CN101050354A - Phase change energy stored microcapsule, preparation method and apparatus - Google Patents
Phase change energy stored microcapsule, preparation method and apparatus Download PDFInfo
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Abstract
This invention relates to method and apparatus for preparing phase-change energy-storage microcapsules. The phase-change energy-storage microcapsules comprise encapsulating material and organic phase-change material. The encapsulating material is composed of a network polymer, which is obtained by reaction between sodium alginate and alkaline earth metal salt. The method comprises: mixing sodium alginate solution and liquid phase-change energy-storage paraffin, and encapsulating by membrane pore method to obtain microcapsules. The obtained phase-change energy-storage microcapsules have such advantages as high chemical and thermal stability, high mechanical strength, and wide applications.
Description
Technical field
The present invention relates to phase-transition energy-storage microcapsules and preparation method thereof and device.
Background technology
The energy is the basis that human society is rely and existed and develop, and along with improving constantly of The development in society and economy and living standards of the people, human demand to the energy increases day by day, will cause the shortage of primary energy source, particularly fossil oil.Therefore, reclaim, store, utilize heat energy more and more to come into one's own.
In production and the life many thermal energy sourcies are arranged, as sun power, Geothermal energy, industrial exhaust heat, used heat etc.The characteristics of these energy are that total amount is big, but have shortcomings such as intermittent and unstable.Phase change energy storage technology utilizes the latent heat of phase change of material, can alleviate the contradiction of energy supply and demand on time-space, therefore in the society that highlights the energy and environmental problem now, phase-changing energy storage material receives much attention in fields such as building materials, weaving, aviation, sun power utilization, national defence and military affairs.
Phase-changing energy storage material comprises inorganics and organism two big classes.Most inorganic-phase variable energy storage materials have corrodibility, and have the shortcoming that cold-peace is separated in phase transition process, influence its use.And organic phase change energy storage material does not in use have above-mentioned shortcoming, and chemical property is stable, and price is also cheap, thus practical application maximum be organic phase change material.Phase-changing energy storage material in use exists problems such as loss, corrosion.In order to address these problems, must encapsulate phase-changing energy storage material.
At present, the encapsulation that phase-changing energy storage material is carried out mainly is divided into two kinds: settingization, microencapsulation.The settingization of phase-changing energy storage material mainly is to carry out phase change material and some propping materials compound, form the solidified phase-changing energy storage material, such as polyethylene-paraffin setting phase change energy storage material etc., some setting phase change energy storage material, there are some and the outside hole that is connected, cause its sealing property poor, need coat the one layer of polymeric film again on its surface.And the granularity of regularization phase-changing energy storage material is bigger, is not suitable for using in some occasion, as whitewashing of spinning field and body of wall.The microencapsulation of phase-changing energy storage material is meant in the phase-changing energy storage material surface ratio and coats one deck solid cyst material more equably or phase-changing energy storage material is scattered in formation multinuclear micro-capsule in the polymer microsphere, thereby reaches the effect of sealing.Comparing its sealing property will get well with settingization, and the phase change material made from microencapsulation is a pressed powder, helps using, transports and preserves.
The preparation method of micro-capsule mainly contains at present: emulsion hud polymerization (publication number CN1695788), polymers soln precipitation polymerization (publication number CN1695789), original position encapsulated (publication number CN1908257) etc., these methods exist many problems in preparation micro-capsule process, for example microcapsule diameter controlled amount degree is little, problem such as preparation process technology and reaction conditions complexity, production serialization degree are low, and limited the application of microencapsulation phase-changing energy storage material.
Material as phase-transition energy-storage microcapsules wall material has multiple, as publication number is that the patent of CN1161364 adopts melmac as micro-capsule wall material, publication number is that the patent of CN1844269 adopts the silica deposit thing as micro-capsule wall material, publication number is that the patent of CN1715359 adopts the animal proteinum acetal as micro-capsule wall material, publication number is that patent employing vinyl and the bi-vinyl type free base monomer of CN1695787 is the outer cover polymer source, or the like, adopt this type of material as the wall material, all need strict control reaction conditions, induced polymer monomer polymerization packing, so operating procedure process complexity, be unsuitable for scale operation, and the micro-capsule of existing microencapsulation method preparation mostly is the monokaryon micro-capsule, has micro-capsule chemical stability and poor heat stability, physical strength is low, problems such as range of application is narrow.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of new phase-transition energy-storage microcapsules is provided.Produce chemical stability and good thermal stability, physical strength height, the wide phase-transition energy-storage microcapsules of range of application by choosing a kind of new encapsulating material.
