CN102268238A - Phase change energy storage material and production method for microcapsules - Google Patents
Phase change energy storage material and production method for microcapsules Download PDFInfo
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- CN102268238A CN102268238A CN2011101548626A CN201110154862A CN102268238A CN 102268238 A CN102268238 A CN 102268238A CN 2011101548626 A CN2011101548626 A CN 2011101548626A CN 201110154862 A CN201110154862 A CN 201110154862A CN 102268238 A CN102268238 A CN 102268238A
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Abstract
The invention discloses a phase change energy storage material and a production method for microcapsules, relates to the phase change energy storage material and a production method for phase change energy storage material microcapsules, and aims to provide the phase change energy storage material with paraffin and/or C11-C14 normal paraffin as a main energy storage material and the production method for the microcapsules. The invention mainly comprises the phase change energy storage material and a capsule wall material which are supplemented by a dispersant and an antifoaming agent. The phase change energy storage material belongs to an organic phase change energy storage material, so that the phenomena of overcooling and separation of similar inorganic materials are avoided, and the phase change energy storage material is a more ideal phase change energy storage material. The paraffin in the organic phase change energy storage material is more ideal when being used as the phase change energy storage material.
Description
Technical field
The present invention relates to the production method of phase-changing energy storage material and phase-changing energy storage material microcapsule.
Background technology
Phase-changing energy storage material can absorb heat (cold) amount or emit heat in environment in its thing phase change process from environment, thereby reaches energy storage and release and regulate energy requirement and the purpose of supply mismatch.It has both the advantage of common building materials and phase change material, can absorb and discharge an amount of heat energy; Can use simultaneously with other traditional building materials; Do not need special knowledge and skills to install and use the accumulation of heat material of construction; The enough standard production equipment production of energy; Considerable energy saving consumption reduction effect is arranged, on economic benefit, have competitiveness.Use more extensive with inanimate matter latent heat of phase change energy storage material at present, because inanimate matter latent heat of phase change energy storage material low price is in one's hands easily, but all existed the cold-peace phenomenon of phase separation, have a strong impact on result of use, yet will be when producing microcapsule with the inorganic-phase variable latent heat storage material, need complicated technological process, so production cost is than higher.
Summary of the invention
The purpose of this invention is to provide a kind of with paraffin and/or C
11～C
14Normal paraffin is the production method of the phase-changing energy storage material and the microcapsule of main energy storage material.
The present invention mainly comprises phase-changing energy storage material and cyst material, is aided with dispersion agent, defoamer again;
Wherein phase-changing energy storage material is paraffin and C
11～C
14At least a material in the normal paraffin or the mixing of two or more materials;
Cyst material is the trimeric cyanamide methylal resin with urea and polyvinyl alcohol modification;
The weight part ratio of phase-changing energy storage material and cyst material is: 75:25～65:35;
Dispersion agent is that gelatine solution, polyocarboxy acid type dispersion agent and anion surfactant cooperation form;
Anion surfactant is meant sodium lauryl sulphate and Sodium dodecylbenzene sulfonate;
Defoamer is an organosilicon emulsion defoaming agents, its usage quantity be after phase-changing energy storage material is made water miscible liquid total amount of liquid 0.003～0.005%.
Paraffin of the present invention and C
11～C
14At least a material of normal paraffin or the mixing material proportion of two or more materials are determined according to the difference of transformation temperature.
The preparation method of phase-changing energy storage material microcapsule of the present invention:
A, in the container that has agitator, condenser and thermometer, add entry and anion surfactant, the gelatine aqueous solution and polyocarboxy acid type dispersion agent, heating;
B, formaldehyde solution is transferred pH value with trolamine, heating, and add trimeric cyanamide, urea, polyvinyl alcohol water solution and water is heated to the mixed solution bleach while stirring, continues to be heated to 80 ℃, and keep 80 ℃ standby;
C, with the heating of paraffin and normal paraffin and fully mix;
D, start stirrer and add the mineral wax mixture in fused c step when a Buwen degree rises to 60 ℃, stable emulsion is made in high-speed stirring emulsification about 10 minutes;
E, add sodium bicarbonate aqueous solution and aqueous citric acid solution when the emulsion temperature rises to 70 ℃, and adjust pH value;
F, add silicone antifoam agent then, add 1/4b at last and go on foot ready modified cyanurotriamide methylal resin solution, spend 40 minutes after beginning slowly drip remaining polymkeric substance;
G, after all polymkeric substance dropwises, add aqueous ammonium chloride solution, continued in 70 ℃～75 ℃ stirring reaction 4 hours, stop heating, begin cooling;
H, after being cooled to below 40 ℃, adjust the pH value of reaction system with aqueous sodium hydroxide solution;
I, dehydration, washing, dehydration, drying draw Powdered phase-changing energy storage material microcapsule product again.
