JP2015038176A - Thermal energy storage material and method of producing thermal energy storage material - Google Patents
Thermal energy storage material and method of producing thermal energy storage material Download PDFInfo
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- 239000011232 storage material Substances 0.000 title claims abstract description 41
- 238000004146 energy storage Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title abstract 2
- 239000012188 paraffin wax Substances 0.000 claims abstract description 125
- 239000000839 emulsion Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000001879 gelation Methods 0.000 claims abstract description 21
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 84
- 239000003349 gelling agent Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 34
- 239000003112 inhibitor Substances 0.000 claims description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 abstract description 67
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000002844 melting Methods 0.000 description 27
- 230000008018 melting Effects 0.000 description 27
- 238000001816 cooling Methods 0.000 description 19
- 238000004781 supercooling Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000499 gel Substances 0.000 description 14
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 230000008014 freezing Effects 0.000 description 10
- 238000007710 freezing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 238000005338 heat storage Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004581 coalescence Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
Description
本発明は、熱エネルギー貯蔵材料および熱エネルギー貯蔵材料の製造方法に関する。 The present invention relates to a thermal energy storage material and a method for producing the thermal energy storage material.
化石燃料に代わる新規エネルギー源の開発は危急の課題である。また、同時に、太陽エネルギー、排熱、ピークオフ電力を有効利用するための技術の開発が求められている。その中で、近年、蓄熱材、蓄熱技術の開発が注目されている。空調システムを例にとると、電気エネルギーを熱エネルギーに変換、あるいは化石燃料（石油、石炭など）を燃やして熱エネルギーを得て温調している。この従来の方法では、化石燃料の枯掲は免れない。そのため、太陽エネルギーや工場や家庭から排出される熱を貯蔵して温調可能、繰り返し使用可能な熱エネルギー貯蔵材料の開発が必要不可欠である。 Developing new energy sources to replace fossil fuels is an urgent issue. At the same time, there is a demand for the development of technology for effectively using solar energy, exhaust heat, and peak-off power. Among them, in recent years, development of heat storage materials and heat storage technologies has attracted attention. Taking an air conditioning system as an example, electric energy is converted into thermal energy, or fossil fuels (oil, coal, etc.) are burned to obtain thermal energy and control the temperature. With this conventional method, the fossil fuel cannot be exhausted. Therefore, it is indispensable to develop thermal energy storage materials that can store solar energy and heat exhausted from factories and homes and can be used for temperature control and can be used repeatedly.
優れた乳化分散性、乳化安定性を示し、低粘度で且つ相変化に伴う吸熱、発熱量の大きい蓄熱材用エマルション組成物が特許文献１および特許文献２に開示されている。ｎ−パラフィンの分離が少なく、冷却時の粘度上昇が少ないパラフィンエマルションが特許文献３に開示されている。乳化剤を用いて相変化物質を水中に分散させ、温度変化に対する安定性を向上させたエマルション型蓄熱材が特許文献４に開示されている。界面活性剤を用いて相変化物質を水中に乳化分散させ、蓄熱材としての形態を安定化させ、耐加工性を向上させた包接型蓄熱材が特許文献５に開示されている。 Patent Document 1 and Patent Document 2 disclose emulsion compositions for heat storage materials that exhibit excellent emulsification dispersibility and emulsification stability, have low viscosity, and have a large endotherm and heat generation accompanying phase change. Patent Document 3 discloses a paraffin emulsion in which separation of n-paraffin is small and viscosity increase at the time of cooling is small. Patent Document 4 discloses an emulsion-type heat storage material in which a phase change material is dispersed in water using an emulsifier, and stability against temperature change is improved. Patent Document 5 discloses a clathrate type heat storage material in which a phase change material is emulsified and dispersed in water using a surfactant, the form as a heat storage material is stabilized, and the processing resistance is improved.
パラフィンは、人間が快適に生活できる温度範囲（１５℃〜３０℃）に融点を有し、過冷却度が小さく、化学的に安定な化合物である。パラフィンを液滴として水中に分散させたエマルション型の蓄熱材は、温度がパラフィンの凝固点以下になっても連続相となる水は凝固しないためパラフィン／水エマルションの流動性は保持される。しかし、パラフィンを液滴として水中に分散させることにより、エマルション中のパラフィン滴の凝固・融解現象は、バルクのパラフィンの凝固・融解現象とは異なり、過冷却度が大きくなる。図９に従来の一般的なパラフィン（ヘキサデカン）と水とのエマルションの示差熱分析測定による測定結果を示す。一般的なパラフィンと水とのエマルションは過冷却現象が起きて融解温度と凝固温度差が大きくなってしまう。これにより、室温付近に凝固点を有するパラフィンであっても、パラフィンを水中に分散させたエマルションでは、凝固点が４℃付近まで低下してしまう。また、パラフィン滴（油滴）が凝固・融解するときに、油結晶が界面膜を破壊することにより、エマルションの不安定化（油と水の相分離）が起こり、パラフィンン水エマルションの熱的安定性（繰り返し安定性）が低い。特許文献１〜５に記載の蓄熱材は、過冷却を防止することが記載されているものの、具体的には示されていなく、著しく抑制できるものではないという課題がある。 Paraffin is a chemically stable compound having a melting point in a temperature range (15 ° C. to 30 ° C.) in which a human can live comfortably, a low degree of supercooling, and the like. In an emulsion-type heat storage material in which paraffin is dispersed in water as droplets, the fluidity of the paraffin / water emulsion is maintained because water that becomes a continuous phase does not coagulate even when the temperature falls below the freezing point of paraffin. However, when the paraffin is dispersed in water as droplets, the solidification / melting phenomenon of the paraffin droplets in the emulsion increases the degree of supercooling unlike the solidification / melting phenomenon of bulk paraffin. FIG. 9 shows the measurement results of a conventional general paraffin (hexadecane) and water emulsion by differential thermal analysis measurement. In general, an emulsion of paraffin and water undergoes a supercooling phenomenon, resulting in a large difference between the melting temperature and the solidification temperature. Thereby, even if it is a paraffin which has a freezing point near room temperature, in the emulsion which disperse | distributed paraffin in water, a freezing point will fall to 4 degreeC vicinity. In addition, when paraffin droplets (oil droplets) solidify and melt, the oil crystals destroy the interfacial film, resulting in destabilization of the emulsion (phase separation of oil and water), and the heat of the paraffin water emulsion Low stability (repetitive stability). Although the heat storage materials described in Patent Documents 1 to 5 are described as preventing supercooling, they are not specifically shown and have a problem that they cannot be remarkably suppressed.
