JPH0419276B2 - - Google Patents

Info

Publication number
JPH0419276B2
JPH0419276B2 JP59048522A JP4852284A JPH0419276B2 JP H0419276 B2 JPH0419276 B2 JP H0419276B2 JP 59048522 A JP59048522 A JP 59048522A JP 4852284 A JP4852284 A JP 4852284A JP H0419276 B2 JPH0419276 B2 JP H0419276B2
Authority
JP
Japan
Prior art keywords
barium
water
sulfate
salt
cryogen
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
Application number
JP59048522A
Other languages
Japanese (ja)
Other versions
JPS60192783A (en
Inventor
Hiroyuki Kii
Tetsuo Wakisono
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Shell Sekiyu KK
Original Assignee
Showa Shell Sekiyu KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Shell Sekiyu KK filed Critical Showa Shell Sekiyu KK
Priority to JP59048522A priority Critical patent/JPS60192783A/en
Publication of JPS60192783A publication Critical patent/JPS60192783A/en
Publication of JPH0419276B2 publication Critical patent/JPH0419276B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は寒剤の改良に関するものであつて、合
成樹脂製袋又は容器内に封入し、これに水を加え
ることによつて冷却時間の長い保冷器として使用
できる寒剤を提供することを目的とするものであ
る。 化学薬剤の溶解熱を利用する寒剤については、
各種のものが知られている。例えば、塩化アンモ
ニウム、チオ硫酸ソーダ5水塩、硫酸カリウムの
3者を水に溶解せしめた寒剤(特公昭45−1712号
公報)、無水硝酸アンモニウムと負の溶解熱を有
して結晶水を保有する物質の両者を混合した寒剤
(特公昭51−27908号公報)等が知られている。 前述2つの発明は何れも化学薬剤を水に溶解し
た際の吸熱反応に利用した寒剤であつて、水に化
学薬剤が溶解して数分後に−5〜−6℃の低温が
得られる。しかし、前記刊行物に記載されている
ものは低温を長時間維持することが因難で、長時
間保冷を必要とするものには必らずしも適当では
ない。 本発明者等は此の種寒剤の改良につき種々研究
の結果、特許請求の範囲に記載した構成とするこ
とによつて、短時間で0℃以下の低温が得られ、
しかも低温の保持時間を従来より長時間とするこ
とのできる寒剤を得ることができた。 即ち、本発明は硫酸ナトリウム(以下芒硝とい
う)、硫酸アンモニウム(以下硫安という)若し
くはカリ明ばん〔KA1(SO4)・12H2O〕からなる
硫酸塩に対し、塩化バリウム、硫酸バリウム若し
くは臭化バリウムから選ばれた1種のバリウム塩
との混合物からなり、水に溶解して負の溶解熱を
生ずると共に、バリウム塩が前記硫酸塩と反応し
て硫酸バリウムの沈殿を形成するように構成され
ていることを特徴とする寒剤である。 本発明に於て使用する芒硝〔Na2SO4
10H2O〕、硫安〔(NH42SO4〕又はカリ明ばん 〔KAl(SO42・12H2O〕は何れも水に易溶性で
あり、溶解時に負の溶解熱を生ずる硫酸塩であ
る。 他方、これと組合せるバリウム塩は塩化バリウ
ム、硫酸バリウム若しくは臭化バリウム等のバリ
ウム塩であつて、水に溶解した場合に、前記硫酸
塩と反応して水に難溶性の硫酸バリウムを形成で
きるものが使用される。もつとも、入手し易いこ
と及び価格の点を考慮すれば前記組合せのうち芒
硝と塩化バリウムとの組合せが最も好都合であ
る。 従来、水に溶解して負の溶解熱を生ずる寒剤
は、塩の溶解が水に対する飽和溶解度に達すると
その後の塩の溶解の進行が止まり、溶液温度が上
昇するまでは冷熱の発生が停止するのを避けるこ
とができない。 本発明は上述の如き欠点を改善するため、溶解
した塩の一部を沈殿させて溶液系から除去し、溶
解を続行させるようにしたものである。例えば芒
硝と塩化バリウムとによつてその反応機構を説明
すれば、水に溶解した芒硝と塩化バリウムは次の
式のように反応して水に難溶性の硫酸バリウムを
形成する。 Na2SO4・10H2O+BaCl2・2H2O →2NaCl+BaSO4↓+12H2O このように、水に難溶性の硫酸バリウムを沈殿
する結果、芒硝及び塩化バリウムはさらに水に対
する溶解を持続でき、従つてこれらの塩が溶解平
衡に達する時間が長時間となり、保冷時間を延長
することができる。 図面は、本発明の寒剤〔(芒硝:
Na2SO410H2O)246gにBaCl2・2H2O188g混合
したものに水202g添加〕と、従来の寒剤
(NH4NO3380gに水170g添加)の温度の経時変
化を示したものであるが、本発明は約20分以内に
3℃に達し、60分経過後約4℃、120分経過後約
7℃、200分経過後約10℃と緩やかに推移し、保
冷時間が延長できることが認められる。 これに対し、従来の寒剤は短時間に−4℃に達
するが、60分経過後約4℃、120分経過後約10℃
に達し、低温保持時間は著しく短かい。尚、この
場合大型の結晶(径3〜6mm程度の塊状)を使用
すれば