium aluminosilicate ceramic and modified lanthanum cerium nitrate in two crucibles, roasting at 280 ℃ for 20min, cooling, transferring the sodium aluminosilicate ceramic into modified lanthanum cerium nitrate powder, and mixing to obtain a material A; continuously heating the material A at 280 ℃ for 60min, cooling, and polishing the surface of the mixture by using sand paper to obtain sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate; wherein the mass ratio of the sodium aluminosilicate ceramic to the modified lanthanum cerium nitrate is 3:5; the modified lanthanum cerium nitrate is calcium-based modified lanthanum cerium nitrate; the crucible is an alumina crucible.
Adding sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate into an acidic graphene oxide aqueous solution (the concentration of graphene oxide is 0.5 mg/mL), uniformly mixing, heating at 120 ℃ for 3 hours, and then filtering, washing and drying to obtain a lanthanum cerium nitrate-sodium aluminosilicate composite material; wherein the mass ratio of graphene oxide to the sodium aluminosilicate ceramic loaded with the modified lanthanum cerium nitrate is 4:11. Wherein the acidic graphene oxide aqueous solution is formed by adding sodium dodecyl sulfonate and hydroiodic acid into a graphene oxide aqueous solution, and the mass ratio of the graphene oxide to the sodium dodecyl sulfonate to the hydroiodic acid is 1:0.11:0.04; the concentration of hydroiodic acid was 45wt%.
Example 2-Heat accumulating energy storing molten salt Material
The lanthanum cerium nitrate-sodium aluminosilicate composite material obtained in preparation example 4 and the calcium-based modified lanthanum cerium nitrate obtained in preparation example 3 were respectively ground to obtain particles of about 100 mesh. Drying the particles at 100 ℃ for 10 hours, and then heating to 200 ℃ for continuous drying for 10 hours for later use;
uniformly mixing 10 parts by weight of particles of the lanthanum cerium nitrate-sodium aluminosilicate composite material, 80 parts by weight of particles of calcium-based modified lanthanum cerium nitrate and 10 parts by weight of potassium nitrate, pre-melting the mixture at 80 ℃ for 2 hours, heating to 100 ℃, continuously melting for 30 minutes, cooling, and grinding into 100-200 meshes of powder to obtain the heat-storage energy-storage molten salt material. The energy storage and release efficiency of the obtained heat storage and energy storage molten salt material is 66.9%.
Preparation example 5-preparation of calcium-based modified lanthanum cerium nitrate
Mixing 1.2 parts by weight of calcium hydroxide with 3.5 parts by weight of lanthanum cerium nitrate to obtain a mixture, vacuum drying the mixture at 100 ℃ for 24 hours, grinding, then heating and roasting at 600 ℃ for 1 hour, cooling and grinding again to obtain the calcium-based modified lanthanum cerium nitrate.
PREPARATION EXAMPLE 6 lanthanum cerium nitrate sodium aluminosilicate composite Material
Mixing sodium aluminosilicate particles subjected to 120 μm screening with calcium oxide powder, carrying out hydraulic compaction under 10MPa, maintaining for 1min, drying at 100 ℃ for 12h, and sintering at 1100 ℃ for 6h to obtain sodium aluminosilicate ceramic; wherein the mass ratio of the sodium aluminosilicate particles to the calcium oxide powder is 8:11.
Respectively placing sodium aluminosilicate ceramic and modified lanthanum cerium nitrate in two crucibles, roasting at 280 ℃ for 20min, cooling, transferring the sodium aluminosilicate ceramic into modified lanthanum cerium nitrate powder, and mixing to obtain a material A; continuously heating the material A at 280 ℃ for 60min, cooling, and polishing the surface of the mixture by using sand paper to obtain sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate; wherein the mass ratio of the sodium aluminosilicate ceramic to the modified lanthanum cerium nitrate is 4:7; the modified lanthanum cerium nitrate is calcium-based modified lanthanum cerium nitrate; the crucible is an alumina crucible.
Adding sodium aluminosilicate ceramic loaded with modified lanthanum cerium nitrate into an acidic graphene oxide aqueous solution (the concentration of graphene oxide is 0.5 mg/mL), uniformly mixing, heating at 130 ℃ for 3 hours, and then filtering, washing and drying to obtain a lanthanum cerium nitrate-sodium aluminosilicate composite material; wherein the mass ratio of graphene oxide to the sodium aluminosilicate ceramic loaded with the modified lanthanum cerium nitrate is 5:13. Wherein the acidic graphene oxide aqueous solution is formed by adding sodium dodecyl sulfonate and hydroiodic acid into a graphene oxide aqueous solution, and the mass ratio of the graphene oxide to the sodium dodecyl sulfonate to the hydroiodic acid is 1:0.11:0.04; the concentration of hydroiodic acid was 45wt%.
Example 3-Heat accumulating energy storing molten salt Material
The lanthanum cerium nitrate-sodium aluminosilicate composite material obtained in preparation example 6 and the calcium-based modified lanthanum cerium nitrate obtained in preparation example 5 were separately ground to obtain particles of about 100 mesh. Drying the particles at 100 ℃ for 10 hours, and then heating to 200 ℃ for continuous drying for 10 hours for later use;
uniformly mixing 10 parts by weight of particles of the lanthanum cerium nitrate-sodium aluminosilicate composite material, 80 parts by weight of particles of calcium-based modified lanthanum cerium nitrate and 10 parts by weight of potassium nitrate, pre-melting the mixture at 80 ℃ for 2 hours, heating to 100 ℃, continuously melting for 30 minutes, cooling, and grinding into 100-200 meshes of powder to obtain the heat-storage energy-storage molten salt material. The energy storage and release efficiency of the obtained heat storage and energy storage molten salt material is 67.2%.
