CN108048044A - Inorganic salts-ceramic base thermal energy storage material and preparation method thereof - Google Patents
Inorganic salts-ceramic base thermal energy storage material and preparation method thereof Download PDFInfo
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- CN108048044A CN108048044A CN201711322766.1A CN201711322766A CN108048044A CN 108048044 A CN108048044 A CN 108048044A CN 201711322766 A CN201711322766 A CN 201711322766A CN 108048044 A CN108048044 A CN 108048044A
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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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B9/00—Stoves for heating the blast in blast furnaces
- C21B9/02—Brick hot-blast stoves
- C21B9/06—Linings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/0056—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using solid heat storage material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
- F27D2017/007—Systems for reclaiming waste heat including regenerators
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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Abstract
The invention belongs to heat accumulating technical fields, specifically disclose a kind of inorganic salts ceramic base thermal energy storage material.In terms of parts by weight, which is prepared by following components：K2CO324~32 parts, CaCO320~28 parts, 6~10 parts of BeO, Si3N410~16 parts and 13~18 parts of SiC.The heat accumulating raw material select and match it is scientific and reasonable, the material internal being sintered out have ultra micro porous structure, the hot property and mechanical performance of material are satisfied by commercial Application demand：1200~1260 DEG C of melting temperature, total 170~190J/g of heat storage capacity, the maximum temperature used reach 1300~1400 DEG C.
Description
Technical field
The invention belongs to heat accumulating technical fields, and in particular to a kind of inorganic salts-ceramic base thermal energy storage material and its
Preparation method.
Background technology
Heat accumulation composite material has been achieved for significantly being in progress from this new concept is generated till now, is material product
Change and its provide basic basis in the application of industrial storage heater and solar power system.But original composite material is all in difference
There are problems that the salt volume in solid-liquid phase-change process collapses the variation that can cause composite material thermal resistance in degree：Fused salt
Evaporation will reduce the share of phase-change material, reduce thermal storage performance.
Present invention aim to improve the performance of inorganic salts thermal energy storage material on the basis of former result of study,
It develops that a kind of heat storage capacity is big, heat release is stable and is avoided that or reduces the material of Evaporation Phenomenon：Can in heat reservoir and
It popularizes and uses in the application of storage heater.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of inorganic salts-ceramic base thermal energy storage material, with
Parts by weight meter, the heat accumulating are prepared by following components：K2CO324~32 parts, CaCO320~28 parts, BeO 6~
10 parts, Si3N410~16 parts and 13~18 parts of SiC.
Preferably, above-mentioned inorganic salts-ceramic base thermal energy storage material, in terms of parts by weight, the heat accumulating is by with the following group
Divide and be prepared：K2CO325~30 parts, CaCO322~25 parts, 6~8 parts of BeO, Si3N412~15 parts and SiC 15~18
Part.
It is furthermore preferred that above-mentioned inorganic salts-ceramic base thermal energy storage material, in terms of parts by weight, the heat accumulating is by following
Component is prepared：K2CO330 parts, CaCO325 parts, 6 parts of BeO, Si3N414 parts and 16 parts of SiC.
Second technical problem to be solved by this invention is to provide the system of above-mentioned inorganic salts-ceramic base thermal energy storage material
Preparation Method, this method specifically include following steps：
(1) by K2CO324~32 parts, CaCO320~28 parts and BeO 6~10 parts are uniformly mixed, and obtain mixture 1, press
According to quality than mixture 1:Absolute ethyl alcohol:BeO porcelain ball=1:0.11~0.14:0.05~0.10, it is added in into mixture 1 anhydrous
Ethyl alcohol and BeO porcelain balls, 2~3h of mixing and ball milling cross 200 mesh sieves, obtain slurry 1；
(2) by Si3N410~16 parts and SiC 13~18 parts are uniformly mixed, and obtain mixture 2, compare mixture according to quality
2:Absolute ethyl alcohol:Al2O3Porcelain ball=1:0.11~0.14:0.05~0.10, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain
Ball, 1~2h of mixing and ball milling cross 200 mesh sieves, obtain slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues 1~2h of ball milling, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering, sintering temperature 1020~1150 after drying
DEG C, 4~5h of sintering time after the completion of sintering, keeps the temperature 20~30min, and natural cooling obtains the compound heat accumulation of inorganic salts-ceramic base
Material.