Another object of the present invention provides the preparation method of described phase-transition energy-storage microcapsules.
Of the present invention also have a purpose to provide the device of realizing described method.
Phase-transition energy-storage microcapsules of the present invention comprises encapsulating material and phase change material, it is characterized in that described encapsulating material is made up of the crosslinking net polymkeric substance that sodium alginate and alkaline-earth metal reactant salt generate, and described phase change material is an organic phase change material.
As preferred version, described encapsulating material accounts for the 5-15% of micro-capsule total mass, and described phase change material accounts for the 95-85% of micro-capsule total mass.
Described organic phase change material is a normal temperature phase-change accumulation energy paraffin.
The preparation method of described phase-transition energy-storage microcapsules is sodium alginate soln to be mixed the back adopt the fenestra method to be encapsulated as micro-capsule with liquid phase-change energy storage paraffin, may further comprise the steps particularly:
(1) sodium alginate soln configuration: sodium alginate, water and tensio-active agent heat in temperature 45-50 ℃ water-bath, are stirred to dissolving fully; Each amounts of components: sodium alginate 3-5 part quality, water 90-98 part quality, tensio-active agent 1-3 part quality;
(2) phase-change accumulation energy paraffin is scattered in the sodium alginate soln: phase-change accumulation energy paraffin is melt into liquid state in 45-50 ℃ of water-bath, with liquid phase-change energy storage paraffin and step (1) sodium alginate soln by 1: the 3-5 mass ratio mixes, under 1000-1500r/min, stir, 40-50 minute, obtain uniform emulsion;
(3) seal and solidify: the emulsion that obtains in the step (2) is packed in the storage tank, the pressurization back is adopted the fenestra method to enter moving phase alkaline-earth metal salt brine solution and is formed gel, generate ganoid multinuclear capsule, through continuing curing, washing, filtration, oven drying at low temperature, obtain described phase-transition energy-storage microcapsules.
As preferred version, the described tensio-active agent of step (1) is Tween-80.
The described moving phase alkaline earth salt of step (3) solute is CaCl
2, concentration is 0.25mol/L.
Step (3) is described to be pressurised into that to adopt nitrogen pressure pressure to the storage tank be 1.2atm.
The porous-film that the described fenestra method of step (3) is used is modification cellulose acetate membrane or modification cellulose mixture film.
The described continuation solidification value of step (3) is 10 ℃, and be 1h set time, and the solidifying agent of employing is a calcium chloride water, and concentration is 0.25mol/L.
The device of realizing the method for the invention comprises nitrogen pot, storage tank, porous-film, solution tank, recycle pump, water bath with thermostatic control, suction pump, hydraulic vortex flow devices; Nitrogen pot to the storage tank pressurization is connected with storage tank, storage tank is connected with porous-film, and porous-film, recycle pump all place solution tank, and solution tank places water bath with thermostatic control, suction pump links to each other with solution tank by pipeline, and hydraulic vortex flow devices links to each other with solution tank with suction pump respectively by pipeline.
The present invention utilizes sodium alginate and alkaline-earth metal ions effect by selecting for use reproducible cheap macromolecular material sodium alginate as wall material macromolecular material precursor, forms cross-linked structure and seals phase change material.
Sodium alginate is a kind of hydrophilic natural polymkeric substance that extracts from sea-tangle, has the sodium salt polymkeric substance of the uronic acid of carboxyl 1,4 type glucoside bond, is the very easily water-soluble and insoluble organic solvent of a kind of natural polymer dielectric medium.When sodium alginate and alkaline-earth metal ions effect, change water-fast Lalgine alkaline earth salt quantitatively into and be coated on encapsulated thing surface formation capsule with chain structure, reaction principle is:
Utilize above-mentioned character, form micro-capsule, and precipitation separation comes out from water.In the actual mechanical process, preparation contains the emulsion of phase change material and sodium alginate, then it is joined Ca
2+In the solution, can seal encystation.
