CN103694965B - A kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product - Google Patents
A kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product Download PDFInfo
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- CN103694965B CN103694965B CN201310726831.2A CN201310726831A CN103694965B CN 103694965 B CN103694965 B CN 103694965B CN 201310726831 A CN201310726831 A CN 201310726831A CN 103694965 B CN103694965 B CN 103694965B
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Abstract
The present invention relates to material processing field, particularly a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product, 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 moulding material; Moulding material is made to the base substrate of hole brick or heat-storing sphere or ceramic honey comb; By body drying, insulation, burn till, cooling, selection. The serviceability temperature of accumulation of heat product prepared by method provided by the invention is high, and can recycle for a long time, and heat storage capacity is stronger.
Description
Technical field
The present invention relates to material processing field, utilize high-temperature phase change heat accumulation material to make accumulation of heat in particular to oneThe method of product.
Background technology
Existing artificial mullite synthesizing or the main difference of cordierite goods technology are raw materials used difference and workA little difference of skill process, its end product is still mainly conventional mullite or the cordierite goods that industry is known, and does not comeStone or cordierite products itself have outstanding high-temperature behavior.
The high-temperature phase change heat accumulation material of report is mainly made with macromolecular material or aluminium alloy, magnesium alloy etc. at present, stillServiceability temperature is lower, general below 800 DEG C. It is reported, in solar energy industry, the high-temperature phase-change of being made by metallic aluminium powderThe upper limit temperature of heat tolerance of heat-storing material can reach 800 DEG C, higher than 800 DEG C have not been reported.
And existing accumulation of heat product is all hole brick, heat-storing sphere and ceramic honey combs of being made up of conventional raw material, these productsAlthough serviceability temperature higher, can reach more than 1000 DEG C, because the heat storage type of existing accumulation of heat product is mainlyPhysics heat absorption mode by material itself is carried out heat storage, and its heat-retaining is limited, and heat absorption heat transfer rate is also slow, at heightUnder temperature situation, itself is easily etched material, and such as hot-blast stove, heating furnace all needs 1300 DEG C of above exotic materialsExisting these high-temperature phase change heat accumulation materials and product can use, so can only be used in the middle low-temperature heat accumulating necks such as solar energyTerritory.
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 solveAbove-mentioned problem.
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, bagDraw together 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 extrude intoMoulding material;
Described moulding 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 in a kind of method of utilizing high-temperature phase change heat accumulation material making accumulation of heat product provided by the invention, powder whereinCoal ash is raw material conventional while preparing mullite or cordierite product material, but the bulk density of metallic silicon power is wherein2.33g/cm3, specific heat capacity is 0.162Kcal/Kg, and fusing point is 1414 DEG C, and melting heat is 50.55KJ/mol, at 1000-1200 DEG CIn following, low thermophase can improve the heat absorption conduction velocity of mullite or cordierite product material, so improve mullite orThe ability of the transferring heat of cordierite product material and absorption heat. In the time of high temperature, the metallic silicon power of accumulation of heat product surface is oxidizedForm the oxidation film of silicon, can prevent the erosion of FeO etc., and then the service life that can improve accumulation of heat product. The oxygen of silicon simultaneouslyCompound film can effectively be protected the metallic silicon power of the material internal of accumulation of heat product, makes it keep simple substance state always.
In the time that the further rising of environment temperature reaches 1414 DEG C, the metallic silicon power of accumulation of heat interiors of products high degree of dispersion starts to meltChange, and carry out extra phase-transition heat-storage process in phase transformation fusion process with the heat absorption capacity of 50.55kJ/mol, in this process, makeAccumulation of heat product, in heat-accumulating process, can be put aside heat more extraly, has namely improved the heat storage capacity of accumulation of heat product.
Simultaneously because the silicon metal powder of accumulation of heat interiors of products can solidify again after fusing cooling, so, metallic silicon powerFusing, process of setting can circulate, this accumulation of heat product can recycle, and the serviceability temperature of this accumulation of heat product existsMore than 1000 DEG C, so the serviceability temperature of accumulation of heat product prepared by method provided by the invention is high, and can circulate and make for a long timeWith, heat storage capacity is stronger.