The present invention belongs to organic phase change energy storage material, does not have the mistake cold-peace phenomenon of phase separation of similar inorganic materials, is comparatively ideal phase-changing energy storage material.And paraffin is even more ideal as phase-changing energy storage material in the organic phase change energy storage material.The major ingredient of paraffin is a normal paraffin, is the mixture of various normal paraffins and a small amount of isoparaffin.Paraffin does not have the fixed fusing point, but a temperature of fusion scope.Different paraffin has fusing point and latent heat separately, and it is neutral that paraffin is, and stable chemical performance is not had an effect with acid (except the nitric acid) and basic solution under the usual conditions, and long-term exposure can not go bad in atmosphere in variable color yet.Since relatively stricter to the use temperature scope of phase-changing energy storage material at present, therefore must adjust the transformation temperature of paraffin.Adopt low-carbon (LC) normal paraffin and paraffin to mix when adjusting eutectic point, the potential heat value of its mixture is than higher, and can adjust any required transformation temperature in 10 ~ 60 ℃ of scopes.
Embodiment
The present invention mainly comprises phase-changing energy storage material and cyst material, is aided with dispersion agent, defoamer again;
Wherein phase-changing energy storage material is paraffin and C
11～C
14At least a material in the normal paraffin or the mixing of two or more materials;
Cyst material is the trimeric cyanamide methylal resin with urea and polyvinyl alcohol modification;
The weight part ratio of phase-changing energy storage material and cyst material is: 75:25～65:35;
Dispersion agent is that gelatine solution, polyocarboxy acid type dispersion agent and anion surfactant cooperation form;
Anion surfactant is meant sodium lauryl sulphate and Sodium dodecylbenzene sulfonate;
Defoamer is an organosilicon emulsion defoaming agents, its usage quantity be after phase-changing energy storage material is made water miscible liquid total amount of liquid 0.003～0.005%.
Paraffin of the present invention and C
11～C
14At least a material of normal paraffin or the mixing material proportion of two or more materials are determined according to the difference of transformation temperature.
The preparation method of phase-changing energy storage material microcapsule of the present invention:
A, in the container that has agitator, condenser and thermometer, add entry and anion surfactant, the gelatine aqueous solution and polyocarboxy acid type dispersion agent, heating;
B, formaldehyde solution is transferred pH value with trolamine, heating, and add trimeric cyanamide, urea, polyvinyl alcohol water solution and water is heated to the mixed solution bleach while stirring, continues to be heated to 80 ℃, and keep 80 ℃ standby;
C, with the heating of paraffin and normal paraffin and fully mix;
D, start stirrer and add the mineral wax mixture in fused c step when a Buwen degree rises to 60 ℃, stable emulsion is made in high-speed stirring emulsification about 10 minutes;
E, add sodium bicarbonate aqueous solution and aqueous citric acid solution when the emulsion temperature rises to 70 ℃, and adjust pH value;
F, add silicone antifoam agent then, add 1/4b at last and go on foot ready modified cyanurotriamide methylal resin solution, spend 40 minutes after beginning slowly drip remaining polymkeric substance;
G, after all polymkeric substance dropwises, add aqueous ammonium chloride solution, continued in 70 ℃～75 ℃ stirring reaction 4 hours, stop heating, begin cooling;
H, after being cooled to below 40 ℃, adjust the pH value of reaction system with aqueous sodium hydroxide solution;
I, dehydration, washing, dehydration, drying draw Powdered phase-changing energy storage material microcapsule product again.
