CN106701034A - Solid composite phase-change thermal storage material and preparation method thereof - Google Patents
Solid composite phase-change thermal storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a solid composite phase-change thermal storage material, belonging to the technical field of energy storage materials. The solid composite phase-change thermal storage material comprises water, sodium carbonate, potassium carbonate, magnesium oxide, kieselguhr, quartz sand and kaolin. The thermal storage material is non-toxic, harmless and free of pollution. The invention further discloses a preparation method of the solid composite phase-change thermal storage material. The preparation method comprises the following steps: stirring, rubbing sand, filtering, performing hydraulic molding, and performing sintering molding. By adopting the preparation method, the thermal storage density is improved, the thermal storage density of the material is 2 times better than that of a common material, the thermal storage material can endure high temperature, can be heated to be greater than 650 DEG C, and is not liable to efflorescence when being used for a long time.
Description
Technical field
The invention belongs to energy storage material technical field, and in particular to a kind of solid composite phase-change heat-storage material and its preparation side
Method.
Background technology
It is more next using new energy, the utilization rate for improving the energy with becoming increasingly conspicuous for energy shortage and problem of environmental pollution
More it is valued by people.Energy storage technologies, as the important method for solving energy supply-demand unbalance, enjoy state
Inside and outside enterprise and the favor of related research institutes.And wherein, the thermal energy storage based on phase-changing energy storage material is application at present
One of energy storage technologies widest in area.
Phase-change accumulation energy is also called latent heat formula energy storage, is using the material of latent heat of phase change mode energy storage in the case of temperature-resistant
Material, carry out storing up due to absorbing/releasing energy when its principle is phase occurs using phase-change material change or structure changes/
Heat release, feature is：Storage density is big, storing discharging thermal process be carried out under conditions of constant temperature, the hot speed of storing discharging has controllability
Deng.In above-mentioned storing discharging thermal process, phase-change material is the medium for realizing phase-change thermal storage, and it absorbs when temperature is higher than transformation temperature
Heat is so as to undergo phase transition i.e. thawing heat accumulation process；When temperature drop, less than transformation temperature when, it is solidification heat release that reverse phase transformation occurs
Process.Using the effect of this accumulation of heat, the heat release of phase-change material, the temperature of surrounding environment can be adjusted, therefore, phase-change accumulation energy material
Material has wide prospect in fields such as building heating, air-conditionings.For building heating, phase-changing energy storage material on the one hand can be with
Alleviate energy supply and demand both sides unmatched contradiction on time, intensity and place, play a part of peak load shifting, reduce air-conditioning or
The operation and maintenance cost of heating system；On the other hand it can reduce the temperature fluctuation in building, improve indoor comfort degree.This
Outward, phase-changing energy storage material is applied in floor heating, unnecessary energy storage can also be got off, until energy supplies the intermittent phase again
Use.
General, material of the phase transition temperature in the range of -50~90 DEG C is divided into normal low temperature phase change heat accumulating, such material
Expect that the application in building and daily life is relatively broad.Material of the phase transition temperature less than 15 DEG C is mainly used in air conditioner refrigerating,
And material of the phase transition temperature between 15~90 DEG C is then widely used in solar energy heat-storage and heat load field.
Inorganic hydrated salt class phase transformation material：Inorganic crystal hydrated salt formula is ABnH2O, due to low cost, prepares letter
It is single, thus have good application prospect.Crystallization water abjection when heat accumulation process is mainly intensification, inorganic salts melt and absorb heat；Cooling
Shi Fasheng inverse process, absorbs the crystallization water and heat release.But easily there is supercooling and phenomenon of phase separation in hydration salt material, causes material to be analysed
Go out, reduce cycle life, seriously restrict practical application.Produce supercooling existing because of the crystallization nucleation poor-performing of crystalline hydrate salt
As.
