CN106978148A - A kind of multiphase medium phase-change heat-storage material and preparation method thereof - Google Patents
A kind of multiphase medium phase-change heat-storage material and preparation method thereof Download PDFInfo
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- CN106978148A CN106978148A CN201710311059.6A CN201710311059A CN106978148A CN 106978148 A CN106978148 A CN 106978148A CN 201710311059 A CN201710311059 A CN 201710311059A CN 106978148 A CN106978148 A CN 106978148A
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- 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
Abstract
The present invention relates to a kind of multiphase medium phase-change heat-storage material and preparation method thereof, its preparation method is：(1) 50~90 parts of hydrated salt class phase transformation material is weighed, with 10~50 parts of the immiscible liquid phase medium of hydrated salt class phase transformation material, 0~0.2 part of grinding-aid dispersant, mixing is heated to fusing；(2) mixture of fusing is cooled to room temperature under disturbed conditions, that is, obtains multiphase medium phase-change heat-storage material.Compared with prior art, multiphase medium system of the invention can solve the problem that crystalline hydrate salt phase-change material caking causes the problem of thermal resistance becomes big, reduces and is subcooled and is separated and improve cyclical stability etc..
Description
Technical field
The present invention relates to technical field of phase change heat storage, more particularly, to a kind of multiphase medium phase-change heat-storage material and its
Preparation method.
Background technology
With the development of human society, the dioxide and monoxide given off in the consumption process of fossil energy is (such as
SO2、CO2, CO) etc. cause greenhouse effects, extreme weather to increase to the earth, environmental pollution the problems such as.Fossil energy belongs to non-renewable
The energy, its limited reserves can not meet people's increasing demand, and world energy supplies day are becoming tight.However, development
Energy storage system significantly more efficient can meet society to efficient and the environment-friendly type energy demand, and wherein thermal energy storage technology is current
With larger attraction.Because, heat reservoir can compensate for temporal mismatch between energy demand and supply, in work
There is broad prospect of application in the fields such as amateurish recuperation of heat, electric power peak load shifting and solar energy heating.
Phase-changing energy storage material has the advantages that high energy storage density, including organic phase change material and inorganic phase-changing material, in storage
Cause extensive concern in energy system development and use.Compared with organic phase change material, inorganic crystal water and salt phase-change material have
Thermal conductivity factor is larger, energy storage density is larger, latent heat of phase change is larger, lower-price characteristic, becomes middle low temperature energy storage phase transformation
An important class in material.But, compared with metal and alloy type phase-change material, the thermal conductivity factor of crystalline hydrate salt phase-change material
It is still smaller, thus heat transfer property is poor, have a strong impact on energy stores speed.To improve its heat transfer property, often through setting
Metal heat-exchange coil pipe of the meter with big heat exchange area is overcome, it is meant that add high material cost.In addition, hydrated salt
Phase-change material, which often has the shortcomings that to be subcooled and is separated, causes its long-term cycle performance decay.Factors above limits hydrated salt
Class phase transformation material large-scale engineering applications and industrialization process.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of multiphase medium phase transformation
Heat accumulating and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of multiphase medium phase-change heat-storage material, includes the component of following parts by weight：Hydrated salt class phase transformation material 50~
90 parts, with 10~50 parts of the immiscible liquid phase medium of hydrated salt class phase transformation material, 0~0.2 part of grinding-aid dispersant.
As preferred embodiment, described hydrated salt class phase transformation material is selected from sal glauberi, calcium chloride hexahydrate, eight
One or more combination in hydronium(ion) barium monoxide or Sodium acetate trihydrate etc..
As above-mentioned preferred embodiment it is further preferred that described hydrated salt class phase transformation material be selected from sal glauberi,
The mixing of two or more in calcium chloride hexahydrate, barium hydroxide octahydrate or Sodium acetate trihydrate, and wherein content is minimum
A kind of quality accounting of phase-change material is usually no more than 1%.
As the further preferred of above-mentioned more preferred, described hydrated salt class phase transformation material is eight hydrated hydroxides
Change barium and Sodium acetate trihydrate in mass ratio 100：1.01 mix.
As preferred embodiment, described liquid phase medium in white oil, conduction oil or dimethicone etc. one
Plant or several combinations.
