CN109021928A - Heat accumulation module and preparation method thereof for heat storage type electric heater - Google Patents
Heat accumulation module and preparation method thereof for heat storage type electric heater Download PDFInfo
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- CN109021928A CN109021928A CN201710433570.3A CN201710433570A CN109021928A CN 109021928 A CN109021928 A CN 109021928A CN 201710433570 A CN201710433570 A CN 201710433570A CN 109021928 A CN109021928 A CN 109021928A
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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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
- F24D13/00—Electric heating systems
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Combustion & Propulsion (AREA)
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- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The heat accumulation module and preparation method thereof that the present invention provides a kind of for heat storage type electric heater is after being mixed with phase-change heat-storage material composition and backing material by the mass ratio of 3:7-7:3, and is sintered what 1-5h was prepared at 200-700 DEG C.The present invention also provides the preparation method of above-mentioned heat accumulation module and its applications in heat storage type electric heater.Heat accumulation module provided by the present invention can guarantee that heat accumulating is heated evenly, and improve heat accumulation/exothermal efficiency, avoid heat accumulating hot-spot, and then can increase its service life；Contact of the heat accumulating with metallic elements can also be avoided simultaneously, prevents the generation of corrosion phenomenon；Modular heat accumulating is easy to install and use, can easily be replaced to module according to actual demand.
Description
Technical field
The heat accumulation module and preparation method thereof that the present invention relates to a kind of for heat storage type electric heater, belongs to heat accumulating technology
Field.
Background technique
Heat storage type electric heater is a kind of electric heating equipment, stores energy using night power grid power load trough period, and
It is indoor heating on daytime.General heat storage type electric heater can complete heat accumulation within the 6-10 hour of electricity price trough period, and complete
It heats within it 24 hours, to reach peak load regulation network, cleaning is for the warm purpose for saving heating cost.Heat storage type electric heater work is former
Reason are as follows: the heat accumulating built in electric heater is heated using heating element resistant to high temperature fever, and is stored.It is needing for room
Between heat when heat is released according to certain rate again.
Existing heat storage type electric heater can realize the demand using trough-electricity for whole day heating to a certain extent, but still have
Following disadvantage restricts its application.Its heat storage capacity is by volumetric constraint.Heat storage type electric heater in the market is the integrated design, i.e.,
Heat storage units and heat-sink unit are an entirety.It is limited by the interior space and aesthetic, the volume of electric heater cannot mistake
Greatly, therefore the quantity of heat storage of heat storage type electric heater is very limited.Lower-powered heat storage type electric heater is even being unable to satisfy daytime just
The demand often warmed oneself.
Therefore it provides a kind of heat accumulation module with more high heat storage amount is to solve the difficulty that current heat storage type electric heater is faced
The technical issues of topic has become this field urgent need to resolve.
Summary of the invention
In order to solve the above shortcomings and deficiencies, the purpose of the present invention is to provide a kind of heat accumulation modules.
The object of the invention is also to provide the preparation methods of above-mentioned heat accumulation module.
The object of the invention is also to provide application of the above-mentioned heat accumulation module in heat storage type electric heater.
The purpose of the present invention is to provide a kind of heat storage type electric heater again comprising the heat accumulation module.
It in order to achieve the above objectives, is with phase-change heat-storage material composition and branch the present invention provides a kind of heat accumulation module
After timbering material is by the mass ratio mixing of 3:7-7:3, and it is sintered what 1-5h was prepared at 200-700 DEG C.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the backing material includes powdered
SiO2、MgO、Al2O3、SiC、ZnO、Bi2O3、CaCO3、Na2CO3、BaCO3And one or more of other ceramic materials is mixed
Close object.Wherein, ceramic material is conventional substances, and those skilled in the art can need from existing ceramic material according to operation
Select suitable material for the present invention.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, with phase-change heat-storage material composition used
Total weight be 100% meter comprising the dispersing agent of the ratio hot reinforcing material of 0.5-10wt%, 0.05-0.5wt%, surplus are
Phase-change heat-storage material.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the phase-change heat-storage material is high density
One of polyethylene, antierythrite, paraffin or fuse salt.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the high density polyethylene (HDPE) (HDPE) is
The polyethylene particle of diameter 1-5mm, purity > 98%；The high density polyethylene (HDPE) is milky.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the antierythrite is not more than for partial size
The particle of 2mm.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the phase transition temperature of the paraffin is 80-
200℃。
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the fuse salt includes unitary salt, two
The combination of one or more of first salt and polybasic salt.Wherein, when the phase-change heat-storage material is fuse salt, the present invention is to molten
Melt the specific usage ratio in salt between unitary salt, binary salt and polybasic salt and do not make specific requirement, those skilled in the art can be with
Need to reasonably adjust the usage ratio between unitary salt, binary salt and polybasic salt according to operation, as long as guaranteeing that this hair may be implemented
Improving eyesight.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the unitary salt includes the alkali gold of nitric acid
Belong to the halide of salt and alkali metal.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the binary salt includes the alkaline earth of nitric acid
The halide of metal salt and alkaline-earth metal.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the dispersing agent includes dodecyl sulphur
The combination of one or more of sour sodium (SDS), neopelex (SDBS) and Arabic gum.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, it is described than hot reinforcing material be metal oxygen
Compound nano particle, the partial size of the nano particle are 10-100nm.