Wherein, the preparation method of above-mentioned inorganic salts-ceramic base thermal energy storage material, the heating that step (4) uses when being sintered
System is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With the heating rate of 5 DEG C/s, 200~
700 DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 700~sintering temperature, 4~5h of sintering time.
Compared with prior art, the beneficial effects of the invention are as follows：Inorganic salts of the present invention-ceramic base thermal energy storage material raw material
Select and match scientific and reasonable, the material internal being sintered out has ultra micro porous structure, and the hot property and mechanical performance of material be equal
Meet commercial Application demand：1200~1260 DEG C of melting temperature, total 170~190J/g of heat storage capacity, the maximum temperature used
Reach 1300~1400 DEG C.
The heat accumulating can be made into the element of variously-shaped (such as spherical, brick shape), is accumulated in the form of packed bed and is formed storage
Hot systems in operation, while utilize the latent heat of inorganic salts and the sensible heat storage thermal energy of composite material.This latent heat/sensible heat is multiple
Collaboration system had not only remain the characteristics of hidden heat energy storage density is big and energy output is stablized, but also can be flowed with sensible heat energy-accumulating medium with heat exchange
The advantages of body direct contact heat transfer, also overcome that latent heat storage system needs to expend a large amount of canisters, tubing and there are fused salts
The shortcomings that corrosion.
The heat accumulating can be used for the storage heater of industrial furnace, ironmaking hot-blast stove waste heat recovery, also have solar energy heat-storage system.
This composite material can be used for the refractory brick or plate that replace traditional storage heater and hot-blast stove, make its amount of stored heat than existing storage heater and
Hot-blast stove refractory brick is 3 times big, and while heat reservoir performance is improved, cost greatly reduces.Economic analysis shows application
The high temperature energy-storage system of this material will make its volume reduce 45% than legacy system, and cost reduces by 20%.
Specific embodiment
The present invention provides a kind of inorganic salts-ceramic base thermal energy storage material, in terms of parts by weight, the heat accumulating by with
Lower component is prepared：K2CO324~32 parts, CaCO320~28 parts, 6~10 parts of BeO, Si3N410~16 parts and SiC 13
~18 parts.
Preferably, above-mentioned inorganic salts-ceramic base thermal energy storage material, in terms of parts by weight, the heat accumulating is by with the following group
Divide and be prepared：K2CO325~30 parts, CaCO322~25 parts, 6~8 parts of BeO, Si3N412~15 parts and SiC 15~18
Part.
It is furthermore preferred that above-mentioned inorganic salts-ceramic base thermal energy storage material, in terms of parts by weight, the heat accumulating is by following
Component is prepared：K2CO330 parts, CaCO325 parts, 6 parts of BeO, Si3N414 parts and 16 parts of SiC.
Further, the present invention also provides the preparation method of above-mentioned inorganic salts-ceramic base thermal energy storage material, this method
Specifically include following steps：
(1) by K2CO324~32 parts, CaCO320~28 parts and BeO 6~10 parts are uniformly mixed, and obtain mixture 1, press
According to quality than mixture 1:Absolute ethyl alcohol:BeO porcelain ball=1:0.11~0.14:0.05~0.10, it is added in into mixture 1 anhydrous
Ethyl alcohol and BeO porcelain balls, 2~3h of mixing and ball milling cross 200 mesh sieves, obtain slurry 1；
(2) by Si3N410~16 parts and SiC 13~18 parts are uniformly mixed, and obtain mixture 2, compare mixture according to quality
2:Absolute ethyl alcohol:Al2O3Porcelain ball=1:0.11~0.14:0.05~0.10, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain
Ball, 1~2h of mixing and ball milling cross 200 mesh sieves, obtain slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues 1~2h of ball milling, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering after drying, the heating system that when sintering uses
Degree is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With the heating rate of 5 DEG C/s, 200~700
DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 700~sintering temperature, 1020~1150 DEG C of sintering temperature, during sintering
Between 4~5h, after the completion of sintering, keep the temperature 20~30min, natural cooling obtains inorganic salts-ceramic base thermal energy storage material.
Heat accumulating of the present invention can be made into the element of variously-shaped (such as spherical, brick shape), and structure is accumulated in the form of packed bed
Into heat reservoir, in operation, while the latent heat of inorganic salts and the sensible heat storage thermal energy of composite material are utilized.This latent heat/aobvious
Hot hybrid system had not only remain the characteristics of hidden heat energy storage density is big and energy output is stablized, but also can be with changing with sensible heat energy-accumulating medium
The advantages of hot fluid direct contact heat transfer, also overcoming latent heat storage system needs to expend a large amount of canisters, tubing and presence
The shortcomings that fused salt corrosion.