本発明は上記課題を解決すべくなされたものであり、その目的とするところは、パラフィン滴が水中に分散されたエマルションの過冷却を著しく抑制した熱エネルギー貯蔵材料および熱エネルギー貯蔵材料の製造方法を提供することにある。 The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to provide a thermal energy storage material in which supercooling of an emulsion in which paraffin droplets are dispersed in water is remarkably suppressed, and a method for producing the thermal energy storage material Is to provide.
上記の目的を達成するため、本発明は次の構成を備える。すなわち、本発明に係る熱エネルギー貯蔵材料は、パラフィンと、水と、油ゲル化剤とを含有し、前記パラフィンが前記油ゲル化剤によってゲル化され、該ゲル化されたパラフィン滴が水中に分散されたエマルションであることを特徴とする。この構成によれば、過冷却を著しく抑制できる。 In order to achieve the above object, the present invention comprises the following arrangement. That is, the thermal energy storage material according to the present invention contains paraffin, water, and an oil gelling agent, the paraffin is gelled by the oil gelling agent, and the gelled paraffin droplets are submerged in water. It is a dispersed emulsion. According to this configuration, supercooling can be remarkably suppressed.
また、本発明において、さらに、油ゲル化防止剤を含有することが好ましい。これによれば、水と混合される前のパラフィンが油ゲル化剤によってゲル化されることを防ぐ。 Moreover, in this invention, it is preferable to contain an oil gelling prevention agent further. This prevents the paraffin before being mixed with water from being gelled by the oil gelling agent.
また、本発明において、さらに、親水性高分子を含有することが好ましい。これによれば、過冷却を著しく抑制して、液相から固相への相転移時間を短くでき、熱的安定性もよくなる。 Further, in the present invention, it is preferable to further contain a hydrophilic polymer. According to this, supercooling is remarkably suppressed, the phase transition time from the liquid phase to the solid phase can be shortened, and the thermal stability is also improved.
また、本発明において、前記パラフィンの含有量が、エマルションの体積に対して、１．０〜５０ｖｏｌ％であることが好ましい。これによれば、適度な熱容量を有し、熱的安定性に優れていることから、液‐固相転移時間、固‐液相転移時間が適度な時間である。また、液相から固相への、または固相から液相への熱伝導性が良くなり、熱エネルギーを効率的に貯蔵、放出できる。 Moreover, in this invention, it is preferable that content of the said paraffin is 1.0-50 vol% with respect to the volume of an emulsion. According to this, since it has an appropriate heat capacity and is excellent in thermal stability, the liquid-solid phase transition time and the solid-liquid phase transition time are appropriate times. Further, the thermal conductivity from the liquid phase to the solid phase or from the solid phase to the liquid phase is improved, and heat energy can be efficiently stored and released.
また、本発明において、前記油ゲル化剤の含有量が、パラフィンの重量に対して、０．１〜１０ｗｔ％であることが好ましい。これによれば、パラフィン滴の分散状態が良く、熱的安定性が良い。 Moreover, in this invention, it is preferable that content of the said oil gelling agent is 0.1-10 wt% with respect to the weight of paraffin. According to this, the dispersion state of the paraffin droplets is good and the thermal stability is good.
また、本発明において、前記パラフィン滴の平均液滴径が、０．１〜１０μｍであることが好ましい。これによれば、パラフィン滴の分散状態が良くなる液滴径の範囲であり、パラフィン滴が崩壊しにくく熱的安定性が良い。 Moreover, in this invention, it is preferable that the average droplet diameter of the said paraffin droplet is 0.1-10 micrometers. According to this, it is the range of the droplet diameter in which the dispersion state of the paraffin droplets is improved, and the paraffin droplets are less likely to collapse and the thermal stability is good.
また、本発明において、前記パラフィンが、ヘキサデカンであることが好ましい。これによれば、生活温度付近に融点があり、熱伝導性が良い。 In the present invention, the paraffin is preferably hexadecane. According to this, there is a melting point near the living temperature, and the thermal conductivity is good.
また、本発明において、前記油ゲル化剤が、Ｎ‐ラウロイル‐Ｌ‐グルタミン酸‐α，γ‐ジ‐ｎ‐ブチルアミドであることが好ましい。これによれば、過冷却を抑制して熱的安定性もよく、さらに市販の油ゲル化剤を使用できてコストを削減できる。 In the present invention, the oil gelling agent is preferably N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide. According to this, supercooling is suppressed and the thermal stability is good, and further, a commercially available oil gelling agent can be used, and the cost can be reduced.
また、本発明において、前記油ゲル化防止剤が、極性有機溶媒であることが好ましい。これによれば、極性有機溶媒をパラフィンおよび水に溶解させることができ、水と接する前のパラフィンがゲル化されることを防止できる。 In the present invention, the oil gelation inhibitor is preferably a polar organic solvent. According to this, the polar organic solvent can be dissolved in paraffin and water, and the paraffin before coming into contact with water can be prevented from being gelled.
また、本発明において、前記親水性高分子がポリビニルピロリドンであることが好ましい。これによれば、エマルションの凝固温度が低下せずに、冷却時間を短くできる。 In the present invention, the hydrophilic polymer is preferably polyvinyl pyrrolidone. According to this, the cooling time can be shortened without lowering the solidification temperature of the emulsion.
