JPH0222784B2 - - Google Patents
Info
- Publication number
- JPH0222784B2 JPH0222784B2 JP265882A JP265882A JPH0222784B2 JP H0222784 B2 JPH0222784 B2 JP H0222784B2 JP 265882 A JP265882 A JP 265882A JP 265882 A JP265882 A JP 265882A JP H0222784 B2 JPH0222784 B2 JP H0222784B2
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- heat
- inorganic salt
- alkaline earth
- earth metal
- 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 16
- 239000000203 mixture Substances 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 239000011232 storage material Substances 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229940013553 strontium chloride Drugs 0.000 description 4
- 229910001631 strontium chloride Inorganic materials 0.000 description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004781 supercooling Methods 0.000 description 4
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229940047908 strontium chloride hexahydrate Drugs 0.000 description 2
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910003514 Sr(OH) Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- CTUDRLGCNRAIEA-UHFFFAOYSA-L calcium;chloride;hydroxide Chemical compound [OH-].[Cl-].[Ca+2] CTUDRLGCNRAIEA-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 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
本発明は、アルカリ金属またはアルカリ土類金
属の無機塩水和物を主体とする蓄熱剤組成物に関
するものである。
一般的に蓄熱を行う方法には、物質の顕熱を利
用する方法と潜熱を利用する方法とがある。顕熱
を利用する方法の代表的な例としては、水や砕石
を用いるものがあるが、この方法は蓄熱装置の容
量や重量が相当大きくなり、また熱の放出に伴い
蓄熱剤自身の温度が低下してしまう欠点がある。
これに対し、無機塩水和物や有機の結晶性物質が
おこす融解等の相変化潜熱を利用する方法は、放
熱に伴う蓄熱剤の温度低下は小さく、また融解等
の相変化潜熱は一般的に大きいので、蓄熱装置を
コンパクト化できる利点がある。
本発明は、この融解潜熱を利用して蓄熱する技
術、とくにアルカリ金属またはアルカリ土類金属
の無機塩水和物を蓄熱剤として用いるのに適する
ように改質する技術に関するものである。
元来無機塩水和物を蓄熱剤として用いる場合、
溶融状態から次第に降温させた時に本来の相変化
温度が過ぎても固化（結晶化）せず放熱しないと
いう過冷却現象が生じる。同時に不溶性物質の晶
出が融解時におこり、融解−固化のヒートサイク
ルをくり返すことにより不溶性物質が増加しつづ
け相分離現象を呈すなどの問題も生じる。
すでに本発明者らは、過冷却現象や相分離現象
の防止について発明し、特開昭57−1391705とし
て提案している。すなわち前記提案は、アルカリ
金属またはアルカリ土類金属の無機塩水和物にホ
ウ酸を添加することを要旨としている。しかし前
記提案をもつてしても、まだ改善の余地があつ
た。そこで本発明者らは、より一層過冷却現象を
防止し、単位重量あたりの有効潜熱量の大きい蓄
熱剤組成物につき鋭意研究を重ねてきた結果、本
発明を完成するに至つた。
すなわち本発明は、アルカリ土類金属の無機塩
水和物と、ホウ酸と、アルカリ土類金属の水酸化
物または無機塩無水物とからなることを特徴とす
る蓄熱剤組成物である。
本発明でいうアルカリ土類金属の無機塩水和物
としては、硫酸マグネシウム６水和物（Mg
（NO3）2・6H2O）、塩化マグネシウム６水和物
（MgCl2・6H2O）、塩化カルシウム６水和物
（CaCl2・6H2O）、塩化ストロンチウム・６水和
物（SrCl2・6H2O）等がある。これらは単独で使
用されるほか２種以上混合して用いてもよい。
ホウ酸の添加量は、水和物の種類によつても若
干異なるが組成物中0.1wt％以上、好ましくは
0.5wt％以上の範囲が好ましい。添加量の上限は
とくに作用効果上限定する必要はないが、多量の
添加はそれだけ蓄熱密度を減少させるので20wt
％以下、好ましくは10wt％くらいまでが実用的
である。
アルカリ土類金属の水酸化物または無機塩無水
物としては、塩化ストロンチウム（SrCl2）、弗化
ストロンチウム（SrF2）、水酸化ストロンチウム
（Sr（OH）2）、塩化バリウム（BaCl2）、弗化バリ
ウム（BaF2）、水酸化バリウム（Ba（OH）2）、塩
化マグネシウム（MgCl2）、弗化マグネシウム
（MgF2）、水酸化マグネシウム（Mg（OH）2）、塩
化カルシウム（CaCl2）、弗化カルシウム
（CaF2）、水酸化塩化カルシウム（Ca（OH）2）等
がある。このうち特に好ましいのは、塩化ストロ
ンチウム、弗化バリウム、水酸化バリウムであ
る。これらの化合物は、必要に応じて１種類また
は２種類以上が選ばれて使用される。添加量は、
組成物中0.1ないし10wt％、好ましくは0.5ないし
5wt％である。添加量が0.5％未満では過冷却防止
の改善効果が小さく、５％を超えると蓄熱密度を
減少させるので好ましくない。
また本発明の蓄熱剤組成物には、必要に応じて
他の添加剤を添加することが行われる。
実施例 １
塩化カルシウム６水和物80重量部と塩化マグネ
シウム６水和物20重量部の混合物に、塩化ストロ
ンチウムを２重量％、ホウ酸を２重量％添加した
もの（10ｇ）を、ガラス製円筒びんに封入し40℃
に加温したのち、５℃に調整した冷水100c.c.が入
つている断熱箱中に入れ、30分後の水温を測定し
た。また水10ｇを入れた円筒びん（40℃）を同じ
５℃の冷水の入つている断熱箱中に入れて30分後
の水温を測定して（フランク試験）、両者の水温
差より蓄熱剤の蓄熱密度に比例した値αを求めめ
た。
α＝（T2−T1）×100／10 （cal／ｇ）
T1：ブランクの水温
T2：蓄熱剤入断熱箱の水温
結果を第１表に示す。
比較例１〜６及び実施例２〜４