Brief description of the drawings
A kind of method stream 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 1Cheng Tu.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is described in further detail below by specific embodiment.
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 discarded object of power plant, and the cost of raw material is low, and easily obtains.
Wherein the addition of flyash is 20-40 part, and the addition of metallic silicon power is 10-40 part.
In order to improve the caking property between each material composition, can also wherein be added associativity clay, according to former materialThe addition ratio of material, the addition of associativity clay is generally 1-10 part.
In flyash, add in the step of metallic silicon power, can also give and wherein add talcum powder, talcous additionFor 10-30 part, add talcum powder to make heat-storing material cordierite material afterwards. In the time not adding talcum powder, make heat-storing materialMullite material.
In flyash, add in the step of metallic silicon power, conventionally also can add in alumine, aluminium oxide, magnesia powderAny one or multiple.
Because the content of the aluminium in flyash is less, less when the content of the aluminium in raw meal coal ash, can not reach techniqueRequire when content, conventionally can add alumine, or aluminium oxide, or magnesia powder, or the mixture of any two or three kinds regulatesThe content of aluminium, and magnesian content.
Wherein alumine, or aluminium oxide, or the addition of the mixture of the two is according to the content of the aluminium in flyashHow much add.
102. after ball mill mixing and ball milling, and mist projection granulating working pressure machine mechanical pressing or use mud extruder are extrudedFor moulding material;
This step is general procedure in common process.
The base substrate of hole brick, heat-storing sphere or ceramic honey comb made by described moulding material by 103.;
104. by described body drying, insulation, burns till, cooling, selection.
Wherein temperature dry, insulation is 1250-1400 DEG C, and the time of described insulation is 4-12 hour.
Naturally after cooling, after pick classification, be finished product accumulation of heat product, this kind of accumulation of heat product is in high-temperature energy-conservation fieldBe widely used, particularly at hot-blast stove, the energy-saving potentials such as heating 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, according to the methodThe accumulation of heat product of making, raw meal coal ash is wherein raw material conventional while preparing mullite or cordierite product material, butThat metallic silicon power low thermophase in lower than 1000 DEG C wherein can improve heat absorption conduction velocity, accumulation of heat product in the time of high temperatureThe oxidation film of the oxidized formation silicon of metallic silicon power on surface, can prevent the erosion of FeO etc., and then can improve mullite or violetThe service life of green stone product material.
The oxidation film of silicon can effectively be protected the metallic silicon power of accumulation of heat interiors of products simultaneously, and it is kept alwaysSimple substance state.
In the time that the further rising of environment temperature reaches 1414 DEG C, the metallic silicon power of the high degree of dispersion of accumulation of heat interiors of products startsFusing, and carry out extra phase-transition heat-storage process in phase transformation fusion process with the heat absorption capacity of 50.55kJ/mol, in this process, makeObtain accumulation of heat product in heat-accumulating process, can put aside extraly heat more, namely improved the accumulation of heat energy of accumulation of heat productPower.
Simultaneously because the silicon metal powder of accumulation of heat interiors of products can solidify again after fusing cooling, so, metallic silicon powerFusing, process of setting can circulate, simultaneously the oxidation film of accumulation of heat product subsurface silicon can be protected accumulation of heat productProtect, and the serviceability temperature of this material is more than 1000 DEG C.
So accumulation of heat product serviceability temperature prepared by method provided by the invention is high, and can recycle for a long time, holdsHeat energy power is stronger.
Utilize accumulation of heat product that accumulation of heat product that method provided by the invention makes and traditional material make in useContrast as following table 1:
Table 1
| The present invention | Tradition accumulation of heat product | |
| Heat storage type | Physics heat absorption+decalescence | Physics heat absorption |
| Diaphragm | The oxidation film of silicon | Nothing |
| Service 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 |
Can be clear that according to table 1, utilize accumulation of heat product prepared by method provided by the invention significantly, in accumulation of heatIn mode, there is larger advantage, changed physical property that conventional accumulation of heat product only relies on self and carried out physics heat absorptionHeat storage type, the phase-transition heat-storage that utilizes accumulation of heat product to carry out in phase transition process, by tying physics heat absorption mutually with decalescenceClose, make accumulation of heat product in heat-accumulating process, except physics heat absorption, also have extra phase-transition heat-storage, improved accumulation of heat productThe heat storage capacity of product and heat storage efficiency.