Organic phase change thermal storage material：Conventional organic heat accumulating mainly includes higher aliphatic hydrocarbon, aromatic hydrocarbon, alcohol and carboxylic acid
Deng, wherein olefin material is most widely used, its formula be CH3(CH2)nCH3, the advantage of organic heat accumulating is good shaped solid, no
Easy generation is separated and is subcooled, corrosivity is smaller, but thermal conductivity factor is smaller compared with inorganic heat accumulating, is easily sent out during use
Raw leakage.
Resin acid class phase transformation material：It is more typical organic heat storage phase-changing material, its formula is CH3(CH2)2nCOOH, fat
The cost of acids phase-change material is 2-2.5 times of paraffin, and unstable properties, volatile and decompose.Generally using graft process or
Sol-gel process and inorganic matter (bentonite/SiO2Deng) compound, to improve thermal storage performance.
Solid-solid phase transition material：The normal low-temperature phase-change energy-storing material of solid-solid mainly includes polyalcohols, inorganic salts and high score
Sub 3 classes.Its advantage is that stable performance, phase transformation Volume Changes are smaller, long service life, but latent heat is low, phase transition temperature is higher, cost
It is higher.(1) polyalcohol generally has various phase transition temperatures, and 2 kinds of polyalcohols are mixed by different proportion can be obtained with phase wider
The thermal energy storage material of temperature scope, but easily occur surfusion in use, it is heated to more than phase transition temperature in addition
When easily form volatile plastic crystal.(2) inorganic salts solid-solid phase transition material is mainly including laminated perovskite class, rhodan ammonium etc..
Laminated perovskite class phase transformation material belongs to organo-metallic compound, and chemical general formula is (nCxH2x+1NH3)MY4.Such heat accumulating
Cycle performance is good, but due to frangible difficult directly utilization, is generally prepared by mixing into composite high-molecular material with macromolecular material.Sulphur
Ammonium cyanide (NH4SCN) as solid-solid phase transition material, there are various phase transformations when being heated to 150 DEG C from room temperature, phase in version enthalpy is higher,
Degree of supercooling is smaller, stable chemical performance.(3) high score subclass solid-solid phase transition material mainly includes cross-linking modified polyethylene, poly- second two
Alcohol etc., long service life, stable performance, without being subcooled and chromatography phenomenon, mechanical property is good, therefore possess good application prospect.
In recent years, many researchers to the physical property of potentially large number of phase-change heat-storage material and its measurement largely grind
Study carefully, at the same encapsulation also to phase-change material and it is encapsulated carried out significant exploration, drawn many valuable results.But
The magnesia brick or magnesium iron synthetic refractory brick that existing solid heat storage material is produced by magnesium ore deposit or iron ore are substituted, and its quality heat accumulation is close
The low, heatproof of degree is low, the easy efflorescence of long-term use, and production process is seriously polluted, and scope is used which greatly limits it.Cause
This, research solid composite phase-change material can overcome that conventional solid heat-storing material (refractory brick) Unit Weight heat accumulation is low, long-term use
Easy pulverizing problem, is made that to meet the composite phase-change material heat accumulating of waste heat heat accumulation requirements at different levels will be promising development side
To being also challenging research topic.
The content of the invention
In order to overcome the shortcomings of described in background technology, the present invention provides a kind of solid composite phase-change heat-storage material and its preparation
Method, the advantage that the method can reach is：(1) storage density of unit mass is improved, i.e., total storage density is by sensible heat and latent heat
Composition, (2) improve temperature in use, and long-term use is not pulverized easily.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of phase-change heat-storage material, in parts by weight, its component includes：Water 5-7 parts, sodium carbonate 40-50 parts, carbonic acid
Potassium 5-10 parts, magnesia 35-45 parts, diatomite 5-10 parts, quartz sand 1-5 parts, kaolin 0.5-2 parts；Wherein, the work of each component
With being respectively：Water is fusion agent；Sodium carbonate and potassium carbonate are phase-change thermal storage material of main part；Magnesia is heat accumulating skeleton；Silicon
Diatomaceous earth is adhesive；Quartz sand is reinforcing agent, for increasing intensity；Kaolin is adhesive.