上記の目的を達成するため、本発明は次の構成を備える。すなわち、本発明に係る熱エネルギー貯蔵材料の製造方法は、パラフィン滴を水中に分散させたエマルションを製造する際に、油ゲル化剤を用い、パラフィンと、油ゲル化剤と、水とを混合して、パラフィンをゲル化させることを特徴とする。この構成によれば、過冷却を著しく抑制した熱エネルギー貯蔵材料の製造方法できる。 In order to achieve the above object, the present invention comprises the following arrangement. That is, the method for producing a thermal energy storage material according to the present invention uses an oil gelling agent and mixes paraffin, an oil gelling agent and water when producing an emulsion in which paraffin droplets are dispersed in water. Then, the paraffin is gelled. According to this structure, the manufacturing method of the thermal energy storage material which suppressed supercooling significantly can be performed.
また、本発明において、さらに、油ゲル化防止剤を用い、前記パラフィンと、前記油ゲル化剤と、前記油ゲル化防止剤とを含有する混合液体を製造し、前記混合液体と、前記水とを混合して、前記混合液体中の前記油ゲル化防止剤を前記水に溶解し、前記混合液体中の前記パラフィンをゲル化させることが好ましい。これによれば、パラフィンがゲル化される時間を制御して、パラフィン滴を分散させたエマルションを製造しやすくすることができる。 Further, in the present invention, an oil gelation inhibitor is further used to produce a mixed liquid containing the paraffin, the oil gelling agent, and the oil gelation inhibitor, and the liquid mixture and the water It is preferable that the oil gelation inhibitor in the mixed liquid is dissolved in the water to gel the paraffin in the mixed liquid. According to this, it is possible to easily manufacture an emulsion in which paraffin droplets are dispersed by controlling the time during which paraffin is gelled.
本発明によれば、パラフィン滴が水中に分散されたエマルションの過冷却を著しく抑制した熱エネルギー貯蔵材料および熱エネルギー貯蔵材料の製造方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thermal energy storage material and the thermal energy storage material which suppressed significantly the supercooling of the emulsion in which the paraffin droplet was disperse | distributed in water can be provided.
以下本発明の実施の形態を詳細に説明する。
本実施形態に係る熱エネルギー貯蔵材料は、パラフィンと水とを含有し、さらに油ゲル化剤を含有してパラフィン滴がゲル化され、パラフィン滴が水中に分散されたエマルションである。油ゲル化剤を加えることで、冷却されてパラフィン滴が凝固するときの結晶核が提供されるのでパラフィン滴が凝固されやすくなり、過冷却が抑制される。これにより、熱エネルギー貯蔵材料の凝固温度（液‐固相転移温度）はパラフィンの凝固点とほとんど変わらない温度となる。さらにこのエマルション中のパラフィン滴同士の合一が抑制されるため、冷却加熱を繰り返して使用してもエマルション中のパラフィン滴は高分散状態を保つ。さらにパラフィンと水に相分離せず、熱的安定性が向上し、繰り返しの使用に耐えられる。
Hereinafter, embodiments of the present invention will be described in detail.
The thermal energy storage material according to the present embodiment is an emulsion containing paraffin and water, further containing an oil gelling agent, in which the paraffin droplets are gelled and the paraffin droplets are dispersed in water. By adding an oil gelling agent, a crystal nucleus is provided when the paraffin droplets are cooled and solidified, so that the paraffin droplets are easily solidified and supercooling is suppressed. As a result, the solidification temperature (liquid-solid phase transition temperature) of the thermal energy storage material becomes a temperature that is almost the same as the freezing point of paraffin. Furthermore, since the coalescence of the paraffin droplets in the emulsion is suppressed, the paraffin droplets in the emulsion maintain a highly dispersed state even when the cooling and heating are repeated. Furthermore, it does not phase-separate into paraffin and water, improves thermal stability, and can withstand repeated use.
製造されたエマルションは、高温側から低温側に温度変化させると、油滴の凝固点付近において熱を放出して凝固する。また、低温側から高温側へ温度変化させると油滴の融解温度付近で熱を吸収して融解する。製造されたエマルションは、相転移温度で熱を吸収・放出可能な材料であり、熱エネルギーを貯蔵できる材料である。また、パラフィンの凝固点温度以下であり、水の凝固点温度付近（２℃）においてパラフィンが凝固していても連続相となる水は凝固しないため、流動性を有するエマルションのままである。 When the produced emulsion is temperature-changed from the high temperature side to the low temperature side, it releases heat near the freezing point of the oil droplets and solidifies. Further, when the temperature is changed from the low temperature side to the high temperature side, the heat is absorbed and melted near the melting temperature of the oil droplets. The produced emulsion is a material that can absorb and release heat at a phase transition temperature, and can store heat energy. Moreover, it is below the freezing point temperature of paraffin, and even if the paraffin is solidified near the freezing point temperature of water (2 ° C.), the water that becomes a continuous phase does not solidify, so that the emulsion remains fluid.
図１は、油ゲル化剤によってゲル化されたパラフィン滴を示す模式図である。図１は、パラフィン内に油ゲル化剤が取り込まれている様子を示し、取り込んだ油ゲル化剤によってパラフィン滴の表面および内部がゲル化され、パラフィン滴全体が半固体状態になっている。
本実施形態で用いるパラフィンは油ゲル化剤によってゲル化される。パラフィンは水中でゲル化され、ゲル化されたパラフィン滴は水中に分散している。ここで、ゲルは完全な固体状態ではなく、固体と液体の性質を維持した半固体状態である。油ゲル化剤中の親油基とパラフィンとの親和力によってパラフィン中に油ゲル化剤が取り込こまれ、パラフィン内部で三次元のネットワークを形成する。この状態が進行すると流動性が失われていき、流動性が極めて低い状態（半固体状態）となる。これにより、ゲル化されて半固体状態のパラフィン滴が水中に分散したエマルションとなる。さらに、パラフィン滴全体がゲル化され、半固体状態であるので、パラフィン滴同士が衝突・接触しても合一が抑制されて、熱的安定性が良くなる。また、パラフィン滴の水中での分散安定性を向上させる効果もある。
FIG. 1 is a schematic diagram showing paraffin droplets gelled by an oil gelling agent. FIG. 1 shows a state in which an oil gelling agent is taken into paraffin. The surface and the inside of the paraffin droplet are gelled by the taken oil gelling agent, and the entire paraffin droplet is in a semi-solid state.
