CN112299766B - Heat storage material and preparation method thereof - Google Patents
Heat storage material and preparation method thereof Download PDFInfo
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- CN112299766B CN112299766B CN202011252418.3A CN202011252418A CN112299766B CN 112299766 B CN112299766 B CN 112299766B CN 202011252418 A CN202011252418 A CN 202011252418A CN 112299766 B CN112299766 B CN 112299766B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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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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- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0082—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability making use of a rise in temperature, e.g. caused by an exothermic reaction
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Combustion & Propulsion (AREA)
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the technical field of energy storage materials, in particular to a heat storage material and a preparation method thereof. The heat storage material is prepared from raw materials including a solid material and an alkaline activator solution; the solid material comprises the following components in parts by weight: 30-50 parts of activated red mud; 30-50 parts of fly ash; 15-50 parts of blast furnace slag; 1-2 parts of carbon nano fiber; 0.5-1 part of sodium lignosulfonate; the alkali activator solution is obtained by mixing raw materials including water glass, sodium hydroxide and water. The activated red mud, the fly ash and the blast furnace slag are used as main raw materials and are matched with the carbon nanofiber and the sodium lignosulfonate, so that the finally obtained heat storage material is high in heat conductivity, small in specific heat capacity, excellent in refractoriness and excellent in mechanical property.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a heat storage material and a preparation method thereof.
Background
Industrial kilns, in particular to large-scale high-temperature industrial kilns, such as tunnel kilns, shuttle kilns, rotary cement kilns and the like, are important thermal equipment in the industries of ceramics, metallurgy, building materials, petrifaction and the like, and the energy consumption of the industrial kilns exceeds 30 percent of the total energy consumption of the national industry. A large amount of high-temperature flue gas is discharged during the operation of the industrial kiln, and the direct discharge of the flue gas into the air not only causes serious environmental pollution, but also wastes a large amount of high-humidity waste heat. The purpose of high efficiency and energy saving can be achieved by recycling waste heat through the heat exchange equipment. Therefore, a high-performance energy storage element with high temperature resistance and good thermal conductivity is very important.
The basic principle of material heat storage is to store some form of heat under specific conditions, and to release and utilize the heat stored in the heat storage material under the condition of heat demand, so as to balance the energy supply and demand. The energy storage material can be divided into sensible heat energy storage material, phase change energy storage material and chemical reaction energy storage material according to the energy storage mode. The sensible heat energy storage technology is simplest and mature in all energy storage materials. The sensible heat storage material stores heat by utilizing the temperature change process of a substance, has a relatively simple heat storage and release process, and is a heat storage material which is applied in a large number in the early stage.
The heat accumulator material mainly adopts sillimanite, kaolin, andalusite and other raw materials with small reserves, additives are added according to a certain proportion, and a ceramic heat accumulator and a honeycomb heat accumulator are manufactured by hot press molding. The invention CN105174978 discloses a process for preparing a heat storage ball, which comprises mixing fly ash, aluminum ash and coal gangue into a ball, rolling and sieving, distributing and sintering to prepare sintered ceramsite for environment-friendly heat storage ball. Although the heat accumulator meets the requirements, the process is complex and the energy consumption is high. CN102603355 discloses a geopolymer porous material prepared from slurry of water glass, slag, fly ash, metakaolin, polypropylene fibers and the like and composite foaming. The product prepared by the invention can be used for heat-insulating building blocks, refractory components of chemical equipment, heat-insulating bricks and the like in building application, but cannot resist high temperature and has low high-temperature strength.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a thermal storage material and a preparation method thereof.
The invention provides a heat storage material, which is prepared from raw materials comprising a solid material and an alkaline activator solution;
the solid material comprises the following components in parts by weight:
the alkali activator solution is obtained by mixing raw materials including water glass, sodium hydroxide and water.
Preferably, the activated red mud is prepared by the following method:
calcining the Bayer process red mud at 790-810 ℃ for 2-3 h to obtain activated red mud.
Preferably, the particle size of the fly ash is less than 45 μm.
Preferably, the average particle size of the blast furnace slag powder is less than 45 μm.
Preferably, the alkaline activator solution is prepared according to the following method:
and uniformly mixing the water glass, the solid alkali and water to obtain an alkali activator solution.
