JPH0323112B2 - - Google Patents
Info
- Publication number
- JPH0323112B2 JPH0323112B2 JP60167599A JP16759985A JPH0323112B2 JP H0323112 B2 JPH0323112 B2 JP H0323112B2 JP 60167599 A JP60167599 A JP 60167599A JP 16759985 A JP16759985 A JP 16759985A JP H0323112 B2 JPH0323112 B2 JP H0323112B2
- Authority
- JP
- Japan
- Prior art keywords
- bromide
- heat storage
- dihydrate
- solubility
- chloride
- 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 - Lifetime
Links
- 238000005338 heat storage Methods 0.000 claims description 21
- 239000011232 storage material Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- 150000004683 dihydrates Chemical class 0.000 claims description 9
- 150000004687 hexahydrates Chemical class 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910001620 barium bromide Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 229910001622 calcium bromide Inorganic materials 0.000 claims 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims 1
- 229910001623 magnesium bromide Inorganic materials 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 hexahydrate halide Chemical class 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- HJKQUBPRUFDVHB-UHFFFAOYSA-N dihydrate;hydrobromide Chemical compound O.O.Br HJKQUBPRUFDVHB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910020361 KCl—LiCl Inorganic materials 0.000 description 1
- 229910013364 LiBr—LiCl Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
Description
〔発明の利用分野〕
本発明は液状蓄熱剤に係り、特に、溶解度が高
くかつ安価な六水塩と二水塩のハロゲン化合物か
ら構成される混合液状蓄熱剤に関する。
〔発明の背景〕
蓄熱剤は、主に比熱、即ち、顕熱の大きい材料
（固体、液体）を用いるものと、融解、若しくは、
気化の相変化による潜熱を利用するものに大別さ
れる。
前者は、水を代表例として他にコンクリートブ
ロツク、岩石等が用いられる蓄熱容量（短熱剤当
りの蓄熱量）が小さいため、大量の蓄熱剤が必要
である。
後者はさらに二つに分けられ、融解潜熱を利用
するものと、気化潜熱を利用するものがある。前
者には塩化カルシウム等を主剤とするものである
が固体であるため取り扱いが不便であり、融解開
始温度と凝固開始温度に大きな差が生じる過冷却
の問題がある（引例 特開昭53−70990号公報）
気化潜熱を利用するものの例は少なく、吸収式
冷凍機を短熱型にした時の臭化リチウム水溶液が
あるのみである。この方式は液状蓄熱剤を用い、
液状蓄熱剤を加熱し水分を蒸発させて、短熱剤を
濃縮することにより熱を濃度差に変えて蓄熱し、
使用時は、濃厚蓄熱剤に水蒸気を吸収させた時に
発生する凝縮潜熱を利用するものである。この方
式は水の凝縮潜熱（凝固潜熱六、七倍）を用いる
ため蓄熱容量が大きく、かつ、濃度差を利用する
ため発生温度を自由に変えられる特長（凝固温度
は一定だが水蒸気吸収温度は、雰囲気圧力と濃度
によつて変わる）がある。しかし、臭化リチウム
水溶液が塩化カルシウム等に比べ非常に高価であ
るので、大容量の蓄熱剤を必要とする蓄熱には不
適とされていた。
一方、液状蓄熱剤として安価な塩化マグネシウ
ムや塩化スルシウム等が考えられるが、溶解度が
小さく、濃度差を利用する気化潜熱法には不向き
である。
吸収冷凍機に用いる吸収剤についても、空冷化
を図り、さらに溶解度を上げるために、他の吸収
剤を混合する混合吸収剤の研究も速められてい
る。例えば、LiBr−LiCl系、LiBr−C2H6O2系、
LiBr−LiSCN系（冷凍、Vol56、No.646，p11）
及びLiCl−CaCl2系（低温度差エネルギーの有効
利用に関する研究・研究成果報告書１，1979年３
月６日発行、p102〜103）があるが、混合比の最
適化等はなされていない。
また、混合蓄熱剤として融解潜熱を利用した溶
融塩の融点調節としてKCl−LiCl系やMgCl2−
KCl系等がある）工業材料Vol26，No.９，p44）。
〔発明の目的〕
本発明の目的は、ハロゲン化合物を適切に混合
することにより、安価で、かつ、溶解度の高い混
合液状蓄熱剤を提供することにある。
〔発明の概要〕
発明者等は、液状蓄熱剤として適用可能な物質
を種々調査検討した所、水和物を形成するハロゲ