The present invention utilizes fenestra method principle design to go out a covering device, with the disperse phase of phase-change accumulation energy paraffin in sodium alginate soln under the effect of pressure, form drop through the fenestra of microporous membrane on the film surface, along under the souring of the external phase of film surface flow, when the diameter of drop reaches a certain value just from the film sur-face peeling, thereby form emulsion.The parameter that influences the fenestra emulsion process mainly comprises porosity, film surface type, emulsifier type and content, disperse phase flow, external phase speed and the operation pressure reduction etc. of membrane micropore aperture and distribution, film.Studies show that under the situation that other parameter is determined, the size of emulsion droplet and the aperture of used film are linear.Under the fully narrow situation of membrane pore size distribution of sizes, can make monodisperse emulsion.The rate of adsorption of emulsifying agent is fast more, and emulsion droplet is just more little.The size that increases emulsion droplet along with external phase speed will reduce, up to reaching a constant value.The aperture of film is more little, and emulsification pressure is just high more.So the porous-film that the present invention uses is general modification cellulose acetate membrane or modification cellulose mixture film.
The present invention compared with prior art has following advantage:
1, the encapsulating material of the micro-capsule that makes of the present invention is sodium alginate and alkaline-earth metal reactive polymeric thing, has good hydrophilicity, the present invention can be applied in the water soluble paint;
2, the microcapsule size adjustable size is controlled, has encapsulated the wax phase change energy storage material efficiently, simply, has widened the range of application of phase-changing energy storage material, has simplified the application of phase-changing energy storage material in producing, living;
3, phase-transition energy-storage microcapsules material preparation process of the present invention is simple, easy to operate, can be continuously produced;
4, the raw material of the present invention's employing is a sodium alginate, is renewable resources, and low price, wide material sources are easy to industrialization promotion.
Description of drawings
Fig. 1 the present invention prepares the device synoptic diagram of described phase-transition energy-storage microcapsules;
Among the figure, the 1-nitrogen pot; The 2-storage tank; 3, the 10-porous-film; The 4-solution tank; The 5-recycle pump; The 6-water bath with thermostatic control; The 7-suction pump; The 8-hydraulic vortex flow devices; 9,13-phase change material and sodium alginate soln emulsion; 11-moving phase; The 12-micro-capsule;
The phase-transition energy-storage microcapsules micro-image that Fig. 2 the present invention prepares;
The phase-transition energy-storage microcapsules that Fig. 3 the present invention prepares shows the size-grade distribution histogram.
Embodiment
Further specify the present invention below in conjunction with the drawings and specific embodiments.
As shown in Figure 1, nitrogen pot 1 to storage tank 2 pressurizations is connected with storage tank 2, storage tank 2 is connected with porous-film 3, porous-film 3, recycle pump 5 all place solution tank 4, solution tank 4 places water bath with thermostatic control 6, suction pump 7 links to each other with solution tank 4 by pipeline, and hydraulic vortex flow devices 8 links to each other with solution tank 4 with suction pump 7 respectively by pipeline.
Embodiment 1
(1) sodium alginate soln configuration
With the sodium alginate of 3 parts of mass fractions, 98 parts of water and 1 part of Tween-80 heating for dissolving in 45 ℃ of water-baths of temperature, and use magnetic stirrer treat that dissolving fully and after solution has certain viscosity, stops to stir stand-by.
(2) phase-change accumulation energy paraffin is scattered in the sodium alginate soln
Phase-change accumulation energy paraffin is melt into liquid state in 45 ℃ water-bath, takes out then, mix with sodium alginate soln, under 1200r/min, stir fast, can obtain uniform O/W type emulsion after about 45 minutes with 1: 4 mass ratio.
