CN1303182C - Phasochange energy storage ceramic particle and its preparation method - Google Patents
Phasochange energy storage ceramic particle and its preparation method Download PDFInfo
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- CN1303182C CN1303182C CNB031289991A CN03128999A CN1303182C CN 1303182 C CN1303182 C CN 1303182C CN B031289991 A CNB031289991 A CN B031289991A CN 03128999 A CN03128999 A CN 03128999A CN 1303182 C CN1303182 C CN 1303182C
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Abstract
The present invention relates to phase-change energy storage haydite and a preparation method thereof. The phase-change energy storage haydite uses a light porous haydite as a basal body, and organic phase-change substances are adsorbed and stored in the phase-change energy storage haydite of which the exterior is coated with a film layer made from polymer-base composite materials. In the preparation method, firstly, the organic phase-change substances are adsorbed and stored in the haydite by adopting a vacuum impregnation method, and then the film layer made from polymer-base composite materials is coated by adopting an immersion method. The phase-change energy storage haydite of the present invention has the advantages of stable energy storage in a long term and high heat exchange efficiency in the process of phase change, and is especially suitable for application in the field of construction, etc. Furthermore, the present invention has the advantages of wide material sources, low price, simple preparation technology and easy realization of industrial production.
Description
Technical field
The present invention relates to a kind of phase-changing energy storage material, be specially a kind of phase-change accumulation energy haydite and preparation method thereof.
Background technology
Energy storage is meant for the moment, the energy on a ground stores with certain form, be used for satisfying At All Other Times and (or) energy requirement in place, for the utilization of eliminating inharmonic contradiction between power supply and demand, improving energy use efficiency and renewable energy source significant values is arranged all.In heating buildings and refrigeration, energy is to obtain to utilize with the form of heat energy, and is therefore, more effective than storing other form energies at these field heat energy storages.According to the energy storage temperature, the heat energy storage technology can be divided into low temperature energy storage and high temperature energy-storage.According to energy storage mechanism, also it can be divided into sensible heat energy storage and hidden heat energy storage.Compare advantages such as hidden heat energy storage has energy storage density height (a high order of magnitude), energy storage-release can temperature-stable, volume is little, easy control with the sensible heat energy storage.Phase change material is the functive of latent heat of phase change energy storage, and U.S. Dow chemical company once carried out technical economical analysis to more than 20000 kinds of phase change materials, thinks wherein that kind has to utilize surplus in the of 200 to be worth, and transformation temperature has contained below 0 ℃ to 1000 ℃.At low temperature range (0 ℃-100 ℃), available phase change material is a lot, as organic phase changing matters such as paraffin (paraffins mixture), lipid acid and derivative thereof and inorganic hydrous salt phase transition material etc., especially organic phase changing matter have phase transition process stablize reversible, transformation temperature can be regulated arbitrarily, latent heat of phase change is big, starting material wide material sources, advantage such as cheap, for the exploitation of low temperature phase change hidden heat energy storage technology provides assurance.At present, the key of latent heat of phase change energy storage technology is transferred to it from the searching of phase change material and selection and is utilized technical.Mainly there are two difficult problems in phase change energy storage technology, and the one, the standing storage problem, the 2nd of phase change material, the heat exchange efficiency problem of phase transition process.Phase change material usually can leak out from the metal that encapsulates them or plastic containers in utilizing process, causes problems such as energy-storage function deterioration and environmental pollution.Secondly, phase change material usually uses with bigger bulk form, causes phase change material not undergo phase transition fully, or needs long time to impel its phase transformation to finish, cause the on the low side or energy wastage of phase change material utilization ratio, partial offset the advantage of latent heat of phase change energy storage.