蓄熱剤組成物の組成を第１表に示す組成とする
以外は、実施例１と同様に行つた。
結果を第１表に示す。
The present invention relates to a heat storage agent composition mainly containing an inorganic salt hydrate of an alkali metal or an alkaline earth metal. Generally, there are two methods for storing heat: one that utilizes the sensible heat of a substance, and the other that utilizes latent heat. A typical example of a method that uses sensible heat is one that uses water or crushed stone, but this method requires a considerably large capacity and weight of the heat storage device, and the temperature of the heat storage agent itself increases as heat is released. It has the disadvantage of decreasing.
On the other hand, methods that utilize the latent heat of phase change caused by inorganic salt hydrates and organic crystalline substances, such as melting, cause a small temperature drop in the heat storage agent due to heat release, and the latent heat of phase change caused by melting, etc. Since it is large, it has the advantage that the heat storage device can be made more compact. The present invention relates to a technology for storing heat using this latent heat of fusion, and in particular to a technology for modifying an inorganic salt hydrate of an alkali metal or alkaline earth metal so that it is suitable for use as a heat storage agent. When originally using an inorganic salt hydrate as a heat storage agent,
When the temperature is gradually lowered from the molten state, a supercooling phenomenon occurs in which the material does not solidify (crystallize) and does not release heat even after the original phase change temperature has passed. At the same time, crystallization of insoluble substances occurs during melting, and as the heat cycle of melting and solidification is repeated, the amount of insoluble substances continues to increase, causing problems such as a phase separation phenomenon. The present inventors have already invented a method for preventing supercooling phenomena and phase separation phenomena, and proposed it in Japanese Patent Application Laid-Open No. 1391705/1983. That is, the gist of the above proposal is to add boric acid to an inorganic salt hydrate of an alkali metal or an alkaline earth metal. However, even with the above proposal, there was still room for improvement. Therefore, the present inventors have conducted extensive research into a heat storage agent composition that further prevents the supercooling phenomenon and has a large amount of effective latent heat per unit weight, and as a result, has completed the present invention. That is, the present invention is a heat storage agent composition comprising an inorganic salt hydrate of an alkaline earth metal, boric acid, and an alkaline earth metal hydroxide or inorganic salt anhydride. In the present invention, the inorganic salt hydrate of alkaline earth metal includes magnesium sulfate hexahydrate (Mg
(NO 3 ) 2・6H 2 O), magnesium chloride hexahydrate (MgCl 2・6H 2 O), calcium chloride hexahydrate (CaCl 2・6H 2 O), strontium chloride hexahydrate (SrCl 2・6H 2 O), etc. These may be used alone or in combination of two or more. The amount of boric acid added varies slightly depending on the type of hydrate, but is preferably 0.1 wt% or more in the composition.