(3) seal and solidify
In the storage tank 2 with emulsion load map 1 shown device that obtains in the step (2), open nitrogen pot 1, make that pressure is 1.2atm in the storage tank 2, open recycle pump 5, after the suction pump 7, open the valve on the loop, emulsion enters in the calcium chloride water of 0.25mol/L after by modification cellulose mixture film fenestra, its surface forms gel at once, generate ganoid micro-capsule, it is that the calcium chloride water of the 0.25mol/L about 10 ℃ continues to solidify 1h that the microballoon of separating by hydraulic vortex flow devices 8 places temperature, treat all cohesions after washing, filter, oven drying at low temperature obtains phase-transition energy-storage microcapsules.
Place Lecia research grade Pianguan County microscope (USD28500[ST2004H0803] transmission and reflection polarizing microscope) to observe down the microstructure of micro-capsule the phase-transition energy-storage microcapsules for preparing, as shown in Figure 2.As can be seen from Figure 2, micro-capsule is a spherical shape, and the hangover amounts of particles is few.The micro-image of micro-capsule is imported IPP (Image-Pro Plus, the exploitation of U.S. Media Cybernetics company) image processing system, adopts the technology of image analysis, statistical study the micro-image of 500 micro-capsules, draw the size-grade distribution situation of micro-capsule.Analytical results as shown in Figure 3.As can be seen from Figure 3, the distribution of sizes of micro-capsule is narrower, and granular size mainly concentrates between the 8-17 μ m.
Embodiment 2
(1) sodium alginate soln configuration
With the sodium alginate of 4 parts of massfractions, 94 parts of water and 2 parts of Tween-80 heating for dissolving in 50 ℃ of water-baths of temperature, and use magnetic stirrer treat that dissolving fully and after solution has certain viscosity, stops to stir stand-by.
(2) phase-change accumulation energy paraffin is scattered in the sodium alginate soln
Phase-change accumulation energy paraffin is melt into liquid state in 50 ℃ water-bath, takes out then, mix with sodium alginate soln, under 1000r/min, stir fast, can obtain uniform O/W type emulsion after about 50 minutes with 1: 3 ratio.
(3) seal and solidify
In the storage tank 2 with emulsion load map 1 shown device that obtains in the step (2), open nitrogen pot 1, make that pressure is 1.2atm in the storage tank 2, open recycle pump 5, after the suction pump 7, open the valve on the loop, emulsion enters in the calcium chloride water of 0.25mol/L after by modification cellulose acetate membrane fenestra, its surface forms gel at once, generate ganoid micro-capsule, it is that the calcium chloride water of the 0.25mol/L about 10 ℃ continues to solidify 1h that the microballoon of separating by hydraulic vortex flow devices 8 places temperature, treat all cohesions after washing, filter, oven drying at low temperature obtains phase-transition energy-storage microcapsules.
Place Lecia research grade Pianguan County microscope (USD28500[ST2004H0803] transmission and reflection polarizing microscope) to observe down the microstructure of micro-capsule the phase-transition energy-storage microcapsules for preparing, find out that micro-capsule is a spherical shape, the hangover amounts of particles is few.The micro-image of micro-capsule is imported IPP (Image-Pro Plus, the exploitation of U.S. MediaCybernetics company) image processing system, adopts the technology of image analysis, statistical study the micro-image of 500 micro-capsules, draw the size-grade distribution situation of micro-capsule.Analytical results shows that the distribution of sizes of micro-capsule is narrower, and granular size mainly concentrates between the 8-17 μ m.
Embodiment 3
(1) sodium alginate soln configuration
With the sodium alginate of 5 parts of massfractions, 90 parts of water and 3 parts of Tween-80 heating for dissolving in 48 ℃ of water-baths of temperature, and use magnetic stirrer treat that dissolving fully and after solution has certain viscosity, stops to stir stand-by.
(2) phase-change accumulation energy paraffin is scattered in the sodium alginate soln
Phase-change accumulation energy paraffin is melt into liquid state in 48 ℃ water-bath, takes out then, mix with sodium alginate soln, under 1500r/min, stir fast, can obtain uniform O/W type emulsion after about 40 minutes with 1: 5 ratio.