Specific embodiment according to the present invention, it is preferable that in heat accumulation module, the metal oxide nanoparticles packet
Include MgO, Al2O3、SiO2、CuO、TiO2And the combination of one or more of ZnO nano particle.
Specific embodiment according to the present invention, wherein the phase-change heat-storage material composition is prepared according to the following steps:
1) it is ground after, being mixed in proportion by phase-change heat-storage material and than hot reinforcing material, is uniformly mixed, is mixed
Object A；
2), mixture A obtained in step 1) is dissolved in deionized water, is stirred evenly, aqueous solution B is obtained；
3), regulating step 2) described in aqueous solution B pH to 9-11, obtain aqueous solution C；
4) substep wet-milling, is carried out to aqueous solution C obtained in step 3) using the grinding bead of different-diameter, to obtain uniformly
Slurry；
5) it, is proportionally added into the dispersing agent into uniform slurry obtained in step 4), is stirred evenly, is obtained through dividing
Liquid after dissipating；
6), under stirring, it is complete to moisture that heating evaporation is carried out to the liquid after being dispersed obtained in step 5)
It is evaporated, obtains the phase-change heat-storage material composition.
Specific embodiment according to the present invention, wherein ground described in the preparation method step 1) of the heat accumulation module
Revolving speed be 100-300rpm, milling time 5-15min.
Wherein, it is ground in step 1) using planetary ball mill, and the planetary ball mill is the routine that this field uses
Equipment, the dismembyator and mill ball of the planetary ball mill are all made of silicon carbide or the manufacture of zirconium oxide material.
Specific embodiment according to the present invention, wherein water-soluble with this in the preparation method step 2) of the heat accumulation module
The gross mass of liquid is 100% meter, and the mass fraction of mixture A is 1-10%.
Wherein, it is stirred in step 2) using blender, blender used is the conventional equipment that this field uses.
Specific embodiment according to the present invention, wherein stirred described in the preparation method step 2) of the heat accumulation module
Revolving speed be 50-100rpm, mixing time 10-20min.
Specific embodiment according to the present invention, wherein 1mol/ is used in the preparation method step 3) of the heat accumulation module
The HCl or NaOH of L carries out pH adjusting.
Specific embodiment according to the present invention, wherein the substep described in the preparation method step 4) of the heat accumulation module
Wet-milling follows the steps below:
First using diameter be 1mm grinding bead with the wet-milling revolving speed of 1800-3000rpm to the aqueous solution C wet-milling 1-
2h；
Using diameter instead again is the grinding bead of 0.5mm with the further wet-milling 1-2h of the wet-milling revolving speed of 1800-3000rpm；
Finally use instead diameter be 0.1mm grinding bead with the wet-milling revolving speed of 1800-3000rpm to aqueous solution C wet-milling 1-2h.
Wherein, it is ground in step 4) using ball mill, and the ball mill is the conventional equipment that this field uses, the pearl
Grinding machine and grinding bead are all made of zirconium oxide or silicon carbide manufacture.
Specific embodiment according to the present invention, wherein stirred described in the preparation method step 5) of the heat accumulation module
Revolving speed be 20-50rpm, mixing time 10-30min.
Wherein, it is stirred in step 5) using blender, blender used is the conventional equipment that this field uses.
Specific embodiment according to the present invention, wherein stirred described in the preparation method step 6) of the heat accumulation module
Revolving speed be 20-50rpm.
Wherein, it is stirred in step 6) using blender, blender used is the conventional equipment that this field uses.
