CN103694965A - Method for fabricating heat accumulation product with high-temperature phase change heat accumulation material - Google Patents
Method for fabricating heat accumulation product with high-temperature phase change heat accumulation material Download PDFInfo
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- CN103694965A CN103694965A CN201310726831.2A CN201310726831A CN103694965A CN 103694965 A CN103694965 A CN 103694965A CN 201310726831 A CN201310726831 A CN 201310726831A CN 103694965 A CN103694965 A CN 103694965A
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Abstract
The invention relates to the field of material processing, in particular to a method for fabricating a heat accumulation product with a high-temperature phase change heat accumulation material. The method comprises the following steps of adding metallic silicon powder into pulverized fuel ash, after mixing and ball-milling with a ball mill, spraying, pelleting, performing machine moulding with a press, or extruding into a molding material with a pug, fabricating the molding material into a green body of a perforated brick, or a heat accumulation ball, or honeycomb ceramic, drying and keeping the green body warm, firing, cooling and picking. The heat accumulation product prepared by the method is high in service temperature and stronger in hear accumulation capacity, and can be recycled for a long term.
Description
Technical field
The present invention relates to material processing field, in particular to a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product.
Background technology
Existing synthetic mullite or the main difference of trichroite goods technology are a little difference of raw materials used difference and technological process, its end product is still mainly conventional mullite or the trichroite goods that industry is known, and mullite or cordierite products itself have outstanding high-temperature behavior.
At present the high-temperature phase change heat accumulation material of report is mainly made with macromolecular material or aluminium alloy, magnesium alloy etc., but use temperature is lower, general below 800 ℃.It is reported, in sun power industry, the upper limit temperature of heat tolerance of the high-temperature phase change heat accumulation material of being made by metallic aluminium powder can reach 800 ℃, higher than 800 ℃ have not been reported.
And existing accumulation of heat product is all hole bricks of being made by conventional raw material, heat-storing sphere and ceramic honey comb, although the use temperature of these products is higher, can reach more than 1000 ℃, but because the heat storage type of existing accumulation of heat product is mainly to carry out heat storage by the physics heat absorption mode of material itself, its heat retention is limited, and heat absorption heat transfer rate is also slow, under high-temperature situation, itself is easily etched material, and such as hotblast stove, process furnace all needs 1300 ℃ of above high temperature materials just can use, so existing these high-temperature phase change heat accumulation materials and product can only be used in the middle low-temperature heat accumulating fields such as sun power.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product, to solve the above problems.
A kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product providing in an embodiment of the present invention, comprises the following steps:
In flyash, add metallic silicon power;
After ball mill mixing and ball milling, mist projection granulating, working pressure machine mechanical pressing or use mud extruder are extruded as formed material;
Described formed material is made to the base substrate of hole brick or heat-storing sphere or ceramic honey comb;
By described body drying, insulation, burn till, cooling, selection.
According to a kind of utilization in the method that high-temperature phase change heat accumulation material makes accumulation of heat product provided by the invention, flyash is wherein starting material conventional while preparing mullite or trichroite product material, but the volume density of metallic silicon power is wherein 2.33g/cm3, specific heat capacity is 0.162Kcal/Kg, fusing point is 1414 ℃, melting heat is 50.55KJ/mol, in below 1000-1200 ℃, low thermophase can improve the heat absorption conduction velocity of mullite or trichroite product material, and then improves the ability of transferring heat and the absorption heat of mullite or trichroite product material.The oxide film of the oxidized formation silicon of the metallic silicon power of accumulation of heat product surface when high temperature, can prevent the erosion of FeO etc., and then the work-ing life that can improve accumulation of heat product.The oxide film of silicon can effectively be protected the metallic silicon power of the material internal of accumulation of heat product simultaneously, makes it keep simple substance state always.
When the further rising of envrionment temperature reaches 1414 ℃, the metallic silicon power of accumulation of heat interiors of products high dispersing starts fusing, and with the heat absorption capacity of 50.55kJ/mol, carry out extra phase-transition heat-storage process in phase transformation melting process, in this process, make accumulation of heat product in heat-accumulating process, can put aside extraly heat more, namely improve the heat storage capacity of accumulation of heat product.
Silicon metal powder due to accumulation of heat interiors of products can solidify again after fusing cooling simultaneously, so, the fusing of metallic silicon power, process of setting can circulate, this accumulation of heat product can recycle, and the use temperature of this accumulation of heat product is more than 1000 ℃, so the use temperature of accumulation of heat product prepared by method provided by the invention is high, and can recycle for a long time, heat storage capacity is stronger.
Accompanying drawing explanation
A kind of method flow diagram that utilizes high-temperature phase change heat accumulation material to make accumulation of heat product that Fig. 1 provides for the embodiment of the present invention 1.
Embodiment
Below by specific embodiment, also by reference to the accompanying drawings the present invention is described in further detail.
A kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product as shown in Figure 1, comprises the following steps:
101. add metallic silicon power in flyash;
Flyash is wherein the waste of power plant, and material cost is low, and easily obtains.
Wherein the add-on of flyash is 20-40 part, and the add-on of metallic silicon power is 10-40 part.
In order to improve the cohesiveness between each material composition, can also wherein be added associativity clay, according to raw-material add-on ratio, the add-on of associativity clay is generally 1-10 part.
In flyash, add in the step of metallic silicon power, can also wherein be added talcum powder, talcous add-on is 10-30 part, adds talcum powder to make heat-storing material cordierite material afterwards.When not adding talcum powder, make heat-storing material mullite material.
In flyash, add in the step of metallic silicon power, conventionally also can add in alumine, aluminum oxide, magnesia powder any one or multiple.
Because the content of the aluminium in flyash is less, the content of the aluminium in raw material powder coal ash is less, in the time of can not reaching processing requirement content; conventionally can add alumine, or aluminum oxide, or magnesia powder; or the mixture of any two or three kinds regulates the content of aluminium, and magnesian content.
Wherein alumine, or aluminum oxide, or the add-on of the mixture of the two adds according to the number of the content of the aluminium in flyash.
102. after ball mill mixing and ball milling, and mist projection granulating working pressure machine mechanical pressing or use mud extruder are extruded as formed material;
This step is general procedure in common process.
103. make the base substrate of hole brick, heat-storing sphere or ceramic honey comb by described formed material;
104. by described body drying, insulation, burns till, cooling, selection.
Wherein temperature dry, insulation is 1250-1400 ℃, and the time of described insulation is 4-12 hour.
After naturally cooling, after pick classification, be finished product accumulation of heat product, this kind of accumulation of heat product is widely used in high-temperature energy-conservation field, and particularly at hotblast stove, the energy-saving potentials such as process furnace are high, require strict place to be frequently applied.
According to a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product provided by the invention, the accumulation of heat product of making according to the method, raw material powder coal ash is wherein starting material conventional while preparing mullite or trichroite product material, but the low thermophase in lower than 1000 ℃ of metallic silicon power wherein can improve heat absorption conduction velocity, the oxide film of the oxidized formation silicon of the metallic silicon power of accumulation of heat product surface when high temperature, can prevent the erosion of FeO etc., and then the work-ing life that can improve mullite or trichroite product material.
The oxide film of silicon can effectively be protected the metallic silicon power of accumulation of heat interiors of products simultaneously, makes it keep simple substance state always.
When the further rising of envrionment temperature reaches 1414 ℃, the metallic silicon power of the high dispersing of accumulation of heat interiors of products starts fusing, and with the heat absorption capacity of 50.55kJ/mol, carry out extra phase-transition heat-storage process in phase transformation melting process, in this process, make accumulation of heat product in heat-accumulating process, can put aside extraly heat more, namely improve the heat storage capacity of accumulation of heat product.
Silicon metal powder due to accumulation of heat interiors of products can solidify again after fusing cooling simultaneously; so; the fusing of metallic silicon power, process of setting can circulate; the oxide film of the product subsurface of accumulation of heat simultaneously silicon can be protected accumulation of heat product, and the use temperature of this material is more than 1000 ℃.
So accumulation of heat product use temperature prepared by method provided by the invention is high, and can recycle for a long time, heat storage capacity is stronger.
Utilize the contrast in use of accumulation of heat product that accumulation of heat product that method provided by the invention makes and traditional material make as following table 1:
Table 1
| ? | The present invention | Tradition accumulation of heat product |
| Heat storage type | Physics heat absorption+decalescence | Physics heat absorption |
| Protective membrane | The oxide film of silicon | Nothing |
| Working life | Hole brick is longer than 10 years, and heat-storing sphere is longer than 5 years | Hole brick 8-10, heat-storing sphere 3-5 |
According to table 1, can be clear that, utilize accumulation of heat product prepared by method provided by the invention significantly, on heat storage type, there is larger advantage, changed the heat storage type that physicals that conventional accumulation of heat product only relies on self is carried out physics heat absorption, the phase-transition heat-storage that utilizes accumulation of heat product to carry out in phase transition process, by physics heat absorption and decalescence are combined, make accumulation of heat product in heat-accumulating process, except physics heat absorption, also have extra phase-transition heat-storage, improved heat storage capacity and the heat storage efficiency of accumulation of heat product.
Fusing because of part metals silicon while particularly making honeycomb ceramic product with this raw material helps nodulizing, and the honeycomb ceramic product obtaining is fine and close, and intensity is higher.
Simultaneously; accumulation of heat product surface prepared by the mullite of preparing according to method provided by the invention or trichroite product material is because there is metallic silicon power; after metallic silicon power is oxidized, become the oxide film of accumulation of heat product; stoped well under hot environment; the erosion to accumulation of heat product such as FeO, the work-ing life of having improved accumulation of heat product.