(3) seal and solidify
In the storage tank 2 with emulsion load map 1 shown device that obtains in the step (2), open nitrogen pot 1, make that pressure is 1.2atm in the storage tank 2, open recycle pump 5, after the suction pump 7, open the valve on the loop, emulsion enters in the calcium chloride water of 0.25mol/L after by modification cellulose acetate membrane fenestra, its surface forms gel at once, generate ganoid micro-capsule, it is that the calcium chloride water of the 0.25mol/L about 10 ℃ continues to solidify 1h that the microballoon of separating by hydraulic vortex flow devices 8 places temperature, treat all cohesions after washing, filter, oven drying at low temperature obtains phase-transition energy-storage microcapsules.
Place Lecia research grade Pianguan County microscope (USD28500[ST2004H0803] transmission and reflection polarizing microscope) to observe down the microstructure of micro-capsule the phase-transition energy-storage microcapsules for preparing, find out that micro-capsule is a spherical shape, the hangover amounts of particles is few.The micro-image of micro-capsule is imported IPP (Image-Pro Plus, the exploitation of U.S. MediaCybernetics company) image processing system, adopts the technology of image analysis, statistical study the micro-image of 500 micro-capsules, draw the size-grade distribution situation of micro-capsule.Analytical results shows that the distribution of sizes of micro-capsule is narrower, and granular size mainly concentrates between the 8-17 μ m.
Claims (9)
1, a kind of phase-transition energy-storage microcapsules comprises encapsulating material and phase change material, it is characterized in that described encapsulating material is made up of the crosslinking net polymkeric substance that sodium alginate and alkaline-earth metal reactant salt generate, and described phase change material is an organic phase change material.
2, phase-transition energy-storage microcapsules according to claim 1 and 2 is characterized in that described organic phase change material is a normal temperature phase-change accumulation energy paraffin.
3, the preparation method of claim 1 or 2 described phase-transition energy-storage microcapsules is characterized in that sodium alginate soln is mixed the back with liquid phase-change energy storage paraffin adopt the fenestra method to be encapsulated as micro-capsule, may further comprise the steps:
(1) sodium alginate soln configuration: sodium alginate, water and tensio-active agent heat in temperature 45-50 ℃ water-bath, are stirred to dissolving fully; Each amounts of components: sodium alginate 3-5 part quality, water 90-98 part quality, tensio-active agent 1-3 part quality;
(2) phase-change accumulation energy paraffin is scattered in the sodium alginate soln: phase-change accumulation energy paraffin is melt into liquid state in 45-50 ℃ of water-bath, with liquid phase-change energy storage paraffin and step (1) sodium alginate soln by 1: the 3-5 mass ratio mixes, under 1000-1500r/min, stir, 40-50 minute, obtain uniform emulsion;
(3) seal and solidify: the emulsion that obtains in the step (2) is packed in the storage tank, the pressurization back is adopted the fenestra method to enter moving phase alkaline-earth metal salt brine solution and is formed gel, generate ganoid multinuclear capsule, through continuing curing, washing, filtration, oven drying at low temperature, obtain described phase-transition energy-storage microcapsules.
4, method according to claim 3 is characterized in that the described tensio-active agent of step (1) is Tween-80.
5, method according to claim 4 is characterized in that the described moving phase alkaline earth salt of step (3) solute is CaCl
2, concentration is 0.25mol/L.
6, method according to claim 5 is characterized in that step (3) is described to be pressurised into that to adopt nitrogen pressure pressure to the storage tank be 1.2atm.
7, method according to claim 6 is characterized in that the porous-film that the described fenestra method of step (3) is used is modification cellulose acetate membrane or modification cellulose mixture film.
8, method according to claim 7 is characterized in that the described continuation solidification value of step (3) is 10 ℃, and be 1h set time, and the solidifying agent of employing is a calcium chloride water, and concentration is 0.25mol/L.