Preferably, the solid base is selected from sodium hydroxide solids.
Preferably, the modulus of the alkali activator solution is 1.4-1.6, and the mixing amount of the water glass is 35-40%.
Preferably, the mass ratio of the solid material to water in the alkali-activator solution is 1: 0.4 to 0.6.
The invention also provides a preparation method of the heat storage material, which comprises the following steps:
and (3) uniformly mixing the solid material and the alkaline activator solution, forming in a mold, and maintaining at constant temperature to obtain the heat storage material.
Preferably, the constant-temperature curing temperature is 58-62 ℃, and the constant-temperature curing time is 23-25 h.
The invention provides a heat storage material, which is a solid waste base heat storage material and is prepared from raw materials comprising a solid material and an alkaline activator solution; the solid material comprises the following components in parts by weight: 30-50 parts of activated red mud; 30-50 parts of fly ash; 15-50 parts of blast furnace slag; 1-2 parts of carbon nano fiber; 0.5-1 part of sodium lignosulfonate; the alkali activator solution is obtained by mixing raw materials including water glass, sodium hydroxide and water. The activated red mud, the fly ash and the blast furnace slag are used as main raw materials and are matched with the carbon nanofiber and the sodium lignosulfonate, so that the finally obtained heat storage material is high in heat conductivity, small in specific heat capacity, excellent in refractoriness and excellent in mechanical property.
The experimental result shows that the pressure of the heat storage material after 28 days is higher than 60 MPa; the pressure of the heat storage material after being sintered for 1 hour at 700 ℃ is not lower than 40MPa, the heat conductivity coefficient of the heat storage material is more than 0.75W/m.K, the specific heat capacity is lower than 2.5J/g.DEG C, and the refractoriness is more than 1600 ℃.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should 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, shall fall within the protection scope of the present invention.
The invention provides a heat storage material, which is prepared from raw materials comprising a solid material and an alkaline activator solution;
the solid material comprises the following components in parts by weight:
the alkali activator solution is obtained by mixing raw materials including water glass, sodium hydroxide and water.
The solid material comprises 30-50 parts by weight of activated red mud. In certain embodiments of the invention, the activated red mud is 30 parts by weight, 50 parts by weight, or 40 parts by weight.
In certain embodiments of the invention, the activated red mud is prepared according to the following method:
calcining the Bayer process red mud at 790-810 ℃ for 2-3 h to obtain activated red mud.
In certain embodiments of the invention, the temperature of the calcination is 800 ℃. In certain embodiments of the invention, the calcination is for a time of 2h or 3 h.
The bayer process red mud source is not particularly limited, and may be generally commercially available.
The solid material also comprises 30-50 parts by weight of fly ash. In certain embodiments of the invention, the fly ash is 40 parts by weight or 30 parts by weight. In certain embodiments of the invention, the fly ash is ground fly ash. The polishing method is not particularly limited in the present invention, and a mechanical polishing method known to those skilled in the art may be used. In certain embodiments of the invention, the fly ash is high silica fly ash, derived from coal fired power plants.
In certain embodiments of the invention, the fly ash has a particle size of less than 45 μm.
The source of the fly ash is not particularly limited in the present invention, and the fly ash may be generally commercially available.
The solid material also comprises 15-50 parts by weight of blast furnace slag powder. In certain embodiments of the invention, the blast furnace slag powder is 28.5 parts by weight, 18.5 parts by weight, or 18.2 parts by weight. In certain embodiments of the invention, the blast furnace slag powder has an average particle size of less than 45 μm. The source of the blast furnace slag powder is not particularly limited, and the blast furnace slag powder can be generally commercially available.
The solid material also comprises 1-2 parts by weight of carbon nanofibers. In certain embodiments of the present invention, the carbon nanofibers are 1 part by weight. The carbon nanofibers of the present invention are not particularly limited in source, and may be commercially available.
The solid material also comprises 0.5-1 part by weight of sodium lignosulphonate. In certain embodiments of the invention, the sodium lignosulfonate is 0.5 parts by weight or 0.8 parts by weight.
The present invention is not particularly limited in the method for preparing the solid material, and in certain embodiments of the present invention, the solid material is prepared according to the following method:
and uniformly mixing the activated red mud, the fly ash, the blast furnace slag powder, the carbon nanofiber and the sodium lignosulfonate to obtain a solid material.
