【発明の詳細な説明】〔産業上の利用分野〕本発明は低温貯蔵性に優れた熱エネルギー貯蔵物質に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal energy storage material with excellent low temperature storage properties.
水和物が融解した状態すなわち熱エネルギーを貯蔵した
状態で安定化し、周囲の雰囲気温度が無機塩水和物の融
点以下の温度になっても結晶化が生じずに熱エネルギー
を貯蔵したままで保存でき、任意の時期に種結晶を投入
したりあるいは電気的刺激を与えると、その時点で結晶
化が起こり熱エネルギーを放出することはすでに知られ
ている（特開昭５９−５３５７８ ）。同公報によれば
、無機塩水和物として酢酸ナトリウム３水和物を使用す
ると、−２０℃まではこのような安定化状態を保ち続け
ることができると記載、されている。The hydrate is stabilized in a molten state, which stores thermal energy, and is stored without crystallization even if the surrounding atmosphere temperature drops below the melting point of the inorganic salt hydrate. It is already known that if a seed crystal is introduced or electrical stimulation is applied at an arbitrary time, crystallization will occur at that point and thermal energy will be released (Japanese Patent Laid-Open No. 59-53578). According to the publication, it is stated that when sodium acetate trihydrate is used as the inorganic salt hydrate, such a stable state can be maintained up to -20°C.
ところで、本発明者らが上記の技術内容につき追試検討
を行ったところ、酢酸ナトリウム３水和物／キサンタン
ガムの系では０℃前後から熱エネルギーの貯蔵安定性が
悪くなって、自己暴発反応によって結晶化が起き発熱し
てしまう可能性のあることが判った。この傾向は、とく
に−１Ｏ℃前後になると顕著になり、多くの場合自己発
熱してしまう。By the way, when the present inventors conducted a follow-up study on the above technical content, they found that in the sodium acetate trihydrate/xanthan gum system, the storage stability of thermal energy deteriorated from around 0°C, and crystallization occurred due to a self-explosion reaction. It was found that there is a possibility that the chemical reaction may occur and cause heat generation. This tendency becomes particularly noticeable at around -10°C, and in many cases self-heating occurs.
このような低温条件下での熱エネルギー貯蔵安定性の欠
如は、厳冬期の北国での使用可能性を打ち消してしまう
ことになる。This lack of thermal energy storage stability under such low-temperature conditions negates the possibility of its use in northern countries during the harsh winter months.
本発明の目的は、上記の従来技術の問題点を解決するこ
とであって、すなわち低温条件下での熱エネルギー貯蔵
安定性に優れた酢酸ナトリウム３水和物／キサンタンガ
ム系の熱エネルギー貯蔵物質を提供することにある。The purpose of the present invention is to solve the above-mentioned problems of the prior art, namely, to provide a sodium acetate trihydrate/xanthan gum-based thermal energy storage material that has excellent thermal energy storage stability under low-temperature conditions. It is about providing.
すなわち本発明は、酢酸すトリウム３水和物、キサンタ
ンガムおよびグリコール類とからなることを特徴とする
熱エネルギー貯蔵物質であって、その好適態様は酢酸ナ
トリウム３水和物１００重量部に対してキサンタンガム
０．５〜５重量部およびグリコール類１〜５０重量部の
割合からなる熱エネルギー貯蔵物質である。That is, the present invention provides a thermal energy storage material characterized by comprising sodium acetate trihydrate, xanthan gum, and glycols, and a preferred embodiment thereof is xanthan gum based on 100 parts by weight of sodium acetate trihydrate. It is a thermal energy storage material consisting of 0.5 to 5 parts by weight and 1 to 50 parts by weight of glycols.
本発明の熱エネルギー貯蔵物質の構成成分の１つである
キサンタンガムは、細菌Ｘａｎｔｈｏｍｏｎａｓｃｏｍ
ｐｅｓ ｔｒ ｔｓの培地より得られるＤ−グルコース
、Ｄ−マンノース、Ｄ−グルクロン酸を構成単位とする
細胞外へテロ多糖であり、これはケルコ社より商品名「
ケルトロル（ＫＥＬＴＲＯＬ ） Ｊあるいは［ケルザ
ン（にＥＬＺＡＮ ） Ｊとして市販されているので容
易に入手できる。Xanthan gum, which is one of the constituents of the thermal energy storage material of the present invention, is produced by the bacterium Xanthomonascoma.
It is an extracellular heteropolysaccharide whose constituent units are D-glucose, D-mannose, and D-glucuronic acid obtained from the culture medium of pestrts.
It is easily available as it is commercially available as KELTROL J or ELZAN J.