The present invention also provides the preparation methods of above-mentioned heat accumulation module comprising following steps:
1) phase-change heat-storage material composition and backing material are mixed by the mass ratio of 3:7-7:3, obtains mixture；
2) mixture obtained in step 1) is sintered at 200-700 DEG C 1-5h, obtains the heat accumulation module.
The present invention also provides application of the above-mentioned heat accumulation module in heat storage type electric heater.
The present invention also provides a kind of heat storage type electric heaters comprising the heat accumulation module.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
Phase-change heat-storage material is mixed with than hot reinforcing material nano particle using preparation method described herein,
Compared with conventional method, specific heat reinforcing material nano particle can be made to be distributed in phase-change heat-storage material composition more uniform；
In addition, the nano particle (than hot reinforcing material) that the application is added can produce the strong coulomb field of force, this coulomb of field of force into
And will affect the molecular arrangement of phase-change heat-storage material around, form it into one layer of fine and close structure；Phase-change material in this configuration
Potential energy well deepen, therefore when store heat, system can absorb more energy before temperature increases in the form of potential energy, from
And the specific heat capacity of lifting system, and then the unit volume heat storage capacity of system is improved, in the base for the quality for not increasing heat-retaining mass
The heat storage capacity of heat storage type electric heater is improved on plinth.
Heat accumulation can be guaranteed by obtaining heat accumulation module to phase-change heat-storage material composition provided by the present invention progress modularization
Material is heated evenly, and is improved heat accumulation/exothermal efficiency, is avoided heat accumulating hot-spot, and then can increase its service life；Institute
In effectively phase-change heat-storage material being wrapped in backing material, in phase transition process, phase-change heat-storage material will not be from branch
It is overflowed in timbering material, so that heat accumulating service life can also be extended, material is avoided to be lost, while heat accumulation material can also be avoided
Expect the contact with metallic elements, prevents the generation of corrosion phenomenon；Modular heat accumulating is easy to install and use, according to reality
Demand easily module can be replaced.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction in detail below
Embodiment carries out following detailed description to technical solution of the present invention, but should not be understood as the limit to enforceable range of the invention
It is fixed.
Embodiment 1
Present embodiments provide a kind of preparation method of heat accumulation module for heat storage type electric heater comprising following step
It is rapid:
1) phase-change heat-storage material composition and backing material (MgO powder) are mixed by the mass ratio of 7:3, is mixed
Object；
2) mixture obtained in step 1) is sintered at 500 DEG C 2h, obtains the heat accumulation module；
Wherein, phase-change heat-storage material composition used in the present embodiment is prepared by the following method to obtain:
Production is based on KNO3-LiNO3The phase-change heat-storage material of (mass ratio 33.5:66.5).Using 1%SiO2As than
Hot reinforcing material, 0.1%SDBS is as dispersing agent.
1) in the mixing step, than hot reinforcing material and phase-change heat-storage material according to aforementioned ratio after mixing
It is placed in planetary ball mill.
Planetary ball mill revolving speed is 100rpm.
Milling time is 15 minutes.
The dismembyator and mill ball of the planetary ball mill are all made of silicon carbide manufacture.
2) it is dissolved in deionized water simultaneously after the completion of grinding by uniformly mixed phase-change heat-storage material and than hot reinforcing material,
It is stirred fused salt 10 minutes using blender with the speed of 50rpm.
Shared mass fraction is 10% in aqueous solution for the phase-change heat-storage material and the mixture than hot reinforcing material.
3) it in pH adjustment step, is adjusted using the HCl or NaOH of 1mol/L.
It is adjusted by pH, above-mentioned deionized water solution pH is adjusted to 10.
4) aqueous solution after pH is adjusted is added in ball mill.
Wet-milling is carried out to above-mentioned aqueous solution using the grinding bead that diameter is 1mm first.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Then use the further wet-milling of grinding bead that diameter is 0.5mm instead.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Then use the further wet-milling of grinding bead that diameter is 0.1mm instead.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Ball mill and grinding bead are all made of silicon carbide manufacture.
5) solution is exported into ball mill, and dispersing agent is added by aforementioned ratio.Then use blender with the speed of 20rpm
Stirring 10 minutes.
6) aqueous solution is subjected to heating evaporation after the completion of dispersion steps.Persistently use blender with 20rpm in evaporation process
Speed be stirred, until moisture is evaporated completely, sample is uniformly mixed, and obtains the phase-change heat-storage material composition.