One of focus of phase change energy storage technology is to use in ecotecture at present.Comprise and adopt the compound technology of preparing of material that phase change material and encapsulation or framework material are combined with each other, make matrix material, for example German BASF AG and the cooperation of Fraunhofer solar energy system institute adopt microcapsulary that phase change material is encapsulated in the high molecular polymer, be prepared into the phase-change accumulation energy plaster, be convenient to use at building field.The advantage of this method is a phase change material storage reliability height, the energy storage good endurance, but cost is higher.What also have is directly compound with phase change material and building product, make building structure have the dual-use function of load-bearing and phase-change accumulation energy simultaneously, people such as for example Canadian Concordia professor Feldman of university infiltrate building product (as plasterboard or porous concrete building blocks etc.) with organic phase changing matter, make building wall board with latent heat of phase change energy-storage function and building block etc.The advantage of this method is that cost is lower, but also exists phase change material in use to leak easily at present, problems such as storage reliability.Still be based on the sensible heat mode heat energy storage of materials such as concrete, cobble in present solar building, though the energy storage density of sensible heat energy storage is not high, volume is bigger, but have with low cost and the advantage energy-storage property long-term stability, therefore, replace the status that the sensible heat heat accumulation can be in building field, the latent heat of phase change energy storage technology is too high and two problems of weather resistance (being the storage reliability of phase change material) of workout cost simultaneously.
Summary of the invention
The objective of the invention is to propose a kind of energy-storage property long-term stability, phase transition process heat exchange efficiency height, and material source phase-changing energy storage material extensive, with low cost and preparation method thereof.
The phase-changing energy storage material that the present invention proposes is a matrix with light porous haydite, and its inner absorption stores organic phase changing matter, and external packets is covered with the polymer matrix composite rete; The porosity of this haydite is 50-80%, and the volume content of organic phase changing matter is 40-70% in the haydite, and the thickness of outer overlay film layer is the 10-100 micron.
Because above-mentioned phase-changing energy storage material is a matrix with the haydite, so be called the phase-change accumulation energy haydite.This phase-change accumulation energy haydite has superior performance, and its transformation temperature is between 5-70 ℃, and phase-change accumulation energy density is greater than 30MJ/m
3, the phase transition process coefficient of heat transfer is greater than 3.0kW/ ℃ of m
3
The haydite matrix of above-mentioned phase-change accumulation energy haydite generally can adopt clay, shale, pearlstone etc., its shape and size dimension without limits, organic phase changing matter generally can adopt paraffin (being paraffins mixture) or lipid acid and derivative thereof etc.; The outer layer copolymer based composites generally adopts resin, emulsion etc. as base material, the metal of employing thermal conductivity height (greater than 10w/mk) or inorganic non-metallic (as aluminium, ferrite, flyash, slag, silicon ash etc.) powder are as filler, make rete have hyposmosis, high heat-transfer performance, the weight ratio that filler accounts for matrix material is 1-4%.
The phase-change accumulation energy preparation method of porcelain granule that the present invention proposes is that employing vacuum infiltration method absorbs haydite and the storage organic phase changing matter; Adopt the method for immersing again, at the outside coated polymer based composites of haydite rete.
Among the above-mentioned preparation method, the step of vacuum infiltration method is as follows: the method that first usefulness vacuumizes extracts the air in the haydite, and vacuum is pressed and generally is higher than 80KPa, under vacuum environment haydite is soaked in the organic phase changing matter solution then; Remove vacuum, continue immersion again and get final product more than 30 minutes.In the inventive method, the porosity of selected haydite requires between 50-80% (mercury penetration method), and the hole connectedness is (image analytical method) between 50-95%.Acid or alkali environment is a neutrality in the hole, and organic phase changing matter is had no side effect, and with suitable large vol and the long-time organic phase changing matter that stores, and protects organic phase changing matter to avoid the external environment effect, prolongs the life-span of its energy-storage function, improves its weather resistance.The enthalpy of phase change of selected organic phase changing matter requires more than 100J/g, and transformation temperature is selected between 5～70 ℃, low price, a large amount of easily the acquisition.The porosity of sealing rete requires less than 5%, and the hole connectedness is less than 2% (image analytical method).