The cyst material that the present invention adopts is the melamine resin with urea and polyvinyl alcohol modification.Finding to adopt melamine resin by the contrast experiment to multiple cyst material and manufacturing process is cyst material, when producing the phase-changing energy storage material microcapsule with situ aggregation method, the easiest operation, and guarantee to wrap up under the non-leakage situation phase-changing energy storage material more than 70% at microcapsule.In cyst material, mix the later thermostability that can improve cyst wall of a spot of urea, mix the toughness that a spot of polyvinyl alcohol can improve later cyst wall.
Producing the phase-changing energy storage material microcapsule, at first is that phase-changing energy storage material is become stable water miscible liquid, and this just needs to be fit to its emulsifying agent.When the small liquid integument of phase-changing energy storage material cyst material parcel, curing back have the good dispersion agent of needs keep good suspended state when separating from liquid phase.So must be with emulsifying agent and the compound use of dispersion agent.Anion surfactant and nonionogenic tenside as the emulsifying agent use, representational have Sodium dodecylbenzene sulfonate, sodium lauryl sulphate and sorbitan stearate, sorbitan monooleate, sorbitan stearic acid polyoxyethylene ether, a sorbitol anhydride oleate Soxylat A 25-7 etc.These tensio-active agents use separately, also can compoundly use.When producing the phase-changing energy storage material microcapsule, being fit to use water soluble organic polymer class dispersion agent, impelling liquid because high score subclass dispersion agent has--liquid disperses and protects the dual function of drop.
The big body technology of the production technique of phase-changing energy storage material microcapsule is as follows: add clear water and blending emulsifiers and dispersion agent in reactor, warming while stirring adds fused phase-changing energy storage material to the specified temperature scope, high-speed stirring is made stable milk sap.In another reactor, add material heated polymerizables such as formaldehyde solution and trimeric cyanamide, urea, polyvinyl alcohol and become modified cyanurotriamide resin solution, standby.After adding an amount of solidifying agent in the phase change material milk sap, drip melamine resin solution and begin parcel (temperature of reaction generally is controlled at 70 ~ 75 ℃).Continue reaction about 4 hours after all resins dropwises, make milk sap become microparticle suspended dispersed liquid fully.The final product through behind washing, centrifuge dehydration, the air stream drying being after the cooling of phase-changing energy storage material micro-capsule dispersion liquid, the neutralization.
Because the effect of tensio-active agent and protective colloid can produce a lot of foams, can have a strong impact on production schedule and quality product at the initial stage of above-mentioned production process emulsifying stage.Therefore should add appropriate amount of defoamer carries out froth breaking.We have selected organosilicon emulsion defoaming agents in many defoamers, and its consumption is 0.003 ~ 0.005% of a whole reaction system gross weight.
Exemplify the exemplary that the present invention produces the phase-changing energy storage material microcapsule below:
Embodiment 1
1, in the there-necked flask that has agitator, condenser and thermometer, adds entry 310g and sodium lauryl sulphate 1.1g, 10% gelatine aqueous solution 11g and polyocarboxy acid type dispersion agent (waterborne pigment dispersant P-19) 4.0kg, begin heating.
2, in beaker, add 37% formaldehyde solution 56g simultaneously, transfer PH=8 with the 0.4g trolamine.Begin heating, and add 18.5g trimeric cyanamide, 8.0g urea, 10% polyvinyl alcohol water solution 6g and 50g water, be heated to the mixed solution bleach while stirring, continue to be heated to 80 ℃, and keep 80 ℃ standby.
3, simultaneously with beaker with 50g58# paraffin and 70g normal paraffin (carbon 14), be heated to 65 ℃ and fully mix.
4, start stirrer and add the fused mineral wax mixture when the temperature in the there-necked flask rises to 60 ℃, stable emulsion is made in high-speed stirring (more than the 1000 commentaries on classics/min) emulsification about 10 minutes.
Add 6% sodium bicarbonate aqueous solution 3.2g and 10% aqueous citric acid solution 20g when 5, the emulsion temperature rises to 70 ℃, pH value in the still is adjusted into 4.5～5.