As preferred embodiment, described grinding-aid dispersant is selected from the copolymer solution containing acidic-group, polycarboxylic acids
It is one or more of compound in ester solution, polyalcohol modified body polymer, α olefin sulfonate polymer etc..Above-mentioned is all kinds of
In grinding-aid dispersant, the copolymer solution containing acidic-group can be selected from the DP-400/DP- of Shanghai great Pan Chemical Co., Ltd.s
400B, polycarboxylate solution can be selected from the DP-464 of Shanghai great Pan Chemical Co., Ltd.s, and polyalcohol modified body polymer can be with
YM-217 selected from Shanghai Yu Mu Chemical Co., Ltd.s, α olefin sulfonate (AOS) polymer can be selected from the wooden chemical industry of Shanghai rain
Co., Ltd YM-103S.
A kind of preparation method of multiphase medium phase-change heat-storage material, comprises the following steps：
(1) formula weighs hydrated salt class phase transformation material, liquid phase medium and grinding-aid dispersant by weight, mixes, heating
To fusing；
(2) mixture of fusing is cooled to room temperature under disturbed conditions, that is, obtains multiphase medium phase-change heat-storage material.
As preferred embodiment, it is defeated that the disturbance in step (2) includes mechanical agitation, electromagnetic distu, ultrasonic wave or pump
Transport the one or more combination of liquid phase medium circulation scouring.
Hydrous salt phase change material of the present invention is latent heat formula energy-accumulating medium, and liquid phase medium is heat exchange medium, and grinding-aid dispersant exists
It can adhere to solid particles surface to reduce the frictional force between solid crystal particle during the liquid-solid phase transformation of phase-change material, contribute to more
Uniformly disperse phase transformation material granule.In exothermic process, because liquid phase medium is oiliness, phase-change material is aqueous, and it was crystallized
Journey can form water-in-oil type state.Two kinds of perturbation schemes of liquid phase medium circulation scouring are transported with mechanical agitation and pump below and illustrate it
Influence to phase change material releases heat process crystallization.For mechanical agitation mode, as liquid state phase change material heat discharges, gradually open
Begin to crystallize, liquid state phase change material can be with a large amount of metastable state liquid in the presence of liquid phase medium and dispersant, and under external force
Pearl is dispersed in liquid phase medium and simultaneously by heat and is conducted to liquid phase medium, treats that its heat release is finished, temperature be down to phase transition temperature with
Under, crystallization is completed, so as to form a large amount of fine crystals particles.Liquid phase medium circulation scouring mode is transported for pump, with liquid
Phase change material releases heat, liquid phase medium enters in the presence of pump from phase-change material bottom, because two-phase density contrast is larger, and liquid phase is situated between
Heat convection occurs for matter floating upward quickly to phase-change material top, this process, while the floating disturbance of liquid phase medium makes phase-change material
Final crystallization forms cellular flow passages structure.
Simple inorganic salts phase-change material is smaller due to thermal conductivity factor, generally requires the heat exchanger of larger heat exchange area
Its heat stored can be made effectively to discharge.And the multiphase medium phase-change heat-storage material that is previously mentioned of the present invention be by liquid phase medium with
The direct heat convection of phase-change material, and phase-change material can form fine particle or cellular flow passages, thus help raising heat exchange effect
Rate.Heretofore described mechanical agitation, electromagnetic distu, ultrasonic wave or pump transport the perturbation schemes such as liquid phase medium circulation scouring in itself
With regard to that can improve its supercooling and be separated, cyclical stability is improved.In addition, liquid phase medium and grinding-aid dispersant can be in disturbed conditions
Under make phase-change material scattered wherein, and exothermic crystallization ultimately forms fine particle or cellular flow passages structure.
Hydrous salt phase change material in the present invention：It is preferred that two or more phase-change material is composited, addition compared with
Few phase-change material can play nucleator effect, it is generally preferable within quality accounting 1%, so to main body phase-change material heat accumulation
It can influence small, contribute to main body phase change material releases heat to crystallize to form fine particle and liquid phase medium heat exchange.
Liquid phase medium：Compound with hydrous salt phase change material, liquid phase medium accounts for 10~50 parts, and the latter accounts for 50~90 parts.For example,
Under mechanical agitation mode, hydrous salt phase change material can be chosen for 70 with liquid phase medium mass ratio:30；Liquid phase is transported in pump to be situated between
Under matter circulation scouring mode, hydrous salt phase change material can choose 85 with liquid phase medium mass ratio:15.If liquid phase medium is very few, meeting
Liquid phase medium is caused to be filled up completely with phase-change material accumulation space, it is impossible to complete the output of pipeline circulated heat.
Grinding-aid dispersant：The excessive dispersant that adds will not increase phase-change material dispersion effect, and heterogeneous system is caused on the contrary
Mobility is not smooth, the crystallization of influence phase-change material and heat exchange.