The present invention adopts the storage medium of haydite as organic phase changing matter, the pore structure of haydite has interior porosity and aperture ratio is big, the very little characteristics of boundary porosity and aperture, the standing storage that is fit to very much the liquid towards material, by outside haydite, increasing a low-permeability rete, further improve the permanent stability of its storage reliability and energy-storage property.Aspect phase-change heat-exchange efficient, because the haydite pore structure is divided into very tiny individuality with organic phase changing matter, increase its phase-change heat-exchange efficient greatly, and haydite pore structure skeleton also can be brought into play the enhancement of heat transfer function of the wing in the similar heat transfer engineering, and these all make the phase-change accumulation energy haydite have very high phase transition process heat exchange efficiency.In addition, ceramsite material wide material sources, price are very cheap, and preparation technology is simple, realize suitability for industrialized production easily.Therefore the phase-change accumulation energy haydite can have advantage with low cost, that energy-storage property is steady in a long-term and the phase transition process heat exchange efficiency is high simultaneously, is highly suitable for field application such as building.The phase-change accumulation energy haydite both can directly obtain to use as finished product, also can be used as the raw material preparing phase-change energy-storage composite material.For example, aspect direct use, can adopt the phase-change accumulation energy haydite to substitute ice hockey, be used for phase change cold-storage equipment, can promote the use of, produce considerable economic benefit at building cold-storage and industrial cold-storage field.Aspect the starting material use, the body of wall that can adopt making such as phase-change accumulation energy haydite, cement or gypsum to have the phase-change accumulation energy function helps building energy conservation.
Embodiment
Embodiment 1
Adopting porosity is that 75.6% swelling clay haydite stores organic phase changing matter, and the maximum particle diameter of haydite is 20 millimeters, and shape approximation is spherical.Selecting fusing point for use is that 45 ℃, enthalpy of phase change are that the paraffin (paraffins mixture) of 200J/g is as organic phase changing matter.The vacuum infiltration parameter is: the pumpdown time is 30 minutes, and vacuum is pressed and is 88.5kPa, and soak time is 30 minutes.The storage capacity of organic phase changing matter in haydite is about 65% (volume ratio).The sealing rete adopts the matrix material of being made up of Resins, epoxy and aluminium powder, and the volume content of aluminium powder is 2%, and the content that adds organic phase changing matter in the phase-change accumulation energy haydite behind the sealing ply is about 63.5%.The transformation temperature of phase-change accumulation energy haydite is 47.5 ℃, and phase-change accumulation energy density is 69.7MJ/m
3, the phase transition process coefficient of heat transfer is 4.2kW/ ℃ of m
3
Embodiment 2
Adopting porosity is that 73.3% swelling clay pottery sand stores organic phase changing matter, and the maximum particle diameter of pottery sand is 3 millimeters, is shaped as elliposoidal.Selecting fusing point for use is that 45 ℃, enthalpy of phase change are that the paraffin (paraffins mixture) of 200J/g is as organic phase changing matter.The vacuum infiltration parameter is: the pumpdown time is 30 minutes, and vacuum is pressed and is 88.5kPa, and soak time is 30 minutes.The storage capacity of organic phase changing matter in haydite is 60%.The sealing membrane layer material adopts sclerosis straight polymer emulsion-based matrix material, and emulsion adopts commercial SBR emulsion, adds the aluminium powder of 2% volume content.The content that adds the middle organic phase changing matter of the phase-change accumulation energy haydite of sealing behind the rete is 59.1%.The transformation temperature of phase-change accumulation energy haydite is 46.5 ℃, and phase-change accumulation energy density is 66.8MJ/m
3, the phase transition process coefficient of heat transfer is 3.8kW/ ℃ of m
3
Embodiment 3
Adopting porosity is that 75.6% swelling clay haydite stores organic phase changing matter, and the maximum particle diameter of haydite is 20 millimeters, and shape approximation is spherical.Selecting fusing point for use is 22 ℃, and enthalpy of phase change is that the butyl stearate of 128.5J/g is an organic phase changing matter.The vacuum infiltration parameter is: the pumpdown time is 30 minutes, and vacuum is pressed and is 88.5kPa, and soak time is 35 minutes.The storage capacity of organic phase changing matter in haydite is 67.5%.The sealing rete adopts the matrix material of being made up of Resins, epoxy and aluminium powder, and the volume content of aluminium powder is 2%.The content that adds organic phase changing matter in the phase-change accumulation energy haydite behind the sealing ply is 65.7%.The transformation temperature of phase-change accumulation energy haydite is 23.1 ℃, and phase-change accumulation energy density is 44.8MJ/m
3, the phase transition process coefficient of heat transfer is 4.3kW/ ℃ of m
3
Claims (6)
1, a kind of phase-change accumulation energy haydite is characterized in that with light porous haydite be matrix, and its inner absorption stores organic phase changing matter, and external packets is covered with the polymer matrix composite rete; The porosity of this haydite is 50-80%, and the volume content of organic phase changing matter is 40-70% in the haydite, and the thickness of outer overlay film layer is the 10-100 micron.