The paraffin used in this embodiment is gelled by an oil gelling agent. Paraffin is gelled in water and the gelled paraffin droplets are dispersed in water. Here, the gel is not in a completely solid state, but in a semi-solid state maintaining the properties of solid and liquid. The oil gelling agent is incorporated into the paraffin by the affinity between the lipophilic group and the paraffin in the oil gelling agent, and a three-dimensional network is formed inside the paraffin. As this state progresses, the fluidity is lost and the fluidity becomes extremely low (semi-solid state). Thereby, it becomes an emulsion in which the semi-solid paraffin droplets are dispersed in water. Furthermore, since the entire paraffin droplets are gelled and are in a semi-solid state, even if the paraffin droplets collide and contact each other, coalescence is suppressed and thermal stability is improved. It also has the effect of improving the dispersion stability of paraffin droplets in water.
油ゲル化剤は油をゲル化させるものであり、パラフィン以外の油もゲル化できるものである。油ゲル化剤は、親油性物質に作用し、親水性物質とは反発するので油水混在の状態から油だけをゲル化させることができる。 The oil gelling agent gels oil and can gel other oil than paraffin. The oil gelling agent acts on the lipophilic substance and repels the hydrophilic substance, so that only the oil can be gelled from a mixed oil / water state.
本実施形態の熱エネルギー貯蔵材料は、パラフィンと、油ゲル化剤と、水とを混合して、製造される。この場合、パラフィン、油ゲル化剤および水を容器に入れ、撹拌して混合してエマルションを製造できる。他にも、パラフィンと油ゲル化剤とを混合してゲル化されたパラフィンのゲルを製造し、パラフィンのゲルと水とを撹拌、混合してエマルションを製造してもよい。
また、本実施形態の熱エネルギー貯蔵材料は、パラフィンと、油ゲル化剤と、油ゲル化防止剤とを含有する混合液体を予め製造し、この混合液体を水に添加して製造してもよい。この混合液体中の油ゲル化防止剤は、混合液体中のパラフィンと油ゲル化剤とが反応して、パラフィンがゲル化されるのを防ぐための物質である。混合液体は水を含まず、流動性を有する液体状態であり、パラフィンはゲル化されていない。この混合液体を水に添加すると、混合液体中の油ゲル化防止剤が水に溶解し、混合液体中のパラフィンのゲル化が始まる。油ゲル化防止剤は水に溶解しやすく、親水性の物質である。このため、混合液体を水に添加すると混合液体中の油ゲル化防止剤は水相に移り、混合液体はパラフィンと、油ゲル化剤とを含有する液体となる。油ゲル化防止剤が抜け、これらすべての液体を混合することでパラフィンと油ゲル化剤との反応が始まり、パラフィン滴が水中に分散されたエマルションが製造される。また、油ゲル化防止剤を用いることにより、低温で、短時間でパラフィン／油ゲル化剤／水エマルションが調製できる利点がある。さらに、油ゲル防止剤の水への溶解性により、パラフィン滴中の油ゲル防止剤の量をコントロールすることができるため、ゲル化したパラフィン滴の粘弾性を制御することができる。
本実施形態で用いる油ゲル化剤は、低温（例えば、ＬＧＢＡの場合は１００℃以下）ではパラフィンに溶解しにくいため、油ゲル化防止剤を用いることにより、油ゲル化剤をパラフィンに溶解させやすくして、低温でも均一に溶解した混合液体が調製できる。
The thermal energy storage material of this embodiment is manufactured by mixing paraffin, an oil gelling agent, and water. In this case, an emulsion can be produced by placing paraffin, an oil gelling agent and water in a container, stirring and mixing. Alternatively, a paraffin gel obtained by mixing paraffin and an oil gelling agent may be manufactured, and the emulsion may be manufactured by stirring and mixing the paraffin gel and water.
Further, the thermal energy storage material of the present embodiment may be manufactured by previously manufacturing a mixed liquid containing paraffin, an oil gelling agent, and an oil gelation preventing agent, and adding the mixed liquid to water. Good. The oil gelation preventing agent in the mixed liquid is a substance for preventing the paraffin in the mixed liquid from reacting with the oil gelling agent and causing the paraffin to gel. The mixed liquid does not contain water and is in a liquid state having fluidity, and the paraffin is not gelled. When this mixed liquid is added to water, the oil gelling inhibitor in the mixed liquid is dissolved in water, and the gelation of paraffin in the mixed liquid starts. The oil gelation inhibitor is easily dissolved in water and is a hydrophilic substance. For this reason, when the mixed liquid is added to water, the oil gelation inhibitor in the mixed liquid moves to the aqueous phase, and the mixed liquid becomes a liquid containing paraffin and an oil gelling agent. The oil gelling agent is removed, and by mixing all these liquids, the reaction between paraffin and the oil gelling agent is started, and an emulsion in which paraffin droplets are dispersed in water is produced. Further, by using an oil gelation inhibitor, there is an advantage that a paraffin / oil gelling agent / water emulsion can be prepared at a low temperature in a short time. Furthermore, since the amount of the oil gel inhibitor in the paraffin droplets can be controlled by the solubility of the oil gel inhibitor in water, the viscoelasticity of the gelled paraffin droplets can be controlled.
The oil gelling agent used in the present embodiment is difficult to dissolve in paraffin at low temperatures (for example, 100 ° C. or less in the case of LGBA). Therefore, by using an oil gelation inhibitor, the oil gelling agent is dissolved in paraffin. This makes it easy to prepare a liquid mixture that is uniformly dissolved even at low temperatures.