It can be used for the storage heater of industrial furnace, ironmaking hot-blast stove waste heat recovery, also have solar energy heat-storage system.It is this compound
Material can be used for the refractory brick or plate that replace traditional storage heater and hot-blast stove, make its amount of stored heat more resistance to than existing storage heater and hot-blast stove
Firebrick is 3 times big, and while heat reservoir performance is improved, cost greatly reduces.Economic analysis shows using this material
High temperature energy-storage system, than legacy system will make its volume reduce 45%, cost reduce by 20%.
The present invention is made further explanation and description below in conjunction with specific embodiment, but is not intended to limit the present invention
Protection domain.
Embodiment 1
The preparation method of inorganic salts-ceramic base thermal energy storage material, this method specifically include following steps：
(1) by K2CO3 24g、CaCO320g and BeO10g are uniformly mixed, and obtain mixture 1, compare mixture according to quality
1:Absolute ethyl alcohol:BeO porcelain ball=1:0.11:0.05, addition absolute ethyl alcohol and BeO porcelain balls into mixture 1, mixing and ball milling 2h,
200 mesh sieves are crossed, obtain slurry 1；
(2) by Si3N410g and SiC 18g are uniformly mixed, and obtain mixture 2, according to quality than mixture 2:Anhydrous second
Alcohol:Al2O3Porcelain ball=1:0.11:0.05, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain ball, mixing and ball milling 1.5h, mistake
200 mesh sieves obtain slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues ball milling 2h, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering after drying, the heating system that when sintering uses
Degree is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With the heating rate of 5 DEG C/s, 200~700
DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 1150 DEG C, sintering time 4.5h of 700~sintering temperature, sintering is completed
Afterwards, 30min is kept the temperature, natural cooling obtains inorganic salts-ceramic base thermal energy storage material.
Embodiment 2
The preparation method of inorganic salts-ceramic base thermal energy storage material, this method specifically include following steps：
(1) by K2CO3 30g、CaCO325g and BeO 6g are uniformly mixed, and obtain mixture 1, compare mixture according to quality
1:Absolute ethyl alcohol:BeO porcelain ball=1:0.13:0.09, addition absolute ethyl alcohol and BeO porcelain balls into mixture 1, mixing and ball milling 3h,
200 mesh sieves are crossed, obtain slurry 1；
(2) by Si3N414g and SiC 16g are uniformly mixed, and obtain mixture 2, according to quality than mixture 2:Anhydrous second
Alcohol:Al2O3Porcelain ball=1:0.13:0.09, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain ball, mixing and ball milling 2h cross 200
Mesh sieve obtains slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues ball milling 2h, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering after drying, the heating system that when sintering uses
Degree is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With the heating rate of 5 DEG C/s, 200~700
DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 1100 DEG C, sintering time 5h of 700~sintering temperature, sintering is completed
Afterwards, 30min is kept the temperature, natural cooling obtains inorganic salts-ceramic base thermal energy storage material.
Embodiment 3
The preparation method of inorganic salts-ceramic base thermal energy storage material, this method specifically include following steps：
(1) by K2CO3 32g、CaCO328g and BeO 6g are uniformly mixed, and obtain mixture 1, compare mixture according to quality
1:Absolute ethyl alcohol:BeO porcelain ball=1:0.14:0.10, addition absolute ethyl alcohol and BeO porcelain balls into mixture 1, mixing and ball milling 3h,
200 mesh sieves are crossed, obtain slurry 1；
(2) by Si3N416g and SiC 13g are uniformly mixed, and obtain mixture 2, according to quality than mixture 2:Anhydrous second
Alcohol:Al2O3Porcelain ball=1:0.14:0.10, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain ball, mixing and ball milling 2h cross 200
Mesh sieve obtains slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues ball milling 2h, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering after drying, the heating system that when sintering uses
Degree is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With the heating rate of 5 DEG C/s, 200~700
DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 1080 DEG C, sintering time 4h of 700~sintering temperature, sintering is completed
Afterwards, 30min is kept the temperature, natural cooling obtains inorganic salts-ceramic base thermal energy storage material.