Wherein, the purity of sodium carbonate, potassium carbonate, magnesia and diatomite technical grade is more than 99%, quartz sand and kaolin
Technical grade purity be more than 80%.Optimal shaping strength, volume and optimal storage density are obtained in setting heat accumulation temperature, separately
The content that the requirement of outer quartz sand, kaolinic purity more than 80% is based primarily upon silicon is high, can increase the ratio of briquetting of gitter brick
With heat accumulation.
Preferably, in parts by weight, its component includes：Water 5-7 parts, 43.15 parts of sodium carbonate, 8.65 parts of potassium carbonate,
1 part of 37.25 parts of magnesia, 7.3 parts of diatomite, 2.65 parts of quartz sand and kaolin, wherein, sodium carbonate, potassium carbonate, magnesia,
Diatomite, quartz sand and kaolinic granularity are -200 mesh.
A kind of solid composite phase-change heat-storage material and preparation method thereof, described method comprises the following steps：
1) stir：Weighing the sodium carbonate of respective quality, potassium carbonate respectively and being put into mixer carries out first time stirring, Ran Houjia
Entering magnesia, diatomite, quartz sand, kaolin carries out second stirring, then the water that adds in the way of spraying, then carries out the
Triple mixing；
2) rub sand with the hands and filter：By step 1) material that obtains is directly placed into oscillating granulator, by all materials whole
Rub sand with the hands in oscillating granulator and filter；
3) shaped by fluid pressure：By step 2) material that obtains carries out shaped by fluid pressure in being fitted into mould；
4) form by a firing：By step 3) shaped by fluid pressure material is sintered, you can prepare.
Preferably, in step (1), the rotating speed of mixer is 20-40r/min when stirring for the first time, and mixing time is 30-
40min, the rotating speed of mixer is 20-40r/min during second stirring, and mixing time is 50-70min；Third time is stirred when stirring
The rotating speed of machine is mixed for 20-40r/min, mixing time is 30-40min.Surveyed according to multiple actual whipping process observation and time
Calculate, this time can just meet and stir.
Preferably, in step (2), the screen pack of oscillating granulator is 80 mesh, and all materials are all at swing
Rub sand filtering in grain machine with the hands once, all material is formed into uniform particle, particle uniformly avoids heat storage brick crack.
Preferably, in step (3), compacting volumetric ratio is 2.5-3.0, there is the weight and density of raw material in formula, into
Have the weight and volume of brick after type, compacting volumetric ratio can be calculated accordingly, the dwell time is 20-30s, allow brick material in mould
There are sufficient flowing time and molding time in tool.
Preferably, in step (4), the heat storage brick for being molded intact is put into high temperature kiln and is burnt till, firing condition
For：100 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, after 100 DEG C of constant temperature 1h, 750 is risen to the speed of 3 DEG C/min
DEG C and constant temperature 1h, be finally down to after room temperature with the speed of 3 DEG C/min and taken out.The process causes that heat accumulating is closely tied with skeleton
Close, curing molding.
It is an advantage of the invention that：
(1) heat accumulating that the present invention is produced is nontoxic, harmless, pollution-free；
(2) the heat accumulating storage density that the present invention is produced is high, higher than common material more than 2 times；
(3) heat accumulating that the present invention is produced can be with high temperature resistant, it is possible to achieve heat accumulating is heated to more than 650 degree；
(4) density is small in itself for the heat accumulating that the present invention is produced, and is half of common heat-storing material density or so；
(5) heat accumulating that the present invention is produced can realize phase-transition heat-storage, substantially increase heat storage capacity, save energy
Source.
Brief description of the drawings
Fig. 1 is sample detection result figure of the invention.