また、本実施形態の熱エネルギー貯蔵材料は、親水性高分子が含まれていてもよく、パラフィンと、水と、油ゲル化剤と、親水性高分子とが含まれる液体を混合して、ゲル化されたパラフィン滴が水中に分散されたエマルションであってもよい。親水性高分子が含まれることで、過冷却を著しく抑制して、液相から固相への相転移時間を短くできる。また、より相分離しにくくなって熱的安定性もよくなる。さらに油ゲル化防止剤が含まれていてもよい。 Moreover, the thermal energy storage material of the present embodiment may contain a hydrophilic polymer, and a liquid containing paraffin, water, an oil gelling agent, and a hydrophilic polymer is mixed. It may be an emulsion in which gelled paraffin droplets are dispersed in water. By including the hydrophilic polymer, supercooling can be remarkably suppressed and the phase transition time from the liquid phase to the solid phase can be shortened. In addition, the phase separation becomes more difficult and the thermal stability is improved. Furthermore, an oil gelation inhibitor may be contained.
エマルション中には、エマルションの体積に対してパラフィンが１．０〜５０ｖｏｌ％含まれていることが好ましい。これにより、エマルションの過冷却が抑制される。また、液相から固相への液‐固相転移時間、固相から液相への固‐液相転移時間はいずれもパラフィンの濃度に比例して長くなる。このため、１．０ｖｏｌ％より少ないとエマルション中のパラフィン滴の量が十分ではなく、潜熱量が小さくなる。また、５０ｖｏｌ％より多いとパラフィンの平均液滴径が大きくなり、パラフィン滴同士の合一が起きて熱的安定性が悪くなる。 The emulsion preferably contains 1.0 to 50 vol% of paraffin with respect to the volume of the emulsion. Thereby, the supercooling of an emulsion is suppressed. In addition, the liquid-solid phase transition time from the liquid phase to the solid phase and the solid-liquid phase transition time from the solid phase to the liquid phase both increase in proportion to the paraffin concentration. For this reason, if it is less than 1.0 vol%, the amount of paraffin droplets in the emulsion is not sufficient, and the amount of latent heat becomes small. On the other hand, if it exceeds 50 vol%, the average droplet diameter of paraffin increases, and coalescence of paraffin droplets occurs, resulting in poor thermal stability.
図２は、エマルションを冷却したときの冷却時間と温度変化、および加熱したときの加熱時間と温度変化の一例を示すグラフである。ここで、凝固温度（液‐固相転移温度（Ｔｆ））および融解温度（固‐液相転移温度（Ｔｍ））は、温度が停滞し始めるときの温度であり、液相から固相への凝固時間（液‐固相転移時間（ｔｆ））は、冷却して４０℃のエマルションが２℃になるまでの時間とし、固相から液相への融解時間（固‐液相転移時間（ｔｍ））は、加熱して−１℃〜１℃のエマルションが２０℃になるまでの時間とする。 FIG. 2 is a graph showing an example of the cooling time and temperature change when the emulsion is cooled, and the heating time and temperature change when heated. Here, the solidification temperature (liquid-solid phase transition temperature (T f )) and the melting temperature (solid-liquid phase transition temperature (T m )) are temperatures at which the temperature starts to stagnate. The solidification time (liquid-solid phase transition time (t f )) is the time required for cooling to 40 ° C emulsion to 2 ° C, and the melting time from solid phase to liquid phase (solid-liquid phase transition) Time (t m )) is the time from heating to -1 ° C to 1 ° C emulsion reaching 20 ° C.
また、エマルション中には、パラフィンの重量に対して油ゲル化剤が、０．１〜１０ｗｔ％含まれていることが好ましい。油ゲル化剤の添加量はエマルションの凝固温度および融解温度に影響がほとんどないが、油ゲル化剤の量が少ないと、パラフィンが架橋されにくくてゲル化しにくく、油ゲル化剤の量が多いとゲル化し過ぎてパラフィン滴の分散性が悪くなる。 Moreover, it is preferable that 0.1-10 wt% of oil gelling agents are contained in the emulsion with respect to the weight of paraffin. The amount of oil gelling agent has almost no effect on the coagulation temperature and melting temperature of the emulsion, but if the amount of oil gelling agent is small, the paraffin is difficult to crosslink and gel, and the amount of oil gelling agent is large. And gelled too much and the dispersibility of the paraffin droplets deteriorates.
本実施形態に用いるパラフィンは、融点が生活温度付近にあり、熱伝導性が良いものを用いる。パラフィンとしては、アルカンを用いることができ、エマルションの融点は混合するアルカンの種類や量で調整できる。パラフィンの融点は１５℃〜３０℃であることが好ましく、例えば、ヘキサデカン、オクタデカン、オクタデセンを用いることができる。ヘキサデカンは融点が１８℃であり、エマルション中のパラフィンが凝固しても水の流動性が失われず熱伝導性が維持される。 As the paraffin used in the present embodiment, a paraffin having a melting point near the living temperature and good thermal conductivity is used. As the paraffin, an alkane can be used, and the melting point of the emulsion can be adjusted by the kind and amount of the alkane to be mixed. The melting point of paraffin is preferably 15 ° C. to 30 ° C., and for example, hexadecane, octadecane, and octadecene can be used. Hexadecane has a melting point of 18 ° C., and even if the paraffin in the emulsion solidifies, the fluidity of water is not lost and the thermal conductivity is maintained.
エマルションはホモジナイザーを用いて混合され、ローター式や超音波式のホモジナイザーを用い、これらを併用してもよい。使用するホモジナイザーの回転速度、混合時間を変えることにより、パラフィン滴の液滴径を変えることができ、ローター式ホモジナイザーと超音波ホモジナイザーを併用するとパラフィン滴の平均液滴径を２００ｎｍ以下にすることができる。パラフィン滴の平均液滴径は特に限定されないが、０．１〜１０μｍであることが好ましい。特に１００〜２００ｎｍであることがより好ましい。パラフィン滴の平均液滴径が０．１〜１０μｍとすることで、パラフィン滴が崩壊しにくくなってパラフィンの合一が起こりにくくなり、熱的安定性が良くなる。 The emulsion may be mixed using a homogenizer, and a rotor type or ultrasonic type homogenizer may be used in combination. By changing the rotation speed and mixing time of the homogenizer used, the droplet size of the paraffin droplets can be changed. When the rotor type homogenizer and the ultrasonic homogenizer are used in combination, the average droplet size of the paraffin droplets can be reduced to 200 nm or less. it can. The average droplet diameter of the paraffin droplets is not particularly limited, but is preferably 0.1 to 10 μm. In particular, the thickness is more preferably 100 to 200 nm. By setting the average droplet diameter of the paraffin droplets to 0.1 to 10 μm, the paraffin droplets are less likely to collapse and the coalescence of the paraffins is less likely to occur, and the thermal stability is improved.