Generally, when rare earth nitrate is used as one of main raw materials of a heat-storage energy-storage molten salt material, it is not easy to improve the energy-storage energy-release efficiency. As can be seen from table 1, the energy storage and release efficiency of the examples of the present invention is improved only slightly as compared with comparative examples 1 and 2. However, the practice is not easy and is not achieved by conventional selection. In addition, the heat storage and energy storage fused salt material has the heat storage required operation temperature of 120-150 ℃ and the binary mixed fused salt heat storage required operation temperature of 260-600 ℃ in comparative example 3. The heat-storage and energy-storage molten salt material has obviously lower operation temperature required by heat storage, is more beneficial to saving energy and improves efficiency.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. The heat-storage energy-storage molten salt material is characterized by being formed by raw materials comprising 10-12 parts by weight of rare earth nitrate-sodium aluminosilicate composite material, 70-80 parts by weight of calcium-based modified rare earth nitrate and 8-10 parts by weight of potassium nitrate;
the rare earth nitrate-sodium aluminosilicate composite material is formed by raw materials comprising sodium aluminosilicate ceramic loaded with modified rare earth nitrate and graphene oxide; wherein, the mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is 4-5:11-15;
the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is formed by raw materials comprising sodium aluminosilicate ceramic and modified rare earth nitrate; wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7; the modified rare earth nitrate is calcium-based modified rare earth nitrate;
the calcium-based modified rare earth nitrate is formed by calcium hydroxide and rare earth nitrate, wherein the mass ratio of the calcium hydroxide to the rare earth nitrate is 0.8-1.2:3-3.5;
wherein the rare earth element in the rare earth nitrate is selected from lanthanum element and/or cerium element.
2. The heat and energy storage molten salt material according to claim 1, wherein the heat and energy storage molten salt material is formed only from 10 to 12 parts by weight of a rare earth nitrate-sodium aluminosilicate composite material, 70 to 80 parts by weight of a calcium-based modified rare earth nitrate, and 8 to 10 parts by weight of potassium nitrate.
3. The method for preparing a heat-accumulating and energy-storing molten salt material according to claim 1 or 2, comprising the steps of:
1) Forming the calcium-based modified rare earth nitrate;
2) Forming the rare earth nitrate-sodium aluminosilicate composite material;
3) And mixing the rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate, melting, cooling, solidifying and grinding to form the heat-storage energy-storage molten salt material.
4. A method of preparation according to claim 3, wherein step 1) comprises the specific steps of:
mixing calcium hydroxide and rare earth nitrate, drying, roasting at 400-600 ℃, and grinding to obtain calcium-based modified rare earth nitrate; wherein the mass ratio of the calcium hydroxide to the rare earth nitrate is 0.8-1.2:3-3.5.
5. A method of preparation according to claim 3, wherein step 2) comprises the specific steps of:
(a) Mixing sodium aluminosilicate with calcium oxide, compacting, drying, sintering at 1000-1200 deg.C for 4-8 h to obtain sodium aluminosilicate ceramic; wherein, the mass ratio of the sodium aluminosilicate to the calcium oxide is 7-8:9-12;
(b) Respectively placing sodium aluminosilicate ceramic and modified rare earth nitrate in two crucibles, roasting at 260-300 ℃ for 15-30 min, cooling, transferring sodium aluminosilicate ceramic into modified rare earth nitrate powder, and mixing to obtain a material A; continuously heating the material A at 260-300 ℃ for 40-80 min, cooling, and polishing the surface of the mixture to obtain sodium aluminosilicate ceramic loaded with modified rare earth nitrate; wherein, the mass ratio of the sodium aluminosilicate ceramic to the modified rare earth nitrate is 3-4:5-7; the modified rare earth nitrate is calcium-based modified rare earth nitrate;
(c) Adding sodium aluminosilicate ceramic loaded with modified rare earth nitrate into an acidic graphene oxide aqueous solution, mixing, heating for 2-5 hours at 120-130 ℃, and then filtering, washing and drying to obtain a rare earth nitrate-sodium aluminosilicate composite material; wherein, the mass ratio of the graphene oxide to the sodium aluminosilicate ceramic loaded with the modified rare earth nitrate is 4-5:11-15; in the acidic graphene oxide aqueous solution, the concentration of graphene oxide is 0.4-0.6 mg/mL.
6. The preparation method of claim 5, wherein the acidic graphene oxide aqueous solution is obtained by adding an auxiliary agent and an inorganic acid to the graphene oxide aqueous solution; wherein the auxiliary agent is selected from one of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid and hydroiodic acid; the mass of the graphene oxide is taken as a reference, the dosage of the auxiliary agent is 9-12 wt%, and the dosage of the inorganic acid is 3-5 wt%.
7. The method according to claim 6, wherein the auxiliary agent is sodium dodecyl sulfonate.
8. The process according to claim 6, wherein the inorganic acid is hydroiodic acid or hydrobromic acid.
9. A method of preparation according to claim 3, wherein step 3) comprises the specific steps of:
mixing the dried rare earth nitrate-sodium aluminosilicate composite material, the calcium-based modified rare earth nitrate and the potassium nitrate, pre-melting for 2-3 hours at 80-90 ℃, then melting for 25-40 minutes at 100-120 ℃, cooling, solidifying, crushing and grinding into 100-200 mesh powder, thus obtaining the heat-storage energy-storage molten salt material.
10. Use of the heat-storage energy-storage molten salt material according to claim 1 or 2 as a heat-storage energy-storage material in photo-thermal power generation.
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