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CN111826126B - Phase change material for low-temperature cold accumulation at-77 to-88 ℃ and preparation method thereof - Google Patents

Phase change material for low-temperature cold accumulation at-77 to-88 ℃ and preparation method thereof Download PDF

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CN111826126B
CN111826126B CN201910326481.8A CN201910326481A CN111826126B CN 111826126 B CN111826126 B CN 111826126B CN 201910326481 A CN201910326481 A CN 201910326481A CN 111826126 B CN111826126 B CN 111826126B
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phase change
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CN111826126A (en
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史全
柴思瑀
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Dalian Institute of Chemical Physics of CAS
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    • C09K5/00Heat-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
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Abstract

本发明公开了一种低温蓄冷相变材料及其制备方法。该方法通过酮类、醛类与烷烃类中的两种或者三种混合来合成蓄冷相变材料。本方法合成的低温相变材料具有相变潜热较高、热稳定性好和制备成本低的优点,易于其在蓄冷方面的有很大应用。

Figure 201910326481

The invention discloses a low temperature cold storage phase change material and a preparation method thereof. In the method, the cold storage phase change material is synthesized by mixing two or three kinds of ketones, aldehydes and alkanes. The low-temperature phase change material synthesized by the method has the advantages of high latent heat of phase change, good thermal stability and low preparation cost, and is easy to be widely used in cold storage.