Specific embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated：
Prepare sample：
1) stir：Weigh respectively 43.15 parts of sodium carbonate, 8.65 parts of potassium carbonate be put into mixer carry out for the first time stir
Mix, be subsequently adding 37.25 parts of magnesia, 7.3 parts of diatomite, 2.65 parts of quartz sand, 1 part of kaolin and stirred for the second time
Mix, the water for then being added in the way of spraying, then carry out third time stirring；
2) rub sand with the hands and filter：By step 1) material that obtains is directly placed into oscillating granulator, by all materials whole
Rub sand with the hands in oscillating granulator and filter；
3) shaped by fluid pressure：By step 2) material that obtains carries out shaped by fluid pressure in being fitted into mould；
4) form by a firing：By step 3) shaped by fluid pressure material is sintered, you can prepare sample.
In step (1), the rotating speed of mixer is 30r/min when stirring for the first time, and mixing time is 35min, second
The rotating speed of mixer is 30r/min during stirring, and mixing time is 60min；The rotating speed of mixer is 30r/ when third time is stirred
Min, mixing time is 30min.According to the multiple observation of actual whipping process and time measuring and calculating, this time can just meet stirs
Mix uniform.
In step (2), the screen pack of oscillating granulator is 80 mesh, and all materials are all rubbed with the hands in oscillating granulator
Sand is filtered once, and all material is formed into uniform particle, and particle uniformly avoids heat storage brick crack.
In step (3), compacting volumetric ratio is 2.7, there is the weight and density of raw material in formula, there is the weight of brick after shaping
Amount and volume, can calculate compacting volumetric ratio 5 or so accordingly, and the dwell time is 28s, allows the material of brick to have in a mold fully
Flowing time and molding time.
In step (4), the heat storage brick for being molded intact is put into high temperature kiln and is burnt till, firing condition is：With 3
DEG C/heating rate of min rises to 100 DEG C from room temperature, after 100 DEG C of constant temperature 1h, 750 DEG C and permanent is risen to the speed of 3 DEG C/min
Warm 1h, takes out after being finally down to room temperature with the speed of 3 DEG C/min.The process causes that heat accumulating is combined closely with skeleton, solidification
Shaping.
Sample detection：
Detected using NETZSCH DSC 204F1Phoenix 240-12-0112-L instruments, the sample matter of use
Amount：70.48mg, instrument sets fixed temperature range：0-690 DEG C, the heating rate 10.0k/min of instrument, the crucible of test：
Pt, the atmosphere and flow velocity of test：N2/30.0ml.Test result is shown in Fig. 1, as shown in Figure 1, with the rising of temperature, phase-change material
Specific heat also gradually rise, the heat accumulation energy of phase-change material also gradually rises, and the material can realize heat accumulation demand completely.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and simultaneously
The non-restriction to implementation method.For those of ordinary skill in the field, can also do on the basis of the above description
Go out the change or variation of other multi-forms.There is no need and unable to be exhaustive to all of implementation method.And thus drawn
Obvious change that Shen goes out or among changing still in protection scope of the present invention.
Claims (7)
1. a kind of phase-change heat-storage material, it is characterised in that in parts by weight, its component includes：Water 5-7 parts, sodium carbonate 40-
50 parts, potassium carbonate 5-10 parts, magnesia 35-45 parts, diatomite 5-10 parts, quartz sand 1-5 parts, kaolin 0.5-2 parts；
Wherein, the purity of sodium carbonate, potassium carbonate, magnesia and diatomite technical grade is more than 99%, quartz sand and kaolinic work
The purity of industry level is more than 80%.
2. a kind of phase-change heat-storage material as claimed in claim 1, it is characterised in that in parts by weight, its component includes：
Water 5-7 parts, 43.15 parts of sodium carbonate, 8.65 parts of potassium carbonate, 37.25 parts of magnesia, 7.3 parts of diatomite, 2.65 parts of quartz sand and height
1 part of ridge soil, wherein, sodium carbonate, potassium carbonate, magnesia, diatomite, quartz sand and kaolinic granularity are -200 mesh.
