JPS6111276B2 - - Google Patents
Info
- Publication number
- JPS6111276B2 JPS6111276B2 JP56121051A JP12105181A JPS6111276B2 JP S6111276 B2 JPS6111276 B2 JP S6111276B2 JP 56121051 A JP56121051 A JP 56121051A JP 12105181 A JP12105181 A JP 12105181A JP S6111276 B2 JPS6111276 B2 JP S6111276B2
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- storage material
- nucleating agent
- added
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005338 heat storage Methods 0.000 claims description 24
- 239000011232 storage material Substances 0.000 claims description 14
- 239000002667 nucleating agent Substances 0.000 claims description 11
- 238000004781 supercooling Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
Description
【発明の詳細な説明】
(1) 発明の目的
過冷却を防止した蓄熱材を提供することを目的
とする。[Detailed description of the invention] (1) Object of the invention An object of the invention is to provide a heat storage material that prevents supercooling.
(2) 従来例
蓄熱方式には大きく分けると、顕熱利用方式、
潜熱利用方式、化学蓄熱方式の３種がある。顕熱
蓄熱は水や砂などの顕熱を利用するもので、一般
に広く用いられているものである。しかし、この
タイプは蓄熱容量が小さいため、装置が大きくな
つてしまう。化学蓄熱は反応熱や希釈熱を利用す
るものであるが、このタイプは反応が関与するた
め制御がむずかしく、装置が複雑になる。これに
対し、潜熱蓄熱は、蓄熱容量が大きいため、装置
のコンパクト化が可能であり、また複雑な装置も
必要としない。(2) Conventional examples Heat storage methods can be roughly divided into sensible heat utilization methods,
There are three types: latent heat utilization method and chemical heat storage method. Sensible heat storage utilizes the sensible heat of water, sand, etc., and is generally widely used. However, this type has a small heat storage capacity, so the device becomes large. Chemical heat storage uses reaction heat and dilution heat, but this type involves reactions, making it difficult to control and the equipment complex. On the other hand, since latent heat storage has a large heat storage capacity, the device can be made more compact and does not require a complicated device.
潜熱型蓄熱材としては、蓄熱容量が大きいこと
などから無機水和物が有望と思われるが、この無
機水和物には過冷却とゆう問題がある。すなわち
冷却すると溶融状態から凝固し、その際凝固熱が
出るのが一般的であるが、無機水和物では冷却し
ても、しばしば凝固せず、溶融状態のままである
ことが多い。これが過冷却現象で、この現象が起
これば、凝固熱が取り出せず、従つて、蓄熱材と
しての意味がなくなる。 Inorganic hydrates seem to be promising as latent heat storage materials because of their large heat storage capacity, but these inorganic hydrates have the problem of supercooling. That is, when cooled, it solidifies from a molten state, and generally generates solidification heat, but inorganic hydrates often do not solidify and remain in a molten state even when cooled. This is a supercooling phenomenon, and if this phenomenon occurs, the heat of solidification cannot be extracted, and therefore the material loses its meaning as a heat storage material.
(3) 発明の構成
本発明はリン酸水素ニナトリウムの水溶液に過
冷却防止用の核剤としてギブサイト構造の水酸化
アルミニウム〔Al（OH）2〕を添加してなる蓄熱材
を提供するものである。(3) Structure of the Invention The present invention provides a heat storage material made by adding aluminum hydroxide [Al(OH) 2 ] having a gibbsite structure as a nucleating agent to prevent supercooling to an aqueous solution of disodium hydrogen phosphate. be.
リン酸−水素ナトリウム〔Na2HPO4・
12H2O〕は融点が36℃、潜熱は100cal/molであ
り、大きな蓄熱量を有し、よつて蓄熱材として利
用可能である。 Phosphate-sodium hydrogen [Na 2 HPO 4・
12H 2 O] has a melting point of 36°C and a latent heat of 100 cal/mol, and has a large amount of heat storage, so it can be used as a heat storage material.