Simultaneously, be generally 8-10 the work-ing life of the hole brick that conventional heat-storing material is made, be generally 3-5 the work-ing life of heat-storing sphere, and the accumulation of heat product of the mullite material of preparing according to method provided by the invention processing, such as be longer than 5 years the working life of heat-storing sphere, and be longer than the working life of hole brick 8 years.The application of the honeycomb ceramic product making by this method on process furnace improves several times than present product life.
Concrete case study on implementation 1:
30 parts, flyash, 5 parts of associativity clays, 65 parts of alumines, the metallic silicon power of additional 25 parts; After mixing and ball milling, mist projection granulating, 400 tons of pressing machine moulding, make 37 hole bricks, drying, 1320-1390 ℃ of sintering, cooling, choose and obtain high-temperature phase-change energy storage 37 hole bricks.
Concrete case study on implementation 2:
35 parts, flyash, 8 parts of associativity clays, 47 parts of alumines, 10 parts of aluminum oxide powders, additional 30 parts of metallic silicon powers; After mixing and ball milling, mist projection granulating, 350 tons of pressing machine moulding, make Φ 70 heat-storing spheres, drying, 1330-1400 ℃ of sintering, cooling, choose and obtain high-temperature phase-change energy storage Φ 70 heat-storing spheres.
Concrete case study on implementation 3:
40 parts, flyash, 10 parts of associativity clays, 30 parts of magnesia powders, 20 parts of aluminum oxide powders, the metallic silicon power of additional 20 parts; After mixing and ball milling, vacuum pugging extrusion molding, makes porous honeycomb ceramic, drying, and 1380 ℃ of sintering, cooling, choose and obtain high-temperature phase-change energy storage porous honeycomb ceramic.
Concrete case study on implementation 4:
20 parts, flyash, 3 parts of associativity clays, 27 parts of magnesia powders, 20 parts of aluminum oxide powders, 10 parts of talcum powder, the metallic silicon power of additional 10 parts; After mixing and ball milling, vacuum pugging extrusion molding, makes porous honeycomb ceramic, drying, and 1400 ℃ of sintering, cooling, choose and obtain high-temperature phase-change energy storage porous honeycomb ceramic.
Concrete case study on implementation 5:
25 parts, flyash, 1 part of associativity clay, 30 parts of magnesia powders, 15 parts of aluminum oxide powders, 30 parts of talcum powder, the metallic silicon power of additional 40 parts; After mixing and ball milling, vacuum pugging extrusion molding, makes porous honeycomb ceramic, drying, and 1390 ℃ of sintering, cooling, choose and obtain high-temperature phase-change energy storage porous honeycomb ceramic.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. utilize high-temperature phase change heat accumulation material to make a method for accumulation of heat product, it is characterized in that, comprise the following steps:
In flyash, add metallic silicon power;
After ball mill mixing and ball milling, mist projection granulating working pressure machine mechanical pressing or use mud extruder are extruded as formed material;
Described formed material is made to the base substrate of hole brick, heat-storing sphere or ceramic honey comb;
By described body drying, insulation, burn till, cooling, selection.
2. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 1, is characterized in that, in the described step that adds metallic silicon power in flyash,
The add-on of described flyash is 20-40 part, and the add-on of described metallic silicon power is 10-40 part.
3. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 1, is characterized in that,
Described dry, insulation, burns till, cooling, in the step of selection,
Described temperature dry, insulation is 1250-1400 ℃, and the time of described insulation is 4-12 hour.
4. according to a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product described in claim 1-3 any one, it is characterized in that,
In the described step that adds metallic silicon power in flyash, also comprise and add associativity clay.
5. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 4, is characterized in that,
The add-on of described associativity clay is 1-10 part.
6. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 4, is characterized in that,
In the described step that adds metallic silicon power in flyash, also comprise and add talcum powder.
7. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 6, is characterized in that,
Described talcous add-on is 10-30 part.
8. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 4, is characterized in that,
In the described step that adds metallic silicon power in flyash,
Also comprise add in alumine, aluminum oxide, magnesia powder any one or multiple.
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Cited By (4)
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| CN104119842A (en) * | 2014-07-17 | 2014-10-29 | 长兴欧利雅磨具磨料厂 | Silicon oxide heat storage ball |
| CN105174978A (en) * | 2015-08-20 | 2015-12-23 | 包头市正唐环保产业有限公司 | Preparation technology of heat storage balls |
| CN105838335A (en) * | 2015-02-03 | 2016-08-10 | 日本揖斐电株式会社 | Quasi-capsule molten salt heat storage material |
| CN114574164A (en) * | 2022-01-07 | 2022-06-03 | 华南理工大学 | Alloy composite phase change material and one-step pressing method thereof |
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| CN105174978A (en) * | 2015-08-20 | 2015-12-23 | 包头市正唐环保产业有限公司 | Preparation technology of heat storage balls |
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| CN114574164A (en) * | 2022-01-07 | 2022-06-03 | 华南理工大学 | Alloy composite phase change material and one-step pressing method thereof |
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