2, phase-change accumulation energy haydite according to claim 1 is characterized in that haydite matrix adopting clay, shale, pearlstone.
3, phase-change accumulation energy haydite according to claim 1 is characterized in that organic phase changing matter is paraffin or lipid acid and derivative thereof.
4, phase-change accumulation energy haydite according to claim 1, it is characterized in that the outer layer copolymer based composites with resin, emulsion as base material, with thermal conductivity greater than the metal of 10w/mk or inorganic non-metallic powder as filler, filler accounts for matrix material weight ratio 1-4%.
5, a kind ofly it is characterized in that adopting the vacuum infiltration method, haydite is absorbed and store organic phase change material as the described phase-change accumulation energy preparation method of porcelain granule of one of claim 1-4; Adopt the method for immersing again, at the outside coated polymer based composites of haydite rete.
6, preparation method according to claim 5 is characterized in that the step of vacuum infiltration method is as follows: earlier by vacuumizing the air that extracts in the haydite, under vacuum environment haydite is soaked in the organic phase changing matter solution then; Remove vacuum, continue again to soak more than 30 minutes.
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| CN1303182C true CN1303182C (en) | 2007-03-07 |
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| CN100341973C (en) * | 2004-09-28 | 2007-10-10 | 北京巨龙博方科学技术研究院 | Process for preparing phase change energy-storage material(PCM) |
| CN102531550B (en) * | 2011-12-22 | 2013-04-24 | 山东大学 | Poly fatty acid shape-stabilized phase change material and preparation method thereof |
| CN103509526B (en) * | 2012-06-17 | 2016-01-20 | 曹雪娟 | Porous base phase-change thermal storage particle and preparation method thereof |
| CN102827583B (en) * | 2012-08-03 | 2015-06-17 | 上海英硕聚合材料股份有限公司 | Phase change composite material and preparation method thereof |
| CN104086134B (en) * | 2014-06-20 | 2017-06-09 | 沈阳建筑大学 | Paraffin/haydite phase-change accumulation energy concrete and preparation method |
| CN104496544A (en) * | 2014-12-30 | 2015-04-08 | 深圳大学 | Phase change energy storage ceramsite and preparation method thereof |
| CN104803701A (en) * | 2015-02-17 | 2015-07-29 | 天津新滨工程技术检测有限公司 | Composite phase-change insulation board and preparation method |
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| CN105036627B (en) * | 2015-07-27 | 2017-09-01 | 浙江方远新材料股份有限公司 | A kind of interconvertibility roofing self-heat conserving haydite concrete |
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| CN112851403A (en) * | 2021-02-04 | 2021-05-28 | 西安建筑科技大学 | Hollow phase change energy storage ceramsite and preparation method thereof |
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| CN114231254B (en) * | 2021-12-14 | 2023-12-22 | 佛山欧神诺陶瓷有限公司 | Composite ceramic material with phase-change temperature regulation and preparation method and application thereof |
| CN116253545B (en) * | 2022-12-28 | 2024-06-11 | 中铁大桥局集团有限公司 | Low-shrinkage ultra-freezing-resistant coarse aggregate ultra-high-performance concrete pavement layer and preparation method thereof |
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