ン化物が安価で、かつ、溶解度も比較的高いこと
に気がついた。さらに、ハロゲン化合物を検討し
た結果、特に、臭化物と塩化物が溶解度、価格、
安全性の点で有利なことがわかつた。
これは、これまで吸収冷凍機で臭化リチウムや
塩化リチウムの水溶液が利用されているゆえんで
ある。
発明者等は、さらに検討を集めた結果、次の新
しい見解を得た。すなわち、大部分のハロゲン化
物の溶解度は(1)常温付近で結晶水をもつものの方
が大きい（例えば結晶水のないKClやNaClは六
水塩をもつMgCl2より溶解度は低い）(2)結晶水の
数が少ない方が大きい例えば二水塩をもつLiClの
方が六水塩をもつMgCl2より溶解度が大きい）(3)
塩化物より臭化物が大きい、（例えばLiClより
LiBrが溶解度が大きい）(4)しかし、単体の物質
での溶解度は液状蓄熱剤として不十分である。
そこで、発明者等は溶解度の向上させるについ
て種々検討した結果、結晶水をもつハロゲン化物
の溶解度は、それに水和する水分子の数に大きく
左右されることを発見し、その水和は共存イオン
（つまり、共存する他のハロゲン化物）によつて
変化することを実験で確認し、ハロゲン化物を混
合することにより、溶解度が向上できることを発
見した。
さらに、混合すべきハロゲン化物は、(1)二水塩
の方が溶解度は高いが高価、(2)六水塩は溶解度は
二水塩より低いが安価なことに着目し、ハロゲン
化物中最も溶解度の高い二水塩の臭化物と安価な
六水塩のハロゲン化物を選定した。
即ち、本発明の要旨は、安価な六水塩のハロゲ
ン化物と溶解度の大きな二水塩の臭化物を適切に
混合することにより、溶解度が高く、かつ、安価
な混合液状蓄熱剤とすることにある。
本発明の対象となる常温付近で二水塩になる代
表的なものにLiBr，BaBr2等の臭化物があり、
常温付近で六水塩になる代表的なものにMgCl2，
CaCl2，NiCl2，CoCl2等の塩化物やMgBr2，
CaBr2，NiBr2，CoBr2等の臭化物がある。
〔発明の実施例〕
以下、本発明を実施例を用いて詳細に説明す
る。
（溶解度測定方法）
第１表に用いた液状潜熱剤（六水塩を主剤、二
水塩添加剤）の種類と温度（温度０℃における主
剤の飽和濃度付近）を示す。
[Field of Application of the Invention] The present invention relates to a liquid heat storage agent, and particularly to a mixed liquid heat storage agent composed of halogen compounds of hexahydrate and dihydrate, which have high solubility and are inexpensive. [Background of the Invention] Heat storage agents mainly use materials (solid, liquid) with large specific heat, that is, sensible heat, and those that use materials that melt or
It is broadly divided into those that utilize the latent heat caused by the phase change of vaporization. The former requires a large amount of heat storage agent since the heat storage capacity (heat storage amount per short heat agent) is small since water is a typical example, but concrete blocks, rocks, etc. are also used. The latter can be further divided into two types: those that utilize latent heat of fusion and those that utilize latent heat of vaporization. The former has calcium chloride as its main ingredient, but it is inconvenient to handle because it is a solid, and there is a problem of supercooling, which causes a large difference between the melting start temperature and solidification start temperature (refer to Japanese Patent Application Laid-Open No. 53-70990). (No. Publication) There are few examples of devices that utilize latent heat of vaporization, and the only example is an aqueous solution of lithium bromide when an absorption refrigerator is converted to a short-heat type. This method uses a liquid heat storage agent,
By heating the liquid heat storage agent to evaporate the moisture and concentrating the short heat agent, heat is converted into a concentration difference and stored.