しかしこれらは容易に過冷却し、このまゝでは
蓄熱材として使用できない。そこで上記のような
核剤を、好ましくは溶解度以上に加える。すると
固体として存在する核剤が、リン酸水素ニナトリ
ウムなどの結晶化に際して、核の働きをし、こゝ
から結晶化が始まる。 However, these materials easily become supercooled and cannot be used as heat storage materials as they are. Therefore, the above-mentioned nucleating agent is preferably added in an amount higher than its solubility. Then, the nucleating agent, which exists as a solid, acts as a nucleus during the crystallization of disodium hydrogen phosphate, etc., and crystallization begins from this point.
一般に、結晶化の過程は、液体から固体の析出
する結晶核の生成過程と、固体である結晶の成長
過程に分けられる。結晶核の発生は、非平衝状態
におけるユラギの現象として統計的に扱われる
が、モデル的には、少数の原子団で構成される結
晶核のかけらともいうべき〓珠が溶液から生成
し、それが成長して結晶核となる過程として捉え
られる。こゝで結晶核はバルクの結晶の構成粒子
（分子、原子、イオン等）が少なくとも単位格子
の数倍以上集つて規則正しい配列をとつたものの
如く考えられる。〓珠は臨界結晶核半径より大き
なものになると成長して、この結晶核となるが、
リン酸水素ニナトリウムなどは〓珠が臨界結晶核
半径以上の大きさになる時のエネルギギヤツプが
大きいため、蓄しい過冷却を示すものと思われ
る。そして、核剤はこのエネルギギヤツプを小さ
くする役割をしているものと考えられる。 In general, the crystallization process can be divided into a process of generating crystal nuclei, in which a solid is precipitated from a liquid, and a process of growing a crystal, which is a solid. The generation of crystal nuclei is treated statistically as a phenomenon of fluctuation in a non-equilibrium state, but according to the model, beads, which can be called fragments of crystal nuclei composed of a small number of atomic groups, are generated from a solution. This can be seen as a process in which it grows and becomes a crystal nucleus. Here, a crystal nucleus can be thought of as a regular arrangement of constituent particles (molecules, atoms, ions, etc.) of a bulk crystal that are gathered together at least several times as many times as the unit cell. 〓When the beads become larger than the critical crystal nucleus radius, they grow and become this crystal nucleus,
Disodium hydrogen phosphate, etc., has a large energy gap when the beads become larger than the critical crystal nucleus radius, so they are thought to exhibit excessive supercooling. The nucleating agent is thought to play a role in reducing this energy gap.
なお、核剤としてのギプサイトタイプのAl
（OH）3の添加量は溶解度以上であるのが好まし
く、上限には特に制限はないが、実用上10重量％
以下が望ましい。また核剤の分散をよくするため
増粘剤等を添加してもよい。増粘剤としては、蓄
熱材に溶解するたとえばカルボキシルメチルセル
ロース（CMC）のような高分子物質である。 In addition, gypsite type Al as a nucleating agent
The amount of (OH) 3 added is preferably equal to or higher than the solubility, and there is no particular upper limit, but in practice it is 10% by weight.
The following are desirable. Further, a thickener or the like may be added to improve the dispersion of the nucleating agent. The thickener is a polymeric substance, such as carboxymethyl cellulose (CMC), which is dissolved in the heat storage material.
なお、蓄熱材の水溶液の濃度は、各々の結晶水
相当水分より若干水分量が多い程度の濃度、すな
わち蓄熱材が一旦結晶化すると、水溶液中の水分
のほとんどが結晶水として消費されるような濃度
とするのが好ましい。 The concentration of the aqueous solution of the heat storage material is such that the water content is slightly higher than the water equivalent to each crystal water, that is, once the heat storage material is crystallized, most of the water in the aqueous solution is consumed as crystal water. It is preferable to set it as concentration.