In certain embodiments of the present invention, the alkaline stimulant solution is prepared according to the following method:
and uniformly mixing the water glass, the solid alkali and water to obtain an alkali activator solution.
In certain embodiments of the invention, the solid base is selected from sodium hydroxide solids.
In some embodiments of the present invention, the step of mixing the water glass, the solid base and the water further comprises standing. In certain embodiments of the invention, the time of standing is 24 hours.
In the invention, the modulus of the water glass is adjusted by adopting solid alkali, and the mixing amount of the water glass is adjusted by adopting water.
In some embodiments of the invention, the modulus of the alkali activator solution is 1.4-1.6, and the water glass content is 35-40%. In certain embodiments of the invention, the modulus of the alkaline stimulant solution is 1.4 or 1.5. In certain embodiments of the present invention, the alkali-activator solution has a water glass loading of 38%.
In certain embodiments of the present invention, the mass ratio of the solid material to water in the alkali-activator solution is 1: 0.4 to 0.6. In certain embodiments, the mass ratio of the solid material to water in the alkali-activator solution is 1: 0.4, 1: 0.5.
the invention also provides a preparation method of the heat storage material, which comprises the following steps:
and (3) uniformly mixing the solid material and the alkaline activator solution, forming in a mold, and maintaining at constant temperature to obtain the heat storage material.
In the preparation method of the heat storage material provided by the invention, the components and the proportion of the adopted raw materials are the same as those in the above, and are not described again.
The invention has no special limitation on the material and the structure of the mould, the material of the mould can be metal or organic glass, and the shape and the size of the mould can be customized according to the requirement.
In some embodiments of the invention, the constant-temperature curing temperature is 58-62 ℃, and the constant-temperature curing time is 23-25 h. In some embodiments, the temperature for constant temperature curing is 60 ℃. In some embodiments, the temperature for constant temperature curing is 24 hours.
In some embodiments of the present invention, after the constant-temperature curing, the mold stripping is further included.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the present invention, the following detailed description of a heat storage material and a method for preparing the same will be given with reference to examples, but it should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all commercially available.
In the embodiment, the heat conductivity coefficient of the heat storage material is detected according to a sphere method in a steady-state heat flow method; detecting the specific heat capacity of the heat storage material according to a comparison method; detecting the refractoriness of the heat storage material according to GB/T7322 and 2017 refractory material refractoriness test method; detecting the compressive strength according to GB/T5072 + 2008 test method for normal temperature compressive strength of refractory materials;
example 1
1. And mechanically grinding the high-silicon fly ash to obtain the fly ash with the particle size of less than 45 microns.
2. Calcining the Bayer process red mud at 800 ℃ for 2h to obtain the activated red mud.
3. Uniformly mixing 30 parts by weight of activated red mud, 40 parts by weight of fly ash, 28.5 parts by weight of blast furnace slag powder, 1 part by weight of carbon nanofiber and 0.5 part by weight of sodium lignosulfonate to obtain 100 parts by weight of solid material.
4. Uniformly mixing water glass, sodium hydroxide solid and 40 parts by weight of water, and standing for 24 hours to obtain an alkaline activator solution; the modulus of the alkali activator solution is 1.4, and the mixing amount of the water glass is 38%.
5. And (3) uniformly mixing the solid material with the alkaline activator solution, forming in a mold, maintaining at the constant temperature of 60 ℃ for 24 hours, and removing the mold to obtain the heat storage material.
The detection shows that the pressure of the heat storage material after 28 days is 70 Mpa; the pressure of the heat storage material after being sintered for 1 hour at 700 ℃ is 62MPa, the heat conductivity coefficient of the heat storage material is 0.78W/m.K, the specific heat capacity is 2.0J/g.DEG C, and the refractoriness is more than 1600 ℃.
Example 2
1. And mechanically grinding the high-silicon fly ash to obtain the fly ash with the particle size of less than 45 microns.
2. Calcining the Bayer process red mud at 800 ℃ for 3h to obtain the activated red mud.
3. Uniformly mixing 50 parts by weight of activated red mud, 30 parts by weight of fly ash, 18.5 parts by weight of blast furnace slag powder, 1 part by weight of carbon nanofiber and 0.5 part by weight of sodium lignosulfonate to obtain 100 parts by weight of solid material.