When used, it utilizes the latent heat of condensation generated when water vapor is absorbed into the concentrated heat storage agent. This method uses the latent heat of condensation of water (6 to 7 times the latent heat of solidification), so it has a large heat storage capacity, and because it uses the difference in concentration, the generated temperature can be changed freely (the solidification temperature is constant, but the water vapor absorption temperature is (depending on atmospheric pressure and concentration). However, since lithium bromide aqueous solution is much more expensive than calcium chloride and the like, it has been considered unsuitable for heat storage requiring a large capacity heat storage agent. On the other hand, inexpensive liquid heat storage agents such as magnesium chloride and sulfium chloride are considered, but their solubility is low and they are not suitable for the latent heat of vaporization method that utilizes concentration differences. Regarding absorbents used in absorption refrigerators, research is being accelerated into mixed absorbents that mix other absorbents in order to achieve air cooling and further increase solubility. For example, LiBr-LiCl system, LiBr-C 2 H 6 O 2 system,
LiBr-LiSCN system (refrigeration, Vol56, No.646, p11)
and LiCl-CaCl 2 system (Research and Research Results Report 1, 1979 3 on Effective Utilization of Low Temperature Difference Energy
(Published on May 6th, p. 102-103), but the mixing ratio has not been optimized. In addition, as a mixed heat storage agent, KCl-LiCl system and MgCl2-
(KCl-based, etc.) Industrial materials Vol. 26, No. 9, p. 44). [Object of the Invention] An object of the present invention is to provide a mixed liquid heat storage agent that is inexpensive and has high solubility by appropriately mixing a halogen compound. [Summary of the Invention] The inventors investigated various substances that can be used as a liquid heat storage agent and found that halides that form hydrates are inexpensive and have relatively high solubility. Furthermore, as a result of examining halogen compounds, we found that bromide and chloride, in particular,
It was found that this method has advantages in terms of safety. This is because absorption refrigerators have traditionally used aqueous solutions of lithium bromide and lithium chloride. As a result of further investigation, the inventors obtained the following new idea. In other words, the solubility of most halides is (1) higher in those with water of crystallization near room temperature (for example, KCl and NaCl without crystallized water have lower solubility than MgCl 2 with hexahydrate) (2) crystallization The smaller the number of water, the greater the solubility (for example, LiCl with dihydrate has higher solubility than MgCl 2 with hexahydrate) (3)
Bromide is larger than chloride (e.g. than LiCl)
(LiBr has high solubility) (4) However, the solubility of a single substance is insufficient as a liquid heat storage agent. As a result of various studies on how to improve solubility, the inventors discovered that the solubility of halides with water of crystallization is greatly influenced by the number of water molecules hydrated with it, and that hydration is influenced by coexisting ions. (In other words, other halides coexisting) confirmed through experiments that the solubility can be improved by mixing halides. Furthermore, we focused on the halides to be mixed: (1) dihydrate has higher solubility but is more expensive, and (2) hexahydrate has lower solubility than dihydrate but is cheaper. A highly soluble dihydrate bromide and an inexpensive hexahydrate halide were selected. That is, the gist of the present invention is to provide a highly soluble and inexpensive mixed liquid heat storage agent by appropriately mixing an inexpensive hexahydrate halide and a highly soluble dihydrate bromide. . Bromides such as LiBr and BaBr2 are typical examples of substances that become dihydrate salts at room temperature, which are the subject of the present invention.
Typical hexahydrate salts at room temperature include MgCl 2 ,
Chlorides such as CaCl 2 , NiCl 2 , CoCl 2 , MgBr 2 ,
There are bromides such as CaBr 2 , NiBr 2 , and CoBr 2 . [Examples of the Invention] The present invention will be described in detail below using Examples. (Solubility measurement method) Table 1 shows the type and temperature (near the saturation concentration of the main ingredient at a temperature of 0°C) of the liquid latent heat agent (hexahydrate as the main ingredient, dihydrate additive) used.
本発明によれば、比較的安価な六水塩と溶解度
の高い二水塩から構成される混合液状蓄熱剤が溶
解度も高く、かつ、安価に作れる。
According to the present invention, a mixed liquid heat storage agent composed of a relatively inexpensive hexahydrate and a highly soluble dihydrate has high solubility and can be produced at low cost.