Compared with prior art, the heterogeneous system that prepared by the present invention is in experience solid-liquid phase transition process, under disturbance
Fine crystals particle or the solid comprising cellular flow passages can be formed, on the one hand, by with the direct heat convection side of liquid phase medium
Formula enhances the heat transfer of charge and discharge thermal process, effectively solves crystalline hydrate salt phase-change material caking and causes the problem of thermal resistance becomes big, separately
On the one hand, heterogeneous system supercooling and phase separation are smaller, and cyclical stability is preferable.
Brief description of the drawings
Fig. 1 is the heat release figure of the phase-change heat-storage material of embodiments of the invention 1；
Fig. 2 is the heat release figure of the phase-change heat-storage material of embodiments of the invention 2；
The heat release datagram of Fig. 3 heat exchange coils of big heat exchange area for built in.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Each raw material in following examples is commercially available prod unless otherwise instructed.
Embodiment 1
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 330kg barium hydroxide octahydrates,
The copolymer solution of 3.33kg Sodium acetate trihydrates, 145kg white oils and 0.33kg containing acidic-group, which is added in suitable vessel, to be obtained
Mixture.(2) mixture, is heated to fusing.(3), by the mixture after fusing under mechanical stirring, it is cooled to room temperature, obtains
To the multiphase medium phase-change heat-storage material for including a large amount of phase-change material particles.
Accompanying drawing 1 is the heat release datagram of multiphase medium material described in embodiment 1.Multiphase medium containers are held from appearance
Product 365L drum, fills heat to 100 DEG C or so, material to be phased starts heat release after being completely melt.In exothermic process, agitator turns
Speed is 35rpm and carries double-deck three bladed paddle (φ 40) stirring multiphase medium material, and liquid phase medium completes recuperated cycle by oil pump,
Liquid phase medium flow 1500L/h, plate type heat exchanger circulating chilled water flow 900L/h.Heat-exchange end is completed in two steps, first phase transformation material
The heat exchange of material and liquid phase medium is extracted the liquid phase medium of high temperature out from container top by oil pump, is sent out by plate type heat exchanger and water
After raw heat convection, the liquid phase medium of low temperature enters from container bottom again, and completing convection current with phase-change material under stirring changes
Heat reaches container top and is changed into the condition of high temperature again.So by reciprocation cycle until heat is paged out.From accompanying drawing 1, with
The reduction of phase-change material temperature, it has an obvious heat release platform at 76 DEG C, and without surfusion.Liquid phase medium temperature -1 is represented
Liquid phase medium and the temperature after phase-change material heat exchange, with phase-change material temperature closely, illustrate that both heat exchange are good.From heat release
From the point of view of power, the heat release power of water side is maximum up to 28kW in the starting stage, and is positively retained at more than 10kW in phase transition process.Put
At the end of heat, liquid phase medium temperature is approached with phase-change material temperature, illustrates that the heat of phase-change material fully discharges.Phase-change material
Heat release is finished, and is changed into a large amount of fine particle crystal.Be computed, this time complete thermal discharge is about 152MJ, this with 70 DEG C of temperature difference
Theoretical quantity of heat storage 152.4MJ is closely.It is real compared with the heat release data of the heat exchange coil of big heat exchange area built in accompanying drawing 3
Apply in example 1, stirring condition can not only suppress phase-change material surfusion, and remain to make liquid phase under without built-in heat exchange coil
The lifting effect of medium temperature -1 is suitable with the lifting effect that power heat release exchange hot coil leaving water temperature is determined in accompanying drawing 3, explanation
The phase-change material thermal resistance of embodiment 1 is low, and heat exchange efficiency is high.
Embodiment 2
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 330kg barium hydroxide octahydrates,
The copolymer solution of 3.33kg Sodium acetate trihydrates, 145kg white oils and 0.33kg containing acidic-group, which is added in suitable vessel, to be obtained
Mixture.(2) mixture, is heated to fusing.(3) mixture after fusing, is transported into white oil in pump to circulate from bottom to top
Wash away, be cooled to room temperature, obtain including the multiphase medium phase-change heat-storage material of cellular flow passages.