While particularly making honeycomb ceramic product with this raw material because the fusing of part metals silicon helps agglomeration, the honeybee obtainingThe densification of nest ceramic, intensity is higher.
Accumulation of heat product table prepared by the mullite of meanwhile, preparing according to method provided by the invention or cordierite product materialFace, because there is metallic silicon power, becomes the oxide film of accumulation of heat product after metallic silicon power is oxidized, stoped well at heightUnder temperature environment, the erosion to accumulation of heat product such as FeO, the service life of having improved accumulation of heat product.
Be generally 8-10, the service life of heat-storing sphere the service life of the hole brick that meanwhile, conventional heat-storing material is madeBe generally 3-5, and the accumulation of heat product of the mullite material of preparing according to method provided by the invention processing, such as heat-storing sphereBe longer than 5 years service life, and be longer than the service life of hole brick 8 years. The honeycomb ceramic product making by the method is on heating furnaceApplication improve 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; Through mixing and ball millingAfter, mist projection granulating, 400 tons of forcing press moulding, make 37 hole bricks, drying, 1320-1390 DEG C of sintering, cooling, choose and obtain highTemperature phase-change accumulation energy 37 hole bricks.
Concrete case study on implementation 2:
35 parts, flyash, 8 parts of associativity clays, 47 parts of alumines, 10 parts of alumina powders, additional 30 parts of metallic silicon powers;After mixing and ball milling, mist projection granulating, 350 tons of forcing press moulding, make Φ 70 heat-storing spheres, drying, 1330-1400 DEG C 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 alumina powders, the metallic silicon power of additional 20 parts;After mixing and ball milling, vacuum pugging extrusion modling, makes porous honeycomb ceramic, drying, 1380 DEG C of sintering, cooling, selection andObtain 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 alumina powders, 10 parts of talcum powder, additional 10 partsMetallic silicon power; After mixing and ball milling, vacuum pugging extrusion modling, makes porous honeycomb ceramic, drying, and 1400 DEG C 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 alumina powders, 30 parts of talcum powder, additional 40 partsMetallic silicon power; After mixing and ball milling, vacuum pugging extrusion modling, makes porous honeycomb ceramic, drying, and 1390 DEG C 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 the skill of this areaArt personnel, the present invention can have various modifications and variations. Within the spirit and principles in the present invention all, to do any repairingProtection scope of the present invention changes, be equal to replacement, improvement etc., within all should be included in.
Claims (5)
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 forming materialMaterial;
Described moulding 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;
Described dry, insulation, burns till, cooling, in the step of selection,
Described temperature dry, insulation is 1250-1400 DEG C, and the time of described insulation is 4-12 hour;
In the described step that adds metallic silicon power in flyash, also comprise and add associativity clay;
In the described step that adds metallic silicon power in flyash,
Also comprise and add alumine, or aluminium oxide, or the mixture of the two.
2. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 1, its feature existsIn, in the described step that adds metallic silicon power in flyash,
The addition of described flyash is 20-40 part, and the addition 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, its feature existsIn,
The addition of described associativity clay is 1-10 part.
4. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 1, its feature existsIn,
In the described step that adds metallic silicon power in flyash, also comprise and add talcum powder.
5. a kind of method of utilizing high-temperature phase change heat accumulation material to make accumulation of heat product according to claim 4, its feature existsIn,
Described talcous addition is 10-30 part.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104119842B (en) * | 2014-07-17 | 2017-05-03 | 长兴欧利雅磨具磨料厂 | Silicon oxide heat storage ball |
| JP2016142484A (en) * | 2015-02-03 | 2016-08-08 | イビデン株式会社 | Sub-capsule molten salt heat storage material |
| CN105174978B (en) * | 2015-08-20 | 2018-06-29 | 内蒙古正唐环保产业有限公司 | A kind of technique for preparing heat-storing sphere |
| 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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