Figure 201910326481

Description

Phase change material for low-temperature cold accumulation at-77 to-88 ℃ and preparation method thereof
Technical Field
The invention relates to the field of phase change energy storage, in particular to a low-temperature cold accumulation phase change material and a preparation method thereof.
Background
With the development of industry, the living standard is improved, so that the world faces the problem of energy crisis. In the aspect of electric energy, particularly in summer, due to the fact that the requirements of people for life are increasingly improved, the difference of electricity consumption in daytime and at night is large due to the use of various electric appliances such as air conditioners and refrigerators, the peak-valley load difference is large, and the load rate of a power grid is reduced. At present, the country encourages to develop low-ebb electricity utilization and can realize 'peak shifting and valley filling'. Meanwhile, with the enhancement of crisis awareness of people, the development of new energy becomes a research hotspot at present. The cold accumulation technology can adjust energy supply and demand, save operation cost and realize high-efficiency and reasonable utilization of energy. The phase change cold storage material can be used as a carrier for storing energy, stores the energy in the low valley of the power load, slowly releases the energy in the peak of the power load, and the like, and has important significance in the aspect of energy conservation.
The cold accumulation technology is a high and new technology for regulating and controlling the environmental temperature by storing sensible heat, latent heat or reaction heat in chemical reaction at high density in the process of changing the state of a working medium. The method has important application value and wide development prospect in the fields of peak-valley balance of electric power, energy conservation and refrigeration transportation of air conditioners, low-temperature storage of substances and the like. For example, the annual power consumption of a 5000-ton refrigerator is about 800 million kilowatt hours, and the total amount of the refrigerator in China reaches 800 million tons; in the aspect of low-temperature logistics, due to different temperature requirements of transported goods, different cold storage technologies need to be researched according to the suitable temperature of the goods.
And nowadays, with the development of scientific technology, the environment required by research can be more accurate, and many experiments need to maintain a specific temperature during the experiment to maintain the reaction to continue, or the temperature environment of the experiment needs to be kept unchanged in order to recycle the sample and to store the sample after the experiment.
The phase change cold storage material is widely applied to various industries, and when a sample needs to be maintained in an ultralow temperature space, most of researches are at a medium-low temperature, and few researches on the phase change material at the ultralow temperature are available. The inorganic phase-change material has serious supercooling phenomenon and phase separation phenomenon, and the stability and the cyclicity are all to be improved. The organic phase-change material has the advantages of no corrosion, no supercooling, no phase separation, stable thermal performance and the like.
Disclosure of Invention
Based on the defects of the background technology, the invention aims to provide the low-temperature cold accumulation phase-change material which has the temperature of-77 to-88 ℃, does not corrode, does not have supercooling, does not have the phase separation phenomenon and has stable thermal performance.
The synthesis of the low-temperature cold accumulation phase-change material comprises the following steps:
(1) mixing ketone, aldehyde and alkane in certain proportion to obtain mixed solution.
(2) The mixture is strictly sealed and stirred at normal temperature for a period of time to be uniformly mixed, and the low-temperature cold accumulation phase-change material is obtained.
Further, the mixing proportion of the prepared low-temperature cold accumulation phase-change material is ketone: aldehydes: 67-85% of alkane and 0-18% of alkane: 0 to 16%.
Furthermore, the ketones adopted by the prepared low-temperature cold accumulation phase change material are one or more of 3-pentanone, 2-pentanone, heptanone and butanone.
Furthermore, the aldehyde adopted by the prepared low-temperature cold accumulation phase change material is one or more of propionaldehyde, butyraldehyde and heptaldehyde.
Furthermore, the alkane adopted by the prepared low-temperature cold accumulation phase change material is one or more of octane, nonane, decane and heptane.
Further, the stirring time for preparing the low-temperature cold accumulation phase change material is 30-60 min.