The material internal that the present invention is sintered out has ultra micro porous structure (micropore size is between 8~20um), material
Hot property and mechanical performance are satisfied by commercial Application demand：1200~1260 DEG C of melting temperature, total 170~190J/ of heat storage capacity
G, the maximum temperature used reach 1300~1400 DEG C.This composite material can be used for replacing traditional storage heater and hot-blast stove
Refractory brick or plate make its amount of stored heat 3 times bigger than existing storage heater and hot-blast stove refractory brick, are improving the same of heat reservoir performance
When, cost greatly reduces.Economic analysis shows the high temperature energy-storage system using this material, will make it than legacy system
Volume reduces 45%, and cost reduces by 20%.
Claims (5)
1. inorganic salts-ceramic base thermal energy storage material, which is characterized in that in terms of parts by weight, the heat accumulating is by following components
It is prepared：K2CO324~32 parts, CaCO320~28 parts, 6~10 parts of BeO, Si3N410~16 parts and SiC 13~18
Part.
2. inorganic salts according to claim 1-ceramic base thermal energy storage material, which is characterized in that, should in terms of parts by weight
Heat accumulating is prepared by following components：K2CO325~30 parts, CaCO322~25 parts, 6~8 parts of BeO, Si3N412~
15 parts and 15~18 parts of SiC.
3. inorganic salts according to claim 1 or 2-ceramic base thermal energy storage material, which is characterized in that with parts by weight
Meter, the heat accumulating are prepared by following components：K2CO330 parts, CaCO325 parts, 6 parts of BeO, Si3N414 parts and SiC
16 parts.
4. the preparation method of any one of claims 1 to 3 inorganic salts-ceramic base thermal energy storage material, which is characterized in that should
Method specifically includes following steps：
(1) by K2CO324~32 parts, CaCO320~28 parts and BeO 6~10 parts are uniformly mixed, and mixture 1 are obtained, according to matter
Amount is than mixture 1:Absolute ethyl alcohol:BeO porcelain ball=1:0.11~0.14:0.05~0.10, add in absolute ethyl alcohol into mixture 1
With BeO porcelain balls, 2~3h of mixing and ball milling crosses 200 mesh sieves, obtains slurry 1；
(2) by Si3N410~16 parts and SiC 13~18 parts are uniformly mixed, and mixture 2 are obtained, according to quality than mixture 2:Nothing
Water-ethanol:Al2O3Porcelain ball=1:0.11~0.14:0.05~0.10, absolute ethyl alcohol and Al are added in into mixture 22O3Porcelain ball,
1~2h of mixing and ball milling crosses 200 mesh sieves, obtains slurry 2；
(3) above-mentioned slurry 1 and slurry 2 are mixed, continues 1~2h of ball milling, crossed 300 mesh sieves, obtain slurry 3；
(4) slurry 3 is added in sintering mold, and extrusion forming carries out high temperature sintering after drying, 1020~1150 DEG C of sintering temperature,
4~5h of sintering time after the completion of sintering, keeps the temperature 20~30min, and natural cooling obtains the compound heat accumulation material of inorganic salts-ceramic base
Material.
5. the preparation method of inorganic salts-ceramic base thermal energy storage material according to claim 4, which is characterized in that step (4)
The temperature increasing schedule used during sintering is：With the heating rate of 5 DEG C/s, room temperature~200 DEG C, 200 DEG C of heat preservation 30min；With 5 DEG C/s's
Heating rate, 200~700 DEG C, 700 DEG C of heat preservation 40min；With the heating rate of 3 DEG C/s, 700~sintering temperature, sintering time 4
~5h.
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| CN108675822A (en) * | 2018-07-09 | 2018-10-19 | 合肥连森裕腾新材料科技开发有限公司 | A kind of heat accumulation ceramic based material and preparation method thereof |
| CN108840699A (en) * | 2018-07-24 | 2018-11-20 | 合肥岑遥新材料科技有限公司 | A kind of heat accumulation type bullet train ceramic matric composite brake block and preparation method thereof |
| CN113174239A (en) * | 2021-04-25 | 2021-07-27 | 中国大唐集团科学技术研究院有限公司西北电力试验研究院 | Preparation method of inorganic salt-ceramic high-temperature phase change composite heat storage material |
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| CN113174239A (en) * | 2021-04-25 | 2021-07-27 | 中国大唐集团科学技术研究院有限公司西北电力试验研究院 | Preparation method of inorganic salt-ceramic high-temperature phase change composite heat storage material |
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