6, then add again and add 1/4 ready modified cyanurotriamide methylal resin solution behind the silicone antifoam agent 0.02g.Beginning slowly drips remaining polymkeric substance after spending 40 minutes, drips (temperature of reaction remains at 70 ℃～75 ℃) in 1.5 hours.
7, after all polymkeric substance dropwises, add 20% aqueous ammonium chloride solution 5.0g.Continuation stirring reaction 4 hours in 70 ℃～75 ℃.Stop heating, begin cooling.
8, after being cooled to below 40 ℃, the pH value of reaction system is adjusted into 7～8 with 10% aqueous sodium hydroxide solution 5.0g.
9, dehydration, washing, dehydration again, drying draws Powdered phase-changing energy storage material microcapsule product 145g.
The about 300kg/m3 of this product unit weight, median size are that 0.0334mm, transformation temperature are that 25 ℃, potential heat value are 120.6j/g.
Embodiment 2
Get 58# paraffin 60g and normal paraffin (carbon-11) 60g as phase-changing energy storage material, other is all operated with same technology of example 1 and prescription and makes phase-changing energy storage material microcapsule 136g.The transformation temperature of obtained phase-changing energy storage material microcapsule is 30 ℃, and potential heat value is 115j/g.
Embodiment 3
Get outside 58# paraffin 50g and sherwood oil (60～90 ℃ of the boiling points) 60g as phase-changing energy storage material, other is all operated with same technology of example 1 and prescription and makes phase-changing energy storage material microcapsule 138g.The transformation temperature of obtained phase-changing energy storage material microcapsule is 10.7 ℃, and potential heat value only is 36.3j/g.
Embodiment 4
Get outside 58# paraffin 30g and the butyl stearate 70g as phase-changing energy storage material, other is all operated with same technology of example 1 and prescription and makes phase-changing energy storage material microcapsule 116g.The transformation temperature of obtained phase-changing energy storage material microcapsule is 12.88 ℃, and potential heat value only is 77.02j/g.
Following table be transformation temperature 42.8 when spending concrete each material of pilot scale use concrete amount synopsis
Claims (3)
1. a phase-changing energy storage material is characterized in that: mainly comprise phase-changing energy storage material and cyst material, be aided with dispersion agent, defoamer again;
Wherein phase-changing energy storage material is paraffin and C
11～C
14At least a material in the normal paraffin or the mixing of two or more materials;
Cyst material is the trimeric cyanamide methylal resin with urea and polyvinyl alcohol modification;
The weight part ratio of phase-changing energy storage material and cyst material is: 75:25～65:35;
Dispersion agent is that gelatine solution, polyocarboxy acid type dispersion agent and anion surfactant cooperation form;
Anion surfactant is meant sodium lauryl sulphate and Sodium dodecylbenzene sulfonate;
Defoamer is an organosilicon emulsion defoaming agents, its usage quantity be after phase-changing energy storage material is made water miscible liquid total amount of liquid 0.003～0.005%.
According to claim 1 the phase-changing energy storage material of book, it is characterized in that: paraffin and C
11～C
14At least a material of normal paraffin or the mixing material proportion of two or more materials are determined according to the difference of transformation temperature.