本実施形態で用いる油ゲル化剤は、パラフィンをゲル化させることができれば特に限定されなく、高分子のポリマーを用い、例としてＮ‐ラウロイル‐Ｌ‐グルタミン酸‐α，γ‐ジ‐ｎ‐ブチルアミドを用いることができる。 The oil gelling agent used in the present embodiment is not particularly limited as long as it can gel paraffin, and a high molecular weight polymer is used, for example, N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide. Can be used.
本実施形態で用いる親水性高分子は、水に溶解するポリビニル系の化合物であり、ポリビニルピロリドンを用いることができる。 The hydrophilic polymer used in the present embodiment is a polyvinyl compound that dissolves in water, and polyvinylpyrrolidone can be used.
本実施形態の熱エネルギー貯蔵材料の凝固温度は、パラフィン自体の融点とほぼ変わらず過冷却が起こりにくい。例えばパラフィンとしてヘキサデカンを用いたとき、熱エネルギー貯蔵材料の凝固温度は、約１８℃となる。 The solidification temperature of the thermal energy storage material of the present embodiment is almost the same as the melting point of the paraffin itself, and supercooling hardly occurs. For example, when hexadecane is used as paraffin, the solidification temperature of the thermal energy storage material is about 18 ° C.
本実施形態で用いる油ゲル化防止剤は、混合液体中のパラフィンと油ゲル化剤とが反応して、パラフィンがゲル化されるのを防ぐための物質であり、親水基と親油基をもつ極性有機溶媒であることが好ましい。極性有機溶媒は特に限定されるものではないが、例として、エタノール、１−プロパノール、２−プロパノール等のアルコールを用いることができる。油ゲル化剤によるパラフィンのゲル化を防止できれば、油ゲル化防止剤の量は特に限定されない。また、本実施形態では界面活性剤を使用しない方が、過冷却が抑制されて熱的安定性が良くなる。 The oil gelation preventing agent used in the present embodiment is a substance for preventing paraffin from gelling due to the reaction of paraffin and oil gelling agent in the mixed liquid. A polar organic solvent is preferable. Although a polar organic solvent is not specifically limited, Alcohol, such as ethanol, 1-propanol, 2-propanol, can be used as an example. The amount of the oil gelation inhibitor is not particularly limited as long as paraffin gelation by the oil gelling agent can be prevented. In the present embodiment, when the surfactant is not used, supercooling is suppressed and thermal stability is improved.
以下、本発明を実施例に基づき詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, although the present invention is explained in detail based on an example, the present invention is not limited to this.
［実施例１］
ヘキサデカンに、ヘキサデカンに対して３ｗｔ％のＮ‐ラウロイル‐Ｌ‐グルタミン酸‐α，γ‐ジ‐ｎ‐ブチルアミド（ＬＧＢＡ）を添加し、１２０℃で加熱してＬＧＢＡを溶解させ、冷却してヘキサデカンゲルを調製した。製造されるエマルションの体積に対してヘキサデカンが３０ｖｏｌ％となるようにヘキサデカンゲルと水を容器に入れた。容器内の液体を歯車回転式ホモジナイザーで２０分間撹拌し、混合し、ヘキサデカン／ＬＧＢＡ／水エマルションを製造した。
[Example 1]
To hexadecane, 3 wt% N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide (LGBA) is added to hexadecane, heated at 120 ° C. to dissolve LGBA, cooled and cooled to hexadecane gel Was prepared. Hexadecane gel and water were put in a container so that hexadecane was 30 vol% with respect to the volume of the emulsion to be produced. The liquid in the container was stirred for 20 minutes with a gear-rotating homogenizer and mixed to produce a hexadecane / LGBA / water emulsion.
［実施例２］
ヘキサデカンと、ヘキサデカンに対して３ｗｔ％のＬＧＢＡと、ヘキサデカンに対して１５ｗｔ％のエタノールとを混合して混合液体を製造した。製造されるエマルションの体積に対してヘキサデカンが３０ｖｏｌ％となるように、混合液体と水を容器に入れた。容器内の液体を歯車回転式ホモジナイザーで２０分間撹拌し、混合し、ヘキサデカン／ＬＧＢＡ／水エマルションを製造した。
[Example 2]
Hexadecane, 3 wt% LGBA with respect to hexadecane, and 15 wt% ethanol with respect to hexadecane were mixed to produce a mixed liquid. The mixed liquid and water were placed in a container so that hexadecane was 30 vol% with respect to the volume of the emulsion to be produced. The liquid in the container was stirred for 20 minutes with a gear-rotating homogenizer and mixed to produce a hexadecane / LGBA / water emulsion.
［実施例３］
ＬＧＢＡの添加量を１ｗｔ％とし、実施例２と同様にしてヘキサデカン／ＬＧＢＡ／水エマルションを製造した。
[Example 3]
The amount of LGBA added was 1 wt%, and a hexadecane / LGBA / water emulsion was produced in the same manner as in Example 2.
［実施例４］
ＬＧＢＡの添加量を５ｗｔ％とし、実施例２と同様にしてヘキサデカン／ＬＧＢＡ／水エマルションを製造した。
[Example 4]
The amount of LGBA added was 5 wt%, and a hexadecane / LGBA / water emulsion was produced in the same manner as in Example 2.