なお、ギブサイトはNa2HPO4・12H2Oにほと
んど溶けず、それ自体、蓄熱材の特性に影響を与
えないという利点を有する。 Incidentally, gibbsite has the advantage that it hardly dissolves in Na 2 HPO 4 .12H 2 O and does not itself affect the properties of the heat storage material.
(4) 実施例
実施例 １
Na2HPO4・12H2Oにギブサイト〔Al（OH）3〕
を1.0重量％加えたものを、蓄熱容器に密閉し
た。このものは33℃で凝固を開始した。この凝固
点は溶解−凝固を50回くり返えさせてもほとんど
変らなかつた。これについての事情を第１図のグ
ラフに表わした。なお、比較のため核剤を加えな
いものについてもグラフに表わした。両者の相違
が明れように表われている。(4) Examples Example 1 Gibbsite [Al(OH) 3 ] in Na 2 HPO 4・12H 2 O
1.0% by weight was added and sealed in a heat storage container. This material started solidifying at 33°C. This freezing point remained almost unchanged even after repeating melting and solidifying 50 times. The circumstances surrounding this are shown in the graph of Figure 1. For comparison, the graph also shows the results without the addition of a nucleating agent. The differences between the two are clearly visible.
実施例 ２
実施例１の組成物にさらに増粘剤としてCMC
を0.1重量％加えた場合も、ほぼ同様の特性を示
し、かつ核剤の分散が良好であつた。Example 2 The composition of Example 1 was further added with CMC as a thickener.
When 0.1% by weight was added, almost the same characteristics were exhibited, and the nucleating agent was well dispersed.
(5) 効 果
本発明はリン酸水素ニナトリウムの水溶液に過
冷却防止用の核剤としてギブサイト構造の水酸化
アルミニウムを添加してなるので過冷却が防止さ
れ、一定温度で吸熱、放熱が安定に行なわれると
いう効果を有する。(5) Effects In the present invention, aluminum hydroxide with a gibbsite structure is added to an aqueous solution of disodium hydrogen phosphate as a nucleating agent to prevent supercooling, so supercooling is prevented and heat absorption and heat radiation are stable at a constant temperature. It has the effect of being carried out.
第１図はNa2HPO4・12H2Oを蓄熱材として使
用した場合の凝固点を示すグラフである。
FIG. 1 is a graph showing the freezing point when Na 2 HPO 4 .12H 2 O is used as a heat storage material.
Claims (1)
止用の核剤としてギブサイト構造の水酸化アルミ
ニウムを添加してなる蓄熱材。 ２ 核剤が溶解度以上の量で添加されていること
を特徴とする特許請求の範囲第１項記載の蓄熱
材。 ３ 増粘剤を添加したことを特徴とする特許請求
の範囲第１項または第２項記載の蓄熱材。[Claims] 1. A heat storage material obtained by adding aluminum hydroxide having a gibbsite structure as a nucleating agent to prevent supercooling to an aqueous solution of disodium hydrogen phosphate. 2. The heat storage material according to claim 1, wherein the nucleating agent is added in an amount exceeding its solubility. 3. The heat storage material according to claim 1 or 2, characterized in that a thickener is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56121051A JPS5822897A (en) | 1981-07-31 | 1981-07-31 | Heat accumulating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56121051A JPS5822897A (en) | 1981-07-31 | 1981-07-31 | Heat accumulating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5822897A JPS5822897A (en) | 1983-02-10 |
| JPS6111276B2 true JPS6111276B2 (en) | 1986-04-02 |
Family
ID=14801611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56121051A Granted JPS5822897A (en) | 1981-07-31 | 1981-07-31 | Heat accumulating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5822897A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02132181A (en) * | 1988-07-08 | 1990-05-21 | Nok Corp | Latent thermal energy storing material |
| JP3621725B2 (en) * | 1994-07-21 | 2005-02-16 | 日本パイオニクス株式会社 | Cryogen |
-
1981
- 1981-07-31 JP JP56121051A patent/JPS5822897A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5822897A (en) | 1983-02-10 |
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