Further, the rotating speed of the prepared low-temperature cold accumulation phase-change material is 300-400 r/min.
Furthermore, the melting point of the prepared low-temperature cold accumulation phase-change material is-77 to-88 ℃.
The reagents involved in the invention are simple and easy to obtain, the operation requirement of preparation is low, and the prepared low-temperature cold accumulation phase-change material is transparent liquid and has the advantages of high phase-change performance, good cycle stability and the like. The product can be applied to the aspects of liquefied natural gas cold energy storage, environmental constant temperature keeping in the experimental process, medicine transportation and the like.
Drawings
FIG. 1 is a DSC curve of the product of example 1.
Detailed Description
Example 1
(1) The heptanone, heptaldehyde and decane were mixed in a molar ratio of 78:12: 10.
(2) And stirring for 30min at normal temperature after strict packaging at 400r/min to obtain a uniform mixed solution, namely the low-temperature cold accumulation phase change material, and the material can still keep good phase change latent heat and temperature phase change performance after 500-30-120 ℃ temperature rise and fall reciprocating thermal cycles.
Example 2
(1) 3-pentanone, octane and decane were mixed in a molar ratio of 88.7:10: 1.3.
(2) And then strictly packaging the materials, and stirring the materials at the normal temperature for 60min at 300r/min to obtain a uniform mixed solution, namely the low-temperature cold accumulation phase change material is prepared.
Example 3
(1) Pentanone and nonane are mixed in a molar ratio of 85: 15.
(2) And then strictly packaging, and stirring at the normal temperature for 45min at 350r/min to obtain a uniform mixed solution, namely preparing the low-temperature cold accumulation phase change material.
Example 4
(1) Hexanone, heptanal and octane are mixed according to a molar ratio of 82:8: 10.
(2) And after strict packaging, stirring at the normal temperature at 350r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 5
(1) Mixing 2-pentanone, propionaldehyde and decane according to a molar ratio of 79:15: 6.
(2) And after strict packaging, stirring at normal temperature at 400r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 6
(1) Mixing butanone, heptaldehyde and nonane according to a molar ratio of 72:13: 15.
(2) And after strict packaging, stirring at the normal temperature at 350r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 7
(1) Hexanone and octane were mixed in a molar ratio of 85: 15.
(2) And after strict packaging, stirring at normal temperature for 30min at 300r/min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 8
(1) 3-pentanone, propionaldehyde and nonane are mixed according to a molar ratio of 67:18: 15.
(2) And after strict packaging, stirring at the normal temperature at 350r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 9
(1) Hexanone, heptane and octane were mixed in a molar ratio of 68:16: 16.
(2) And after strict packaging, stirring at normal temperature at 400r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Example 10
(1) 3-pentanone, heptanal and butyraldehyde are mixed according to a molar ratio of 84:7: 9.
(2) And after strict packaging, stirring at normal temperature for 30min at 300r/min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Comparative example 1
(1) Heptanone, propionaldehyde and octane were mixed in a molar ratio of 90:5: 5.
(2) And then strictly packaging and stirring at the normal temperature for 30min at 300r/min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Comparative example 2
(1) Butanone, heptaldehyde and decane were mixed in a molar ratio of 60:25: 15.
(2) And then strictly packaging and stirring at the normal temperature at 350r/min for 30min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Comparative example 3
(1) 3-pentanone, nonane and octane were mixed in a molar ratio of 30:10: 60.
(2) And then strictly packaging the materials, and stirring the materials at the normal temperature for 30min at 400r/min to obtain a uniform mixed solution, namely the low-temperature cold accumulation phase change material is prepared.
Comparative example 4
(1) Heptanone, propionaldehyde and butane were mixed in a molar ratio of 50:25: 25.
(2) And then strictly packaging and stirring at the normal temperature for 30min at 300r/min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Comparative example 5
(1) Butanone, heptaldehyde and octane were mixed in a molar ratio of 35:12: 53.
(2) And then strictly packaging and stirring at the normal temperature for 30min at 300r/min to obtain a uniform mixed solution, thus obtaining the low-temperature cold accumulation phase change material.
Table 1 properties of low-temperature phase change cold storage materials obtained in examples 1 to 3
Figure BDA0002036358120000061
Table 1 properties of low-temperature phase change cold storage materials obtained in examples 1 to 3
Figure BDA0002036358120000062