［実施例５］
水の重量に対して２ｗｔ％のポリビニルピロリドン（親水性高分子：ＰＶＰ）を水に添加した。実施例２と同様の混合液体を製造し、製造されるエマルションの体積に対してヘキサデカンが３０ｖｏｌ％となるように混合液体とＰＶＰを含む水を容器に入れた。実施例２と同様にして、ヘキサデカン／ＬＧＢＡ／ＰＶＰ／水エマルションを製造した。
[Example 5]
2 wt% polyvinylpyrrolidone (hydrophilic polymer: PVP) was added to water based on the weight of water. A mixed liquid similar to that of Example 2 was produced, and water containing the mixed liquid and PVP was placed in a container so that hexadecane was 30 vol% with respect to the volume of the produced emulsion. In the same manner as in Example 2, a hexadecane / LGBA / PVP / water emulsion was produced.
［比較例１］
水の重量に対して２ｗｔ％のドデシル硫酸ナトリウム（界面活性剤：ＳＤＳ）を水に添加した。実施例２と同様の混合液体を製造し、製造されるエマルションの体積に対してヘキサデカンが３０ｖｏｌ％となるように混合液体とＳＤＳを含む水を容器に入れた。実施例２と同様にして、ヘキサデカン／ＬＧＢＡ／ＳＤＳ／水エマルションを製造した。
[Comparative Example 1]
2 wt% sodium dodecyl sulfate (surfactant: SDS) based on the weight of water was added to water. A mixed liquid similar to that of Example 2 was produced, and water containing the mixed liquid and SDS was placed in a container so that hexadecane was 30 vol% with respect to the volume of the produced emulsion. In the same manner as in Example 2, a hexadecane / LGBA / SDS / water emulsion was produced.
図３（Ａ）は、実施例２（ＬＧＢＡ３ｗｔ％）、実施例３（ＬＧＢＡ１ｗｔ％）、実施例４（ＬＧＢＡ５ｗｔ％）で製造したヘキサデカン／ＬＧＢＡ／水エマルションを冷却したときの冷却時間と温度変化を示すグラフである。図３（Ｂ）は、各ＬＧＢＡ濃度における凝固温度と凝固時間を示すグラフである。ＬＧＢＡの濃度が変化してもヘキサデカン滴の凝固時間はほとんど変わらず、凝固温度は１８℃であった。ヘキサデカンの凝固点とほぼ同じ温度であり、ヘキサデカン滴中のゲルネットワークが過冷却を抑制した。 FIG. 3 (A) shows the cooling time and temperature change when the hexadecane / LGBA / water emulsion produced in Example 2 (LGBA 3 wt%), Example 3 (LGBA 1 wt%), and Example 4 (LGBA 5 wt%) was cooled. It is a graph to show. FIG. 3 (B) is a graph showing the coagulation temperature and coagulation time at each LGBA concentration. Even when the concentration of LGBA was changed, the coagulation time of the hexadecane droplet was hardly changed, and the coagulation temperature was 18 ° C. The temperature was almost the same as the freezing point of hexadecane, and the gel network in the hexadecane droplet suppressed supercooling.
図４（Ａ）は、実施例２〜４で製造したヘキサデカン／ＬＧＢＡ／水エマルションを加熱したときの加熱時間と温度変化を示すグラフである。図４（Ｂ）は、各ＬＧＢＡ濃度における融解温度と融解時間を示すグラフである。ＬＧＢＡの濃度が増加するとヘキサデカン滴の融解時間は短縮された。融解温度は各ＬＧＢＡ濃度に対してほとんど変化しなかった。 FIG. 4A is a graph showing the heating time and temperature change when the hexadecane / LGBA / water emulsion produced in Examples 2 to 4 was heated. FIG. 4B is a graph showing the melting temperature and melting time at each LGBA concentration. As the LGBA concentration increased, the melting time of the hexadecane droplets was shortened. The melting temperature hardly changed for each LGBA concentration.
図５は、実施例２〜４で製造したヘキサデカン／ＬＧＢＡ／水エマルションの調製後の状態を示す外観写真である。また、エマルションを冷却、加熱し、それぞれ冷却後、加熱後の状態を示す外観写真である。調製後の各ＬＧＢＡ濃度のエマルションは、ヘキサデカン滴が分散している。ＬＧＢＡが１〜３ｗｔ％の間では、添加量が増加するに連れてエマルション中のヘキサデカン滴の分散性が高くなる。また、ＬＧＢＡが３〜５ｗｔ％の間では、添加量が増加するに連れてエマルション中のヘキサデカン滴が合一して、クリーミング状態となりやすくなる。このため、ＬＧＢＡが０．１〜１０ｗｔでは過冷却を著しく抑制できるが、エマルションの重量に対してＬＧＢＡを３ｗｔ％添加したときのエマルションは、冷却と加熱を繰り返してもヘキサデカン滴の分散性が高くて熱的安定性が最も良く、好適である。 FIG. 5 is an appearance photograph showing the state after preparation of the hexadecane / LGBA / water emulsion produced in Examples 2-4. Moreover, it is an external appearance photograph which shows the state after cooling and heating an emulsion, and after cooling, respectively. In the emulsion of each LGBA concentration after preparation, hexadecane droplets are dispersed. When LGBA is 1 to 3 wt%, the dispersibility of hexadecane droplets in the emulsion increases as the amount added increases. Moreover, when LGBA is 3 to 5 wt%, as the addition amount increases, hexadecane droplets in the emulsion are coalesced, and a creaming state is likely to occur. For this reason, when LGBA is 0.1 to 10 wt, supercooling can be remarkably suppressed, but the emulsion when LGBA is added at 3 wt% with respect to the weight of the emulsion has high dispersibility of hexadecane droplets even if cooling and heating are repeated. And has the best thermal stability.