The addition nano particle SiO that the present embodiment is prepared is measured using scan-type differential thermal analyzer respectively2Phase transformation
Heat accumulating composition and it is not added with nano particle SiO2Obtained phase-change heat-storage material composition (the composition and the present embodiment
The difference for the phase-change heat-storage material composition being prepared is only that it does not add nano particle SiO2, other components and preparation
Method is identical as the present embodiment composition) specific heat average value, analysis the result shows that: the present embodiment add nano particle SiO2
The specific heat average value of obtained phase-change heat-storage material composition is 2.11kJ/kg/K, and is not added with nano particle SiO2It obtains
The specific heat average value of phase-change heat-storage material composition is 1.84kJ/kg/K.
The heat accumulation module and be not added with nano particle SiO that measurement the present embodiment is prepared respectively again2Obtained phase transformation storage
(difference for the phase-change heat-storage material composition that the composition is prepared with the present embodiment is only that it does not have to hot material composition
Add nano particle SiO2, other components and preparation method are identical as the present embodiment composition) average thermal conductivity, test knot
Fruit shows: being not added with nano particle SiO2The average thermal conductivity of obtained phase-change heat-storage material composition is 0.48W/m/K, and this
The average thermal conductivity for the heat accumulation module that embodiment obtains is up to 30W/m/K.
It can be seen that the heat accumulation module average thermal conductivity with higher that the present embodiment is prepared, therefore its heat accumulation/put
The thermal efficiency is higher, can be to avoid hot-spot.
Embodiment 2
Present embodiments provide a kind of preparation method of heat accumulation module for heat storage type electric heater comprising following step
It is rapid:
1) by phase-change heat-storage material composition and backing material (Al2O3Powder) it is mixed by the mass ratio of 3:7, it is mixed
Object；
2) mixture obtained in step 1) is sintered at 670 DEG C 2h, obtains the heat accumulation module；
Wherein, phase-change heat-storage material composition used in the present embodiment is prepared by the following method to obtain:
Production is based on CaCl2The phase-change heat-storage material of-NaCl (mass ratio 52.8:47.2).Using 1%SiO2As than
Hot reinforcing material, 0.1%SDBS is as dispersing agent.
1) in the mixing step, than hot reinforcing material and phase-change heat-storage material according to aforementioned ratio after mixing
It is placed in planetary ball mill.
Planetary ball mill revolving speed is 100rpm.
Milling time is 15 minutes.
The dismembyator and mill ball of the planetary ball mill are all made of silicon carbide manufacture.
2) it is dissolved in deionized water simultaneously after the completion of grinding by uniformly mixed phase-change heat-storage material and than hot reinforcing material,
It is stirred fused salt 10 minutes using blender with the speed of 50rpm.
Shared mass fraction is 10% in aqueous solution for the phase-change heat-storage material and the mixture than hot reinforcing material.
3) it in pH adjustment step, is adjusted using the HCl or NaOH of 1mol/L.
It is adjusted by pH, above-mentioned deionized water solution pH is adjusted to 10.
4) aqueous solution after pH is adjusted is added in ball mill.
Wet-milling is carried out to above-mentioned aqueous solution using the grinding bead that diameter is 1mm first.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Then use the further wet-milling of grinding bead that diameter is 0.5mm instead.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Then use the further wet-milling of grinding bead that diameter is 0.1mm instead.
Wet-milling revolving speed is 1800rpm.
Milling time is 1 hour.
Ball mill and grinding bead are all made of silicon carbide manufacture.
5) solution is exported into ball mill, and dispersing agent is added by aforementioned ratio.Then use blender with the speed of 20rpm
Stirring 10 minutes.
6) aqueous solution is subjected to heating evaporation after the completion of dispersion steps.Persistently use blender with 20rpm in evaporation process
Speed be stirred, until moisture is evaporated completely, sample is uniformly mixed, and obtains the phase-change heat-storage material composition.
The addition nano particle SiO that the present embodiment is prepared is measured using scan-type differential thermal analyzer respectively2Phase transformation
Heat accumulating composition and it is not added with nano particle SiO2Obtained phase-change heat-storage material composition (the composition and the present embodiment
The difference for the phase-change heat-storage material composition being prepared is only that it does not add nano particle SiO2, other components and preparation
Method is identical as the present embodiment composition) specific heat average value, analysis the result shows that: the present embodiment add nano particle SiO2
The specific heat average value of obtained phase-change heat-storage material composition is 0.81kJ/kg/K, and is not added with nano particle SiO2It obtains
The specific heat average value of phase-change heat-storage material composition is 0.76kJ/kg/K.