3. the preparation method of phase-changing energy storage material microcapsule is characterized in that:
A, in the container that has agitator, condenser and thermometer, add entry and anion surfactant, the gelatine aqueous solution and polyocarboxy acid type dispersion agent, heating;
B, formaldehyde solution is transferred pH value with trolamine, heating, and add trimeric cyanamide, urea, polyvinyl alcohol water solution and water is heated to the mixed solution bleach while stirring, continues to be heated to 80 ℃, and keep 80 ℃ standby;
C, with the heating of paraffin and normal paraffin and fully mix;
D, start stirrer and add the mineral wax mixture in fused c step when a Buwen degree rises to 60 ℃, stable emulsion is made in high-speed stirring emulsification about 10 minutes;
E, add sodium bicarbonate aqueous solution and aqueous citric acid solution when the emulsion temperature rises to 70 ℃, and adjust pH value;
F, add silicone antifoam agent then, add 1/4b at last and go on foot ready modified cyanurotriamide methylal resin solution, spend 40 minutes after beginning slowly drip remaining polymkeric substance;
G, after all polymkeric substance dropwises, add aqueous ammonium chloride solution, continued in 70 ℃～75 ℃ stirring reaction 4 hours, stop heating, begin cooling;
H, after being cooled to below 40 ℃, adjust the pH value of reaction system with aqueous sodium hydroxide solution;
I, dehydration, washing, dehydration, drying draw Powdered phase-changing energy storage material microcapsule product again.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527305A (en) * | 2012-01-09 | 2012-07-04 | 东北林业大学 | Preparation method of spherical beta-cyclodextrin/ melamine resin phase change energy storage materials |
| CN102732228A (en) * | 2012-07-11 | 2012-10-17 | 中国科学院广州能源研究所 | Constant-temperature phase change energy storage material |
| CN106833540A (en) * | 2017-01-19 | 2017-06-13 | 苏州鸿凌达电子科技有限公司 | Phase-changing energy storage material microcapsules and its manufacture craft |
| CN107722943A (en) * | 2017-11-09 | 2018-02-23 | 北京林业大学 | A kind of preparation method of wax phase change microcapsules |
| CN110295500A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of material treatment method for making pure-cotton fabric have imitative mercerising cool feeling |
| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| WO2021098656A1 (en) * | 2019-11-18 | 2021-05-27 | 深圳先进技术研究院 | Phase-change energy storage microcapsule using organic silazane polymer resin as shell material and preparation method therefor |
| CN114870760A (en) * | 2022-05-13 | 2022-08-09 | 湖北大学 | Preparation method of inorganic shell material phase change microcapsule |
| CN116350727A (en) * | 2022-12-27 | 2023-06-30 | 北京蜜蜂堂生物医药股份有限公司 | Beeswax paste for wax therapy and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555401A (en) * | 2008-04-10 | 2009-10-14 | 中国科学院化学研究所 | Microcapsule of organic phase change energy storage material and preparation method thereof |
-
2011
- 2011-06-10 CN CN 201110154862 patent/CN102268238B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555401A (en) * | 2008-04-10 | 2009-10-14 | 中国科学院化学研究所 | Microcapsule of organic phase change energy storage material and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527305A (en) * | 2012-01-09 | 2012-07-04 | 东北林业大学 | Preparation method of spherical beta-cyclodextrin/ melamine resin phase change energy storage materials |
| CN102732228A (en) * | 2012-07-11 | 2012-10-17 | 中国科学院广州能源研究所 | Constant-temperature phase change energy storage material |
| CN102732228B (en) * | 2012-07-11 | 2014-04-02 | 中国科学院广州能源研究所 | Constant-temperature phase change energy storage material |
| CN106833540A (en) * | 2017-01-19 | 2017-06-13 | 苏州鸿凌达电子科技有限公司 | Phase-changing energy storage material microcapsules and its manufacture craft |
| CN107722943A (en) * | 2017-11-09 | 2018-02-23 | 北京林业大学 | A kind of preparation method of wax phase change microcapsules |
| CN110295500A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of material treatment method for making pure-cotton fabric have imitative mercerising cool feeling |
| CN110295500B (en) * | 2018-03-23 | 2022-05-31 | 上海水星家用纺织品股份有限公司 | Fabric finishing method for enabling pure cotton fabric to have silky light cool feeling |
| WO2021098656A1 (en) * | 2019-11-18 | 2021-05-27 | 深圳先进技术研究院 | Phase-change energy storage microcapsule using organic silazane polymer resin as shell material and preparation method therefor |
| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| CN114870760A (en) * | 2022-05-13 | 2022-08-09 | 湖北大学 | Preparation method of inorganic shell material phase change microcapsule |
| CN114870760B (en) * | 2022-05-13 | 2023-08-29 | 湖北大学 | Preparation method of inorganic shell material phase-change microcapsule |
| CN116350727A (en) * | 2022-12-27 | 2023-06-30 | 北京蜜蜂堂生物医药股份有限公司 | Beeswax paste for wax therapy and preparation method thereof |
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