Claims (9)

1. 一种低温蓄冷相变材料,其特征在于:由酮类,以及醛类、烷烃类中的一种或二种以上混合而成;1. A low-temperature cold storage phase change material, characterized in that: by mixing one or more of ketones, and aldehydes, alkanes; 酮类为 3-戊酮、2-戊酮、庚酮、丁酮中的一种或二种以上;相变材料中酮类: 醛类:烷烃类摩尔比例为 67~85%:0~18%:0~16%;相变材料中醛类、烷烃类中的一种或二种以上所占的摩尔比例大于等于 15%;醛类为丙醛、丁醛、庚醛中的一种或二种以上;The ketones are one or more of 3-pentanone, 2-pentanone, heptanone and butanone; the ketones in the phase change material: aldehydes: alkanes in a molar ratio of 67~85%: 0~18 %: 0~16%; the molar ratio of one or more of aldehydes and alkanes in the phase change material is greater than or equal to 15%; the aldehydes are one or more of propionaldehyde, butyraldehyde, and heptanal two or more; 烷烃类为辛烷、壬烷、癸烷中的一种或二种以上。The alkanes are one or more of octane, nonane and decane. 2.根据权利要求 1 所述的低温蓄冷相变材料,其特征在于:相变材料中酯类:醇类:烷烃类的摩尔比例为 78-79%:11-12%:9-10%。2. The low temperature cold storage phase change material according to claim 1, wherein the molar ratio of esters: alcohols: alkanes in the phase change material is 78-79%: 11-12%: 9-10%. 3.根据权利要求 1或2所述的低温蓄冷相变材料,其特征在于:所述有机低温相变材料的熔点为-77~-88℃。3. The low temperature cold storage phase change material according to claim 1 or 2, wherein the organic low temperature phase change material has a melting point of -77~-88°C. 4.一种权利要求 1所述的低温蓄冷相变材料的制备方法,其特征在于: 包括以下步骤:4. A method for preparing a low temperature cold storage phase change material according to claim 1, characterized in that: comprising the following steps: 1)将酮类,以及醛类与烷烃类中一种或两种物质按比例混合,得到混合溶液;酮类为3-戊酮、2-戊酮、庚酮、丁酮中的一种或多种;摩尔混合比例为酮类: 醛类:烷烃类为 67~85%:0~18%:0~16%;1) Mix one or both of ketones, aldehydes and alkanes in proportion to obtain a mixed solution; the ketones are one of 3-pentanone, 2-pentanone, heptanone, and butanone or A variety of; the molar mixing ratio is ketones: aldehydes: alkanes are 67~85%: 0~18%: 0~16%; 2)将混合溶液密封在常温下进行搅拌使其混合均匀,得到低温蓄冷相变材2) The mixed solution is sealed and stirred at room temperature to make it evenly mixed to obtain a low temperature cold storage phase change material 料。material. 5.根据权利要求 4所述的低温蓄冷相变材料的制备方法,其特征在于: 所述步骤(1)中醛类为丙醛、丁醛、庚醛中的一种或多种;5 . The method for preparing a low temperature cold storage phase change material according to claim 4 , wherein: in the step (1), the aldehydes are one or more of propionaldehyde, butyraldehyde, and heptanaldehyde; 6 . 所述步骤(1)中烷烃为辛烷、壬烷、癸烷中的一种或多种。In the step (1), the alkane is one or more of octane, nonane and decane. 6.根据权利要求 4所述的低温蓄冷相变材料的制备方法,其特征在于:所6. The preparation method of the low temperature cold storage phase change material according to claim 4, wherein: 述步骤(2)中搅拌时间为 30~60min。The stirring time in the above step (2) is 30~60min. 7.根据权利要求 4所述的低温蓄冷相变材料的制备方法,其特征在于: 所述步骤(2)中转速为 300~400r/min。7 . The method for preparing a low temperature cold storage phase change material according to claim 4 , wherein: the rotational speed in the step (2) is 300-400 r/min. 8 . 8.一种权利要求 1-3 任一所述低温蓄冷相变材料的应用,其可应用于低温条件下储能。8. An application of the low temperature cold storage phase change material according to any one of claims 1-3, which can be used for energy storage under low temperature conditions. 9.根据权利要求 8所述的低温蓄冷相变材料的应用,其特征在于:产品可应用于实验中保持环境恒温,药品的运输或液化天然气冷能储存等方面过程中。9. The application of the low-temperature cold storage phase change material according to claim 8, wherein the product can be used in the process of maintaining a constant temperature of the environment in experiments, transporting medicines or storing liquefied natural gas cold energy.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513648A (en) * 2015-01-15 2015-04-15 宁海德宝立新材料有限公司 Phase-change cold accumulation composite material based on butanediol
CN104531081A (en) * 2015-01-15 2015-04-22 宁海德宝立新材料有限公司 Phase change cold accumulation composite material based on polyethylene glycol
CN107474800A (en) * 2017-08-30 2017-12-15 北京赛科凌科技有限责任公司 A kind of cool storage material, regenerator and cold-accumulating refrigerating apparatus
CN107502298A (en) * 2017-08-23 2017-12-22 中国人民解放军军事医学科学院野战输血研究所 A kind of low temperature solid-liquid phase change agent for storage of coldness and preparation method and application
CN107709509A (en) * 2015-06-19 2018-02-16 株式会社钟化 Cool storage material composition, cool storage material and transport box

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513648A (en) * 2015-01-15 2015-04-15 宁海德宝立新材料有限公司 Phase-change cold accumulation composite material based on butanediol
CN104531081A (en) * 2015-01-15 2015-04-22 宁海德宝立新材料有限公司 Phase change cold accumulation composite material based on polyethylene glycol
CN107709509A (en) * 2015-06-19 2018-02-16 株式会社钟化 Cool storage material composition, cool storage material and transport box
CN107502298A (en) * 2017-08-23 2017-12-22 中国人民解放军军事医学科学院野战输血研究所 A kind of low temperature solid-liquid phase change agent for storage of coldness and preparation method and application
CN107474800A (en) * 2017-08-30 2017-12-15 北京赛科凌科技有限责任公司 A kind of cool storage material, regenerator and cold-accumulating refrigerating apparatus

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