本発明の他の成分であるグリコール類としては、たとえ
ばエチレングリコール、プロピレングリコール、トリメ
チレングリコール、テトラメチレングリコール、１，３
−ブタンジオール、１，４−ブタンジオール、１．５−
ベンタンジオール、ジエチレングリコール、トリエチレ
ングリコール等を例示でき、これらは各単独で用いても
よいし２種以上混合して用いてもかまわない。Examples of glycols that are other components of the present invention include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3
-butanediol, 1,4-butanediol, 1.5-
Examples include bentanediol, diethylene glycol, triethylene glycol, etc., and these may be used alone or in a mixture of two or more.
本発明の熱エネルギー貯蔵物質は、酢酸ナトリウム３水
和物と前記のキサンタンガムおよびグリコール類とから
構成される。このうち酢酸ナトリウム３水和物は熱エネ
ルギー貯蔵の主体を成すものであって、潜熱型の熱エネ
ルギー貯蔵性を示す。The thermal energy storage material of the present invention is composed of sodium acetate trihydrate, the above-mentioned xanthan gum, and glycols. Among these, sodium acetate trihydrate is the main component of thermal energy storage, and exhibits latent heat type thermal energy storage properties.
キサンタンガムは、溶融して熱エネルギーを貯蔵してい
る酢酸ナトリウム３水和物をその状態で安定して保持す
ると共に、融解状態の熱エネルギー貯蔵物質をヒドロゲ
ル状に固定して系内における組成分布を均一化し、相分
離現象を起こしにくくする役目を有する。グリコール類
は低温下での酢酸ナトリウム３水和物／キサンタンガム
系の暴発反応を防止して自己発熱を起こさないようにし
、低温条件下での熱エネルギー貯蔵安定性を増す役目を
有する。このような各成分の役目から、熱エネルギー貯
蔵物質としての性能を充分に発揮するための各成分の組
成割合は、酢酸ナトリウム３水和物１ｏｏｉｉ部に対し
てキサンタンガムが０．５〜５重量部とくに１〜３重量
部、グリコール類が１〜５０重量部とくに１〜１５重量
部である。Xanthan gum stably maintains the molten sodium acetate trihydrate that stores thermal energy in that state, and fixes the molten thermal energy storage material in a hydrogel form to control the composition distribution within the system. It has the role of homogenizing and making it difficult for phase separation to occur. Glycols have the role of preventing the explosive reaction of the sodium acetate trihydrate/xanthan gum system at low temperatures, preventing self-heating, and increasing the thermal energy storage stability under low temperature conditions. Considering the role of each component, the composition ratio of each component to fully exhibit its performance as a thermal energy storage material is 0.5 to 5 parts by weight of xanthan gum per 10 parts of sodium acetate trihydrate. Particularly 1 to 3 parts by weight, and 1 to 50 parts by weight of glycols, particularly 1 to 15 parts by weight.
本発明の熱エネルギー貯蔵物質の他の態様として、本発
明の目的を損なわない範囲で、酢酸ナトリウム３水和物
以外の他の無機塩水和物やキサンタンガム以外の他の親
水性多糖類を配合させてもかまわない。As another embodiment of the thermal energy storage material of the present invention, other inorganic salt hydrates other than sodium acetate trihydrate and other hydrophilic polysaccharides other than xanthan gum may be blended within a range that does not impair the purpose of the present invention. It doesn't matter.
本発明の熱エネルギー貯蔵物質を利用してその熱挙動を
発現させるには次の如き方法を例示することができる。The following methods can be exemplified to utilize the thermal energy storage material of the present invention to exhibit its thermal behavior.
まず熱エネルギーを貯蔵させるには、本発明の熱エネル
ギー貯蔵物質が充填された任意形状の容器を太陽光線に
晒し太陽熱を貯蔵させる方法、夜間の低価格電力を利用
してヒーター発熱を行い、その熱を貯蔵させる方法、排
ガスや温排水の熱を熱交換方式により貯蔵させる方法、
回転機械の余剰動力を利用して発電を行いヒーター発電
を実施し貯蔵させる方法、エンジンの如き内燃機関の余
剰熱を貯蔵させる方法などがある。First, in order to store thermal energy, a container of any shape filled with the thermal energy storage material of the present invention is exposed to sunlight to store solar heat, and a heater generates heat using low-cost electricity at night. A method of storing heat, a method of storing heat from exhaust gas and heated wastewater using a heat exchange method,
There are methods such as a method of generating electricity using surplus power of a rotating machine and storing the power generated by a heater, and a method of storing surplus heat of an internal combustion engine such as an engine.
以上のようにして熱エネルギー貯蔵物質に蓄えられた熱
エネルギーを取り出すには、種結晶を投入する方法、先
端部分に本発明と同じ構成かグリコール類を除いた構成
の熱エネルギー貯蔵物質の結晶固化物を有した棒状体で
もって刺激を与える方法、電流でもって刺激を与える方
法などがある。In order to extract the thermal energy stored in the thermal energy storage material as described above, there is a method of introducing a seed crystal, and a method of crystallizing the thermal energy storage material having the same structure as the present invention or the structure excluding glycols at the tip part. There are methods of applying stimulation using a rod-shaped object, and methods of applying stimulation using electric current.