3. a kind of preparation method of solid composite phase-change heat-storage material, it is characterised in that described method comprises the following steps：
1) stir：Weighing the sodium carbonate of respective quality, potassium carbonate respectively and being put into mixer carries out first time stirring, is subsequently adding oxygen
Changing magnesium, diatomite, quartz sand, kaolin carries out second stirring, the water for then being added in the way of spraying, then carries out third time
Stirring；
2) rub sand with the hands and filter：By step 1) material that obtains is directly placed into oscillating granulator, all materials all shaken
Rub sand in pendulum-type granulator with the hands and filter；
3) shaped by fluid pressure：By step 2) material that obtains carries out shaped by fluid pressure in being fitted into mould；
4) form by a firing：By step 3) shaped by fluid pressure material is sintered, you can prepare.
4. a kind of preparation method of solid composite phase-change heat-storage material as claimed in claim 3, it is characterised in that in step
(1) in, the rotating speed of mixer is 20-40r/min when stirring for the first time, and mixing time is 30-40min, is stirred during second stirring
The rotating speed of machine is mixed for 20-40r/min, mixing time is 50-70min；The rotating speed of mixer is 20-40r/ when third time is stirred
Min, mixing time is 30-40min.
5. a kind of preparation method of solid composite phase-change heat-storage material as claimed in claim 4, it is characterised in that in step
(2) in, the screen pack of oscillating granulator is 80 mesh, and all materials all rub sand filtering with the hands once in oscillating granulator.
6. a kind of preparation method of solid composite phase-change heat-storage material as claimed in claim 5, it is characterised in that in step
(3) in, compacting volumetric ratio is 2.5-3.0, and the dwell time is 20-30s.
7. a kind of solid composite phase-change heat-storage material as claimed in claim 6 and preparation method thereof, it is characterised in that in step
(4) in, the heat storage brick for being molded intact is put into high temperature kiln and is burnt till, firing condition is：With the heating rate of 3 DEG C/min
Rise to 100 DEG C from room temperature, after 100 DEG C of constant temperature 1h, 750 DEG C and constant temperature 1h risen to the speed of 3 DEG C/min, finally with 3 DEG C/
The speed of min is taken out after being down to room temperature.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446556A (en) * | 2017-07-19 | 2017-12-08 | 山东中信能源联合装备股份有限公司 | Inorganic nano composite material regenerative block and preparation method thereof |
| CN107828384A (en) * | 2017-10-20 | 2018-03-23 | 华北电力大学 | A kind of core shell structure for the anti-fused salt volatilization of high-temperature phase-change heat storage material |
| CN109233753A (en) * | 2018-12-03 | 2019-01-18 | 安徽恒明工程技术有限公司 | A kind of phase change heat storage material and preparation method thereof |
| CN109908932A (en) * | 2019-02-25 | 2019-06-21 | 苏斌 | A kind of catalysis phase transformation medium ball and preparation method thereof of methanol burning |
| US10626238B2 (en) | 2018-07-27 | 2020-04-21 | King Fahd University Of Petroleum And Minerals | Calcium-doped magnesium carbonate-polymer-based synergistic phase change composite |
| CN111454693A (en) * | 2020-01-10 | 2020-07-28 | 北京科技大学 | Method for improving strength of fused salt phase change heat storage material by using phenolic resin |
| CN112503798A (en) * | 2020-11-30 | 2021-03-16 | 中国科学院金属研究所 | Use of materials with anomalous piezothermal effects in solid state refrigeration and/or heat storage |
| CN112736343A (en) * | 2020-12-29 | 2021-04-30 | 深圳市依卓尔能源有限公司 | Power supply radiating through heat-conducting phase-change composite material and preparation method thereof |