図６（Ａ）は、実施例２（Ｎｏ ｓｕｒｆａｃｔａｎｔ）、実施例５（ＰＶＰ）、比較例１（ＳＤＳ）で製造したエマルションを冷却したときの冷却時間と温度変化を示すグラフである。図６（Ｂ）は、凝固温度と凝固時間を示すグラフである。ＳＤＳを添加すると、界面活性剤を添加していないエマルションより凝固温度が低下して８℃になる。またＰＶＰを添加すると、凝固点は、界面活性剤を添加していないエマルションと同じ１８℃でヘキサデカンの凝固点と同じであり、過冷却が抑制された。凝固時間は、ほぼ同じである。 FIG. 6 (A) is a graph showing the cooling time and temperature change when the emulsions produced in Example 2 (No surfactant), Example 5 (PVP), and Comparative Example 1 (SDS) were cooled. FIG. 6B is a graph showing the solidification temperature and the solidification time. When SDS is added, the coagulation temperature is lowered to 8 ° C. from the emulsion without addition of the surfactant. Moreover, when PVP was added, the freezing point was the same as the freezing point of hexadecane at 18 ° C., which was the same as that of the emulsion to which no surfactant was added, and supercooling was suppressed. The clotting time is almost the same.
図７（Ａ）は、実施例２、実施例５、比較例１で製造したエマルションを加熱したときの加熱時間と温度変化を示すグラフである。図７（Ｂ）は、融解温度と融解時間を示すグラフである。ＳＤＳを添加すると、界面活性剤を添加していないエマルションより融解時間が２０分短縮した。また、ＰＶＰを添加すると、融解時間は、界面活性剤を添加していないエマルションより４０分短縮した。また、融解温度はＰＶＰを添加したエマルションは、界面活性剤を添加していないエマルションおよびＳＤＳを添加したエマルションより、上昇した。 FIG. 7A is a graph showing the heating time and temperature change when the emulsions produced in Example 2, Example 5, and Comparative Example 1 were heated. FIG. 7B is a graph showing the melting temperature and the melting time. When SDS was added, the melting time was shortened by 20 minutes compared to the emulsion without addition of surfactant. Moreover, when PVP was added, the melting time was 40 minutes shorter than that of the emulsion to which no surfactant was added. The melting temperature of the emulsion added with PVP was higher than that of the emulsion not added with the surfactant and the emulsion added with SDS.
図８は、ヘキサデカン／ＬＧＢＡ／水エマルション（実施例２）、ＰＶＰを含むエマルション（実施例５）、ＳＤＳを含むエマルション（比較例１）の調製後の状態を示す外観写真である。また、エマルションを冷却、加熱し、それぞれ冷却後、加熱後の状態を示す外観写真である。実施例５および比較例１のいずれの場合でも、ヘキサデカン滴の分散性が高く、冷却と加熱を繰り返してもヘキサデカンの分散性が良い。調製後のＳＤＳを含むエマルション（比較例１）は、ヘキサデカン滴が分散し、冷却して加熱してもヘキサデカン滴の合一が起きないので、熱安定性が良い。また、調製後のＰＶＰを含むエマルション（実施例５）も同様にヘキサデカン滴が分散し、冷却して加熱してもヘキサデカン滴の合一が起きないので、さらに熱安定性が良い。 FIG. 8 is an appearance photograph showing a state after preparation of a hexadecane / LGBA / water emulsion (Example 2), an emulsion containing PVP (Example 5), and an emulsion containing SDS (Comparative Example 1). Moreover, it is an external appearance photograph which shows the state after cooling and heating an emulsion, and after cooling, respectively. In any case of Example 5 and Comparative Example 1, the dispersibility of hexadecane droplets is high, and the dispersibility of hexadecane is good even when cooling and heating are repeated. The emulsion containing the prepared SDS (Comparative Example 1) has good thermal stability because hexadecane droplets are dispersed, and even when cooled and heated, coalescence of the hexadecane droplets does not occur. Further, the emulsion containing PVP after preparation (Example 5) is similarly dispersed in hexadecane droplets, and even when cooled and heated, coalescence of the hexadecane droplets does not occur, so that the thermal stability is further improved.
Claims (12)
前記パラフィンと、前記油ゲル化剤と、前記油ゲル化防止剤とを含有する混合液体を製造し、
前記混合液体と、前記水とを混合して、前記混合液体中の前記油ゲル化防止剤を前記水に溶解し、前記混合液体中の前記パラフィンをゲル化させることを特徴とする請求項１１に記載の熱エネルギー貯蔵材料の製造方法。 Furthermore, using an oil gelation inhibitor,
Producing a liquid mixture containing the paraffin, the oil gelling agent, and the oil gelling inhibitor;
12. The mixed liquid and the water are mixed, the oil gelation inhibitor in the mixed liquid is dissolved in the water, and the paraffin in the mixed liquid is gelled. A method for producing the thermal energy storage material according to 1.
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| JP2019038975A (en) * | 2017-08-29 | 2019-03-14 | 国立大学法人信州大学 | Emulsion type heat storage material and method for manufacturing the same |
| US20220177765A1 (en) * | 2016-09-20 | 2022-06-09 | Aspen Aerogels, Inc. | Aerogel composites including phase change materials |
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| JPH1192758A (en) * | 1997-09-19 | 1999-04-06 | Nippon Shokubai Co Ltd | Heat-storing agent composition and production thereof |
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| JP2006008760A (en) * | 2004-06-23 | 2006-01-12 | Seiko Polymer Corp | Latent heat storage material composition |
| JP2009292993A (en) * | 2008-06-09 | 2009-12-17 | Alcare Co Ltd | Heat-storing gel and cold or warm-keeping material using the same |
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| JPH1192758A (en) * | 1997-09-19 | 1999-04-06 | Nippon Shokubai Co Ltd | Heat-storing agent composition and production thereof |
| JP2004211056A (en) * | 2002-12-19 | 2004-07-29 | Nippon Shokubai Co Ltd | Heat storage material and heat storage system using heat storage material |
| JP2006008760A (en) * | 2004-06-23 | 2006-01-12 | Seiko Polymer Corp | Latent heat storage material composition |
| JP2009292993A (en) * | 2008-06-09 | 2009-12-17 | Alcare Co Ltd | Heat-storing gel and cold or warm-keeping material using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20220177765A1 (en) * | 2016-09-20 | 2022-06-09 | Aspen Aerogels, Inc. | Aerogel composites including phase change materials |
| JP2019038975A (en) * | 2017-08-29 | 2019-03-14 | 国立大学法人信州大学 | Emulsion type heat storage material and method for manufacturing the same |
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