Accompanying drawing 2 is certain heat release datagram of multiphase medium material described in embodiment 2.Hold the selection of multiphase medium containers
Volume 365L drum, fills heat to 100 DEG C or so, material to be phased starts heat release after being completely melt.In exothermic process, liquid phase is situated between
Matter pumps circulation scouring from bottom to top by oil pump and completes recuperated cycle, liquid phase medium flow 1500L/h, plate type heat exchanger cold water
Circular flow 900L/h.Heat-exchange end is completed in two steps, and the heat exchange of phase-change material and liquid phase medium first passes through oil pump by high temperature
Liquid phase medium is extracted out from container top, and after heat convection occurs for plate type heat exchanger and water, the liquid phase medium of low temperature is calm again
Device bottom enters, and complete heat convection arrival container top with phase-change material during rising on itself is changed into high temperature shape again
State.So by reciprocation cycle until heat is paged out.From accompanying drawing 3, with the reduction of phase-change material temperature, it is at 76 DEG C
There is an obvious heat release platform, and without obvious surfusion.Liquid phase medium temperature -1 is represented after liquid phase medium and phase-change material heat exchange
Temperature, with phase-change material temperature closely, illustrate that both heat exchange are good.Heat release is finished, phase-change material formation cellular flow passages
Structure, and its apparent density is less than liquid phase medium density.It is computed, 40 DEG C of this heat release is about with the effective thermal discharge of upper circulation water
132.1MJ, this is approached with the theoretical quantity of heat storage 142.3MJ under 60 DEG C of temperature difference.It is built-in with big heat exchange area with accompanying drawing 3
The heat release data of heat exchange coil are compared, the experimental test result of embodiment 2 explanation, are only relied on pumping liquid phase medium and are circulated from bottom to top
Washing away disturbance and remaining to realize makes the lifting effect of liquid phase medium temperature -1 be put with determining power in accompanying drawing 3 under without built-in heat exchange coil
The lifting effect of heat exchange hot coil leaving water temperature quite, illustrates that the phase-change material thermal resistance of embodiment 2 is low, heat exchange efficiency is high.
Embodiment 3
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 24kg sal glauberis, the water of 24kg six
Calcium chloride, 2kg Sodium acetate trihydrates, 50kg conduction oils and 0.01kg polycarboxylate solution are added in suitable vessel and mixed
Thing.(2) mixture, is heated to fusing.(3), by the mixture after fusing under mechanical stirring, it is cooled to room temperature, is wrapped
Multiphase medium phase-change heat-storage material containing a large amount of phase-change material particles.
Embodiment 4
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 70kg sal glauberis, 30kg heat conduction
Oil, 0.1kg polycarboxylates solution, the polyalcohol modified body polymer of 0.1kg are added in suitable vessel and obtain mixture.(2), will
The mixture is heated to fusing.(3) mixture after fusing, is cooled to room temperature under electromagnetic distu, multiphase medium phase transformation is obtained
Heat accumulating.
Embodiment 5
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1) it is, that 90kg sal glauberis, 10kg is white
Oil, 0.1kg α olefin sulfonates (AOS) polymer are added in suitable vessel and obtain mixture.(2), the mixture is heated
To fusing.(3) mixture after fusing, is cooled to room temperature under ultrasonication, multiphase medium phase-change heat-storage material is obtained.
Embodiment 6
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 59.5kg barium hydroxide octahydrates,
0.5kg Sodium acetate trihydrates, 20kg conduction oils, 20kg white oils, 0.1kg polycarboxylates solution, 0.08kg polycarboxylates solution are added
Mixture is obtained into suitable vessel.(2) mixture, is heated to fusing.(3), the mixture after fusing is disturbed in electromagnetism
Under dynamic, it is cooled to room temperature, obtains multiphase medium phase-change heat-storage material.
Embodiment 7
A kind of multiphase medium phase-change heat-storage material, its preparation process includes：(1), by 59.5kg barium hydroxide octahydrates,
0.5kg Sodium acetate trihydrates, 15kg conduction oils, 15kg white oils, 15kg dimethicones, 0.1kg polycarboxylates solution, 0.08kg gather
Carboxylic acid ester solution, which is added in suitable vessel, obtains mixture.(2) mixture, is heated to fusing.(3), by after fusing
Mixture is cooled to room temperature under electromagnetic distu, obtains multiphase medium phase-change heat-storage material.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (7)
1. a kind of multiphase medium phase-change heat-storage material, it is characterised in that include the component of following parts by weight：Hydrated salt class phase transformation
50~90 parts of material, with 10~50 parts of the immiscible liquid phase medium of hydrated salt class phase transformation material, 0~0.2 part of grinding-aid dispersant.
2. a kind of multiphase medium phase-change heat-storage material according to claim 1, it is characterised in that described hydration salt phase
Become one or more combination of the material in sal glauberi, calcium chloride hexahydrate, barium hydroxide octahydrate or Sodium acetate trihydrate.