本発明は以上の構成をとることにより、■ 酢酸ナトリ
ウム３水和物が１度融解して熱エネルギーを蓄えた状態
になるとヒドロゲル状の安定状態となり、酢酸ナトリウ
ム３水和物の融解温度未満、とくに氷点下の低温条件に
なっても結晶化せず安定状態が保持され続ける、■ ヒ
ドロゲル状の安定状態であると、振動や衝撃といった力
学的刺激に反応しなくなり、運搬や保管に神経を使う必
要がない、■ 安定状態は半永久的に持続する、■ 任意の時期、任意の温度条件下（酢酸ナトリウム３
水和物の融点未満）いつでも貯蔵熱を取り出すことがで
きる、■ 何回でも繰り返し使用が可能である、といった優れ
た効果を示す。By adopting the above configuration, the present invention has the following advantages: (1) When sodium acetate trihydrate is melted once and stored thermal energy, it becomes a hydrogel-like stable state, which is lower than the melting temperature of sodium acetate trihydrate; In particular, it does not crystallize and remains stable even in sub-zero low temperature conditions.■ If it is in a hydrogel-like stable state, it does not respond to mechanical stimuli such as vibrations or shocks, making transportation and storage difficult. ■ The stable state lasts semi-permanently. ■ Any time and under any temperature conditions (sodium acetate 3
(below the melting point of the hydrate), the stored heat can be taken out at any time, and ■ it can be used repeatedly.
本発明の熱エネルギー貯蔵物質は以上に示した作用効果
を利用して各種の分野に応用が可能であり、たとえば釣
やダイビングといったレジャー用又は軍隊のサバイバル
用のインスタントカイロ、家庭用ルームヒーター、自動
車エンジンの冬期プレヒーター、熱感応型ミサイルの囮
といったものに利用できる。そのほか太陽熱の貯蔵、熱
の遠隔地への輸送などにも利用できる。The thermal energy storage material of the present invention can be applied to various fields by utilizing the above-mentioned effects, such as instant hand warmers for leisure use such as fishing and diving, for military survival, home room heaters, and automobiles. It can be used as a winter preheater for engines and as a decoy for heat-sensitive missiles. It can also be used to store solar heat and transport heat to remote locations.
以下に本発明の内容を好適な例でもって説明するが、本
発明はこれらの実施例に限定されるものではない。The content of the present invention will be explained below using preferred examples, but the present invention is not limited to these examples.
実施例１後述する酢酸ナトリウムの３モル倍量の純水を７５℃に
加温し、次いでキサンタンガム６ｇを配合し攪拌混合し
た。キサンタンガムが均一に分散したこの系内に、さら
に酢酸ナトリウム１８１ｇおよび表１に示す化合物を３
０ｇ配合して攪拌混合を続け、熱エネルギー貯蔵物質を
得た。得られた該貯蔵物は、熱エネルギーを貯蔵した融
解状態である。次に、この熱エネルギー貯蔵物質を均等
量になるよう３本の試験管に分割した。そして、同様の
操作を合計５回繰り返した。Example 1 Pure water in an amount of 3 moles of sodium acetate, which will be described later, was heated to 75° C., and then 6 g of xanthan gum was added and mixed with stirring. Into this system in which xanthan gum was uniformly dispersed, 181 g of sodium acetate and 3 of the compounds shown in Table 1 were added.
0g of the mixture was mixed and stirring was continued to obtain a thermal energy storage material. The resulting store is in a molten state that stores thermal energy. Next, this thermal energy storage material was divided into three test tubes in equal amounts. Then, the same operation was repeated a total of 5 times.
このようにして得られた試験管充填熱エネルギー貯蔵物
質を、−１５℃で５日間保存し、暴発反応を起こして結
晶化し自己発熱を生じたサンプルを調べた。このとき、
上述の１回の熱エネルギー貯蔵物質製造で出来る３本の
試験管充填サンプルのうち１本でも暴発反応を起こせば
、他の２本も暴発反応を起こしたものとして、暴発サン
プル数を算出した。結果を表１に示す。これによりグリ
コール系化合物を添加した場合、暴発サンプル数が０と
非常に優れた効果が認められる。The thus obtained thermal energy storage material filled in a test tube was stored at -15°C for 5 days, and samples that caused an explosive reaction, crystallized, and self-heated were examined. At this time,
The number of explosive samples was calculated based on the assumption that if even one of the three test tube filled samples produced in the above-mentioned single production of the thermal energy storage material caused an explosive reaction, the other two also caused an explosive reaction. The results are shown in Table 1. As a result, when a glycol-based compound is added, the number of explosive samples is 0, which indicates a very excellent effect.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
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