第１図、第２図は本発明各物質を混合した時の
物質毎の混合比（重量比）と溶解度の関係を表わ
す一実施例の特性図、第３図は塩化物同志を混合
した時の混合比と溶解度を表わす従来例の特性
図、第４図は本発明の物質共通の混合比（モル
比）と溶解度の関係を表わす実施例の結果を示す
図である。
Ｘ……添加率。
Figures 1 and 2 are characteristic diagrams of an example showing the relationship between the mixing ratio (weight ratio) and solubility for each substance when the substances of the present invention are mixed, and Figure 3 is a characteristic diagram when chlorides are mixed together. FIG. 4 is a characteristic diagram of a conventional example showing the mixing ratio and solubility of the substances of the present invention, and FIG. X...Addition rate.
Claims (1)
温付近で二水塩を形成する臭化物と、塩化カルシ
ウム、塩化ニツケル、塩化コバルト、塩化マグネ
シウム、臭化カルシウム、臭化ニツケル、臭化コ
バルトまたは臭化マグネシウムから選ばれた常温
付近で六水塩を形成するハロゲン化物とを混合し
た水溶液からなることを特徴とする混合液状蓄熱
剤。 ２ 特許請求の範囲第１項において、二水塩と六
水塩の和に対する二水塩の添加率（モル比）を
0.55〜0.9にしたことを特徴とする混合液状蓄熱
剤。[Scope of Claims] 1. A bromide selected from lithium bromide and barium bromide that forms a dihydrate at around room temperature, calcium chloride, nickel chloride, cobalt chloride, magnesium chloride, calcium bromide, nickel bromide, A mixed liquid heat storage agent comprising an aqueous solution mixed with a halide selected from cobalt bromide or magnesium bromide that forms a hexahydrate at around room temperature. 2 In claim 1, the addition rate (molar ratio) of dihydrate to the sum of dihydrate and hexahydrate is
A mixed liquid heat storage agent characterized by having a concentration of 0.55 to 0.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167599A JPS6230183A (en) | 1985-07-31 | 1985-07-31 | Mixed liquid heat storage agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167599A JPS6230183A (en) | 1985-07-31 | 1985-07-31 | Mixed liquid heat storage agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230183A JPS6230183A (en) | 1987-02-09 |
| JPH0323112B2 true JPH0323112B2 (en) | 1991-03-28 |
Family
ID=15852754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60167599A Granted JPS6230183A (en) | 1985-07-31 | 1985-07-31 | Mixed liquid heat storage agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6230183A (en) |
-
1985
- 1985-07-31 JP JP60167599A patent/JPS6230183A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6230183A (en) | 1987-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4637888A (en) | Reversible phase change composition for storing energy | |
| JPH0225947B2 (en) | ||
| JPH09291272A (en) | Heat storage material | |
| JPS5827830B2 (en) | heat storage material | |
| EP0255928B1 (en) | Hydrated calcium bromide reversible phase change composition | |
| CN106318330A (en) | Preparation method of phase-change energy storage material and phase-change energy storage material | |
| CA1173643A (en) | Reversible phase change compositions of calcium chloride hexahydrate with a potassium salt | |
| US4406806A (en) | Thermal energy storage | |
| US4540502A (en) | Heat storage material | |
| JPH0323112B2 (en) | ||
| JPS6257674B2 (en) | ||
| JPH11335660A (en) | Cool storage material | |
| JPS6230182A (en) | Heat-accumulating liquid mixture | |
| WO1997007175B1 (en) | Eutectic drying composition and method | |
| JP2572690B2 (en) | Coolant | |
| JPH0292987A (en) | Cold storage material composition | |
| JPS588711B2 (en) | heat storage material | |
| JPH01252875A (en) | Vapor absorbing medium | |
| JPH0365838B2 (en) | ||
| JPH05331457A (en) | Heat storage composition | |
| US4783277A (en) | Absorption-type refrigerator | |
| JP3801784B2 (en) | Absorption-type heat pump aqueous solution composition | |
| JPH0416508B2 (en) | ||
| JPS59109577A (en) | Heat storage material | |
| JPS6356918B2 (en) |