4. Uniformly mixing water glass, sodium hydroxide solid and 50 parts by weight of water, and standing for 24 hours to obtain an alkaline activator solution; the modulus of the alkali activator solution is 1.5, and the mixing amount of the water glass is 38%.
5. And (3) uniformly mixing the solid material with the alkaline activator solution, forming in a mold, maintaining at the constant temperature of 60 ℃ for 24 hours, and removing the mold to obtain the heat storage material.
The detection shows that the pressure of the heat storage material after 28 days is 61 Mpa; the pressure of the heat storage material after being sintered for 1 hour at 700 ℃ is 40MPa, the heat conductivity coefficient of the heat storage material is 0.88W/m.K, the specific heat capacity is 1.9J/g.DEG C, and the refractoriness is more than 1600 ℃.
Example 3
1. And mechanically grinding the high-silicon fly ash to obtain the fly ash with the particle size of less than 45 microns.
2. Calcining the Bayer process red mud at 800 ℃ for 3h to obtain the activated red mud.
3. Uniformly mixing 40 parts by weight of activated red mud, 40 parts by weight of fly ash, 18.2 parts by weight of blast furnace slag powder, 1 part by weight of carbon nanofiber and 0.8 part by weight of sodium lignosulfonate to obtain 100 parts by weight of solid material.
4. Uniformly mixing water glass, sodium hydroxide solid and 40 parts by weight of water, and standing for 24 hours to obtain an alkaline activator solution; the modulus of the alkali activator solution is 1.5, and the mixing amount of the water glass is 38%.
5. And (3) uniformly mixing the solid material with the alkaline activator solution, forming in a mold, maintaining at the constant temperature of 60 ℃ for 24 hours, and removing the mold to obtain the heat storage material.
The detection shows that the pressure of the heat storage material after 28 days is 78 Mpa; the pressure of the heat storage material after being sintered for 1 hour at 700 ℃ is 45MPa, the heat conductivity coefficient of the heat storage material is 0.96W/m.K, the specific heat capacity is 2.1J/g.DEG C, and the refractoriness is more than 1600 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A heat storage material is prepared from raw materials including solid materials and an alkaline activator solution;
the solid material comprises the following components in parts by weight:
30-50 parts of activated red mud;
30-50 parts of fly ash;
15-50 parts of blast furnace slag powder;
1-2 parts of carbon nano fiber;
0.5-1 part of sodium lignosulfonate;
the activated red mud is prepared by the following method:
calcining the Bayer process red mud at 790-810 ℃ for 2-3 h to obtain activated red mud;
the alkali activator solution is obtained by mixing raw materials including water glass, sodium hydroxide and water.
2. The thermal storage material according to claim 1, wherein the particle size of the fly ash is less than 45 μm.
3. The thermal storage material according to claim 1, wherein the average particle size of the blast furnace slag powder is less than 45 μm.
4. The heat storage material according to claim 1, wherein the alkali-activator solution is prepared by the following method:
and uniformly mixing the water glass, the sodium hydroxide solid and the water to obtain the alkali activator solution.
5. The heat-storage material according to claim 1, wherein the modulus of the alkali-activator solution is 1.4 to 1.6, and the content of water glass is 35 to 40%.
6. The heat storage material according to claim 1, wherein the mass ratio of the solid material to water in the alkali-activator solution is 1: 0.4 to 0.6.
7. A method for producing the heat storage material according to claim 1, comprising the steps of:
and (3) uniformly mixing the solid material and the alkaline activator solution, forming in a mold, and maintaining at constant temperature to obtain the heat storage material.
8. The preparation method according to claim 7, wherein the temperature of the constant-temperature curing is 58-62 ℃, and the time of the constant-temperature curing is 23-25 h.
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| CN114014629A (en) * | 2021-10-18 | 2022-02-08 | 广西新发展交通集团有限公司 | Red mud-based ECC material and preparation method thereof |
| CN114477959A (en) * | 2022-03-16 | 2022-05-13 | 南京宇清环境科技有限公司 | Heat storage ceramic based on blast furnace slag and preparation method thereof |
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| CN104045374A (en) * | 2014-06-26 | 2014-09-17 | 刘海锋 | Red mud porous material |
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