3. a kind of multiphase medium phase-change heat-storage material according to claim 2, it is characterised in that described hydration salt phase
Become material in sal glauberi, calcium chloride hexahydrate, barium hydroxide octahydrate or Sodium acetate trihydrate two or more
Mixing, and a kind of quality accounting of the wherein minimum phase-change material of content is no more than 1%.
4. a kind of multiphase medium phase-change heat-storage material according to claim 3, it is characterised in that described hydration salt phase
Become material into barium hydroxide octahydrate and Sodium acetate trihydrate in mass ratio 100：1.01 mix.
5. a kind of multiphase medium phase-change heat-storage material according to claim 1, it is characterised in that described liquid phase medium choosing
From one or more of combinations in white oil, conduction oil or dimethicone.
6. a kind of preparation method of multiphase medium phase-change heat-storage material as claimed in claim 1, it is characterised in that including following
Step：
(1) formula weighs hydrated salt class phase transformation material, liquid phase medium and grinding-aid dispersant by weight, mixes, is heated to melting
Change；
(2) mixture of fusing is cooled to room temperature under disturbed conditions, that is, obtains multiphase medium phase-change heat-storage material.
7. a kind of preparation method of multiphase medium phase-change heat-storage material according to claim 6, it is characterised in that step
(2) disturbance in includes one or more of groups that mechanical agitation, electromagnetic distu, ultrasonic wave or pump transport liquid phase medium circulation scouring
Close.
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| CN201710311059.6A CN106978148A (en) | 2017-05-05 | 2017-05-05 | A kind of multiphase medium phase-change heat-storage material and preparation method thereof |
| CN201710774988.0A CN107502299B (en) | 2017-05-05 | 2017-08-31 | Multi-phase medium phase-change heat storage material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502299A (en) * | 2017-05-05 | 2017-12-22 | 江苏启能新能源材料有限公司 | A kind of multiphase medium phase-change heat-storage material and preparation method thereof |
| CN108084972A (en) * | 2018-01-18 | 2018-05-29 | 上海交通大学 | Low temperature hydrated salt phase-change heat accumulation medium and its preparation and application |
| DE102017008115A1 (en) * | 2017-08-26 | 2019-02-28 | Hans-Jürgen Maaß | Storage of thermal energy with phase change material |
| CN110387216A (en) * | 2019-08-15 | 2019-10-29 | 广东工业大学 | It is a kind of that phase-change heat-storage material and the preparation method and application thereof being subcooled steadily in the long term |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439286A (en) * | 2018-10-09 | 2019-03-08 | 中山市陶净科技有限公司 | Can fast cooling composition |
| CN115418195A (en) * | 2022-08-18 | 2022-12-02 | 嘉兴赛曼泰克新材料有限公司 | Composite phase-change heat storage material for lithium battery pack heat management and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285664A (en) * | 2007-04-09 | 2008-10-15 | 李建民 | Supercritical phase-change intensified heat diffusion method and its heat-transfer medium and applications |
| CN101880520B (en) * | 2010-06-09 | 2013-04-17 | 中国科学院深圳先进技术研究院 | Inorganic hydrated salt silica phase-change material and preparation method thereof |
| CN105505329B (en) * | 2015-12-29 | 2018-10-30 | 华南理工大学 | A method of reducing supercooling degree of hydrous salt phase change material by adding anti-solvent |
| CN106978148A (en) * | 2017-05-05 | 2017-07-25 | 江苏启能新能源材料有限公司 | A kind of multiphase medium phase-change heat-storage material and preparation method thereof |
-
2017
- 2017-05-05 CN CN201710311059.6A patent/CN106978148A/en not_active Withdrawn
- 2017-08-31 CN CN201710774988.0A patent/CN107502299B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502299A (en) * | 2017-05-05 | 2017-12-22 | 江苏启能新能源材料有限公司 | A kind of multiphase medium phase-change heat-storage material and preparation method thereof |
| DE102017008115A1 (en) * | 2017-08-26 | 2019-02-28 | Hans-Jürgen Maaß | Storage of thermal energy with phase change material |
| CN108084972A (en) * | 2018-01-18 | 2018-05-29 | 上海交通大学 | Low temperature hydrated salt phase-change heat accumulation medium and its preparation and application |
| CN110387216A (en) * | 2019-08-15 | 2019-10-29 | 广东工业大学 | It is a kind of that phase-change heat-storage material and the preparation method and application thereof being subcooled steadily in the long term |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107502299B (en) | 2020-10-30 |
| CN107502299A (en) | 2017-12-22 |
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