The heat accumulation module and be not added with nano particle SiO that measurement the present embodiment is prepared respectively again2Obtained phase transformation storage
(difference for the phase-change heat-storage material composition that the composition is prepared with the present embodiment is only that it does not have to hot material composition
Add nano particle SiO2, other components and preparation method are identical as the present embodiment composition) average thermal conductivity, test knot
Fruit shows: being not added with nano particle SiO2The average thermal conductivity of obtained phase-change heat-storage material composition is 6.5W/m/K, and this
The average thermal conductivity for the heat accumulation module that embodiment obtains is up to 25W/m/K.
It can be seen that the heat accumulation module average thermal conductivity with higher that the present embodiment is prepared, therefore its heat accumulation/put
The thermal efficiency is higher, can be to avoid hot-spot.
Claims (10)
1. a kind of heat accumulation module, it is after being mixed with phase-change heat-storage material composition and backing material by the mass ratio of 3:7-7:3,
And it is sintered what 1-5h was prepared at 200-700 DEG C.
2. heat accumulation module according to claim 1, which is characterized in that the backing material includes powdered SiO2、MgO、
Al2O3、SiC、ZnO、Bi2O3、CaCO3、Na2CO3、BaCO3And the mixture of one or more of other ceramic materials.
3. heat accumulation module according to claim 1 or 2, which is characterized in that with the gross weight of the phase-change heat-storage material composition
Amount is 100% meter comprising the dispersing agent of the ratio hot reinforcing material of 0.5-10wt%, 0.05-0.5wt%, surplus are that phase transformation is stored up
Hot material.
4. heat accumulation module according to claim 3, which is characterized in that the phase-change heat-storage material be high density polyethylene (HDPE),
One of antierythrite, paraffin or fuse salt；
Preferably, the high density polyethylene (HDPE) is the polyethylene particle of diameter 1-5mm, purity > 98%；
It is further preferred that the antierythrite is the particle that partial size is not more than 2mm；
It is further preferred that the phase transition temperature of the paraffin is 80-200 DEG C.
5. heat accumulation module according to claim 4, which is characterized in that the fuse salt includes unitary salt, binary salt and more
The combination of one or more of first salt；
Preferably, the unitary salt includes the alkali metal salt of nitric acid and the halide of alkali metal；
It is further preferred that the binary salt includes the alkali salt of nitric acid and the halide of alkaline-earth metal.
6. heat accumulation module according to claim 3, which is characterized in that the dispersing agent includes lauryl sodium sulfate, ten
The combination of one or more of dialkyl benzene sulfonic acids sodium and Arabic gum.
7. heat accumulation module according to claim 3, which is characterized in that it is described than hot reinforcing material be metal oxide nano
Particle, the partial size of the nano particle are 10-100nm；
Preferably, the metal oxide nanoparticles include MgO, Al2O3、SiO2、CuO、TiO2And one in ZnO nano particle
Kind or several combinations.
8. the preparation method of the described in any item heat accumulation modules of claim 1-7 comprising following steps:
1) phase-change heat-storage material composition and backing material are mixed by the mass ratio of 3:7-7:3, obtains mixture；
2) mixture obtained in step 1) is sintered at 200-700 DEG C 1-5h, obtains the heat accumulation module.
9. application of the described in any item heat accumulation modules of claim 1-7 in heat storage type electric heater.
10. a kind of heat storage type electric heater comprising the described in any item heat accumulation modules of claim 1-7.
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| CN201710433570.3A CN109021928A (en) | 2017-06-09 | 2017-06-09 | Heat accumulation module and preparation method thereof for heat storage type electric heater |
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| CN201710433570.3A CN109021928A (en) | 2017-06-09 | 2017-06-09 | Heat accumulation module and preparation method thereof for heat storage type electric heater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021246429A1 (en) * | 2020-06-03 | 2021-12-09 | 三菱パワー株式会社 | Heat storage body cartridge and heat storage device |
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| CN1328107A (en) * | 2000-06-13 | 2001-12-26 | 广东工业大学 | Composite inorganic salt/ceramic-base heat-accumulating material and its preparing process |
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Application publication date: 20181218 |