9, realize the device of one of claim 3-8 described method, it is characterized in that comprising nitrogen pot, storage tank, porous-film, solution tank, recycle pump, water bath with thermostatic control, suction pump, hydraulic vortex flow devices; Nitrogen pot to the storage tank pressurization is connected with storage tank, storage tank is connected with porous-film, and porous-film, recycle pump all place solution tank, and solution tank places water bath with thermostatic control, suction pump links to each other with solution tank by pipeline, and hydraulic vortex flow devices links to each other with solution tank with suction pump respectively by pipeline.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012075747A1 (en) * | 2010-12-10 | 2012-06-14 | 东南大学 | Paraffin phase change energy storage materials and preparation method thereof |
| CN104910869A (en) * | 2015-06-12 | 2015-09-16 | 陕西理工学院 | Controllable preparation device of organic composite phase-change energy storage material |
| CN104927778A (en) * | 2015-06-12 | 2015-09-23 | 陕西理工学院 | Controllable preparation method for organic composite phase change energy storage material |
| CN105013413A (en) * | 2015-07-14 | 2015-11-04 | 贵州华益能环保科技有限公司 | Preparation and application for greenhouse anti-freezing phase change energy storage capsule |
| CN108048045A (en) * | 2017-11-28 | 2018-05-18 | 大连理工大学 | A kind of enhanced thermal conduction organic composite shaping phase-change material and preparation method thereof |
| CN108102614A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of organic composite shaping phase-change material and preparation method thereof |
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| CN108854876A (en) * | 2018-08-22 | 2018-11-23 | 南京林业大学 | A kind of paraffin/cellulose diacetate phase-change microcapsule and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012075747A1 (en) * | 2010-12-10 | 2012-06-14 | 东南大学 | Paraffin phase change energy storage materials and preparation method thereof |
| CN104910869A (en) * | 2015-06-12 | 2015-09-16 | 陕西理工学院 | Controllable preparation device of organic composite phase-change energy storage material |
| CN104927778A (en) * | 2015-06-12 | 2015-09-23 | 陕西理工学院 | Controllable preparation method for organic composite phase change energy storage material |
| CN104927778B (en) * | 2015-06-12 | 2017-12-05 | 陕西理工学院 | A kind of controllable method for preparing of organic composite phase-changing energy storage material |
| CN104910869B (en) * | 2015-06-12 | 2017-12-22 | 陕西理工学院 | A kind of controllable preparation device of organic composite phase-changing energy storage material |
| CN105013413A (en) * | 2015-07-14 | 2015-11-04 | 贵州华益能环保科技有限公司 | Preparation and application for greenhouse anti-freezing phase change energy storage capsule |
| CN108102613A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of anti-mildew organic composite shaping phase-change material and preparation method thereof |
| CN108102614A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of organic composite shaping phase-change material and preparation method thereof |
| CN108048045A (en) * | 2017-11-28 | 2018-05-18 | 大连理工大学 | A kind of enhanced thermal conduction organic composite shaping phase-change material and preparation method thereof |
| CN108102614B (en) * | 2017-11-28 | 2020-12-11 | 大连理工大学 | Organic composite shape-stabilized phase-change material and preparation method thereof |
| CN108048045B (en) * | 2017-11-28 | 2021-02-26 | 大连理工大学 | Heat-conducting enhanced organic composite shape-stabilized phase change material and preparation method thereof |
| US11479701B2 (en) | 2017-11-28 | 2022-10-25 | Dalian University Of Technology | Thermal conduction enhanced organic composite shape-stabilized phase change material and preparation method thereof |
| CN108149514A (en) * | 2017-12-20 | 2018-06-12 | 常德金德新材料科技股份有限公司 | Transfer paper and preparation method thereof |
| CN108149514B (en) * | 2017-12-20 | 2020-12-22 | 常德金德新材料科技股份有限公司 | Transfer paper and preparation method thereof |
| CN108854876A (en) * | 2018-08-22 | 2018-11-23 | 南京林业大学 | A kind of paraffin/cellulose diacetate phase-change microcapsule and preparation method thereof |
| CN108854876B (en) * | 2018-08-22 | 2021-01-01 | 南京林业大学 | Paraffin/cellulose diacetate phase change microcapsule and preparation method thereof |
| CN110067736A (en) * | 2019-05-23 | 2019-07-30 | 宁波大学 | A kind of pumping system for liquid with precise control flow based on liquid metal |
| CN114014690A (en) * | 2021-12-13 | 2022-02-08 | 安徽创新秸秆利用有限公司 | High-strength continuous porous shale straw sintered brick and preparation method thereof |
| CN115246731A (en) * | 2021-12-21 | 2022-10-28 | 兰州理工大学 | Phase-change gypsum block and preparation method thereof |
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