| CN113197337A (en) * | 2021-04-28 | 2021-08-03 | 河南中烟工业有限责任公司 | Heating cigarette cooling section containing layered perovskite and preparation method thereof |
| CN113429940A (en) * | 2021-07-12 | 2021-09-24 | 华中科技大学 | Nano silicon carbide reinforced heat storage composite phase change heat storage material and preparation method thereof |
| CN113587198A (en) * | 2021-07-27 | 2021-11-02 | 常州二维暖烯科技有限公司 | Manufacturing process of heat storage heater |
| CN114644906A (en) * | 2020-12-17 | 2022-06-21 | 国家电投集团科学技术研究院有限公司 | Composite phase-change heat storage material and preparation method thereof |
| WO2022254450A1 (en) * | 2021-06-01 | 2022-12-08 | Vazirani Automotive Pvt. Ltd. | Powder mixture for heat dissipation and components having the powder mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107446556A (en) * | 2017-07-19 | 2017-12-08 | 山东中信能源联合装备股份有限公司 | Inorganic nano composite material regenerative block and preparation method thereof |
| CN107828384A (en) * | 2017-10-20 | 2018-03-23 | 华北电力大学 | A kind of core shell structure for the anti-fused salt volatilization of high-temperature phase-change heat storage material |
| US10626238B2 (en) | 2018-07-27 | 2020-04-21 | King Fahd University Of Petroleum And Minerals | Calcium-doped magnesium carbonate-polymer-based synergistic phase change composite |
| US11306189B2 (en) | 2018-07-27 | 2022-04-19 | King Fahd University Of Petroleum And Minerals | Polyethylene glycol phase change composite |
| US11434339B2 (en) | 2018-07-27 | 2022-09-06 | King Fahd University Of Petroleum And Minerals | Method for making a PEG phase change composite |
| CN109233753A (en) * | 2018-12-03 | 2019-01-18 | 安徽恒明工程技术有限公司 | A kind of phase change heat storage material and preparation method thereof |
| CN109908932A (en) * | 2019-02-25 | 2019-06-21 | 苏斌 | A kind of catalysis phase transformation medium ball and preparation method thereof of methanol burning |
| CN109908932B (en) * | 2019-02-25 | 2020-05-05 | 苏斌 | Catalytic phase change medium ball for methanol combustion and preparation method thereof |
| CN111454693A (en) * | 2020-01-10 | 2020-07-28 | 北京科技大学 | Method for improving strength of fused salt phase change heat storage material by using phenolic resin |
| CN111454693B (en) * | 2020-01-10 | 2021-06-08 | 北京科技大学 | Method for improving strength of fused salt phase change heat storage material by using phenolic resin |
| CN112503798A (en) * | 2020-11-30 | 2021-03-16 | 中国科学院金属研究所 | Use of materials with anomalous piezothermal effects in solid state refrigeration and/or heat storage |
| CN114644906B (en) * | 2020-12-17 | 2023-06-23 | 国家电投集团科学技术研究院有限公司 | Composite phase-change heat storage material and preparation method thereof |
| CN114644906A (en) * | 2020-12-17 | 2022-06-21 | 国家电投集团科学技术研究院有限公司 | Composite phase-change heat storage material and preparation method thereof |
| CN112736343A (en) * | 2020-12-29 | 2021-04-30 | 深圳市依卓尔能源有限公司 | Power supply radiating through heat-conducting phase-change composite material and preparation method thereof |
| CN113197337A (en) * | 2021-04-28 | 2021-08-03 | 河南中烟工业有限责任公司 | Heating cigarette cooling section containing layered perovskite and preparation method thereof |
| WO2022254450A1 (en) * | 2021-06-01 | 2022-12-08 | Vazirani Automotive Pvt. Ltd. | Powder mixture for heat dissipation and components having the powder mixture |
| CN113429940B (en) * | 2021-07-12 | 2022-05-20 | 华中科技大学 | Nano silicon carbide reinforced heat storage composite phase-change heat storage material and preparation method thereof |
| CN113429940A (en) * | 2021-07-12 | 2021-09-24 | 华中科技大学 | Nano silicon carbide reinforced heat storage composite phase change heat storage material and preparation method thereof |
| CN113587198A (en) * | 2021-07-27 | 2021-11-02 | 常州二维暖烯科技有限公司 | Manufacturing process of heat storage heater |
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Application publication date: 20170524 |