A range of 0.5wt% or more is preferable. The upper limit of the amount added does not need to be particularly limited in terms of effectiveness, but adding a large amount will reduce the heat storage density accordingly, so 20wt
% or less, preferably up to about 10 wt%, is practical. Examples of alkaline earth metal hydroxides or inorganic salt anhydrides include strontium chloride (SrCl 2 ), strontium fluoride (SrF 2 ), strontium hydroxide (Sr(OH) 2 ), barium chloride (BaCl 2 ), and strontium fluoride (SrF 2 ). Barium chloride (BaF 2 ), barium hydroxide (Ba(OH) 2 ), magnesium chloride (MgCl 2 ), magnesium fluoride (MgF 2 ), magnesium hydroxide (Mg(OH) 2 ), calcium chloride (CaCl 2 ) , calcium fluoride (CaF 2 ), calcium hydroxide chloride (Ca(OH) 2 ), etc. Among these, particularly preferred are strontium chloride, barium fluoride, and barium hydroxide. One or more of these compounds may be selected and used as required. The amount added is
0.1 to 10 wt% in the composition, preferably 0.5 to 10 wt%
It is 5wt%. If the amount added is less than 0.5%, the effect of improving supercooling prevention will be small, and if it exceeds 5%, the heat storage density will be reduced, which is not preferable. Further, other additives may be added to the heat storage agent composition of the present invention as necessary. Example 1 A mixture of 80 parts by weight of calcium chloride hexahydrate and 20 parts by weight of magnesium chloride hexahydrate, to which 2% by weight of strontium chloride and 2% by weight of boric acid were added (10g), was placed in a glass cylinder. Sealed in a bottle at 40℃
After heating it to 5°C, it was placed in an insulated box containing 100cc of cold water adjusted to 5°C, and the water temperature was measured 30 minutes later. In addition, a cylindrical bottle (40℃) containing 10g of water was placed in an insulated box containing cold water at 5℃ and the water temperature was measured 30 minutes later (Frank test). The value α proportional to the heat storage density was determined. α=(T 2 −T 1 )×100/10 (cal/g) T 1 : Water temperature of blank T 2 : Water temperature of insulated box containing heat storage agent The results are shown in Table 1. Comparative Examples 1 to 6 and Examples 2 to 4 The same procedure as in Example 1 was conducted except that the composition of the heat storage agent composition was changed to the composition shown in Table 1. The results are shown in Table 1.
【表】
実施例 ５
塩化カルシウム６水和物90重量部と塩化ストロ
ンチウム６水和物（SrCl2・6H2O）10重量部の混
合物に、塩化ストロンチウム２重量％およびホウ
酸２重量％を添加したものについて、実施例１と
同様に行つた。その結果αは32cal／ｇであつた。[Table] Example 5 To a mixture of 90 parts by weight of calcium chloride hexahydrate and 10 parts by weight of strontium chloride hexahydrate (SrCl 2 6H 2 O), 2% by weight of strontium chloride and 2% by weight of boric acid were added. The same procedure as in Example 1 was conducted for the sample. As a result, α was 32 cal/g.
Claims (1)
と、アルカリ土類金属の水酸化物または無機塩無
水物とからなることを特徴とする蓄熱剤組成物。1. A heat storage agent composition comprising an alkaline earth metal inorganic salt hydrate, boric acid, and an alkaline earth metal hydroxide or inorganic salt anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP265882A JPS58120093A (en) | 1982-01-13 | 1982-01-13 | Composition of heat accumulating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP265882A JPS58120093A (en) | 1982-01-13 | 1982-01-13 | Composition of heat accumulating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58120093A JPS58120093A (en) | 1983-07-16 |
| JPH0222784B2 true JPH0222784B2 (en) | 1990-05-21 |
Family
ID=11535437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP265882A Granted JPS58120093A (en) | 1982-01-13 | 1982-01-13 | Composition of heat accumulating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58120093A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6264854B1 (en) * | 1995-09-07 | 2001-07-24 | Claude Q. C. Hayes | Heat absorbing temperature control devices and method |
| CN108822802B (en) * | 2018-04-23 | 2021-02-26 | 西北大学 | Aluminum-encapsulated quaternary disodium hydrogen phosphate dodecahydrate-based phase-change heat storage material |
-
1982
- 1982-01-13 JP JP265882A patent/JPS58120093A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58120093A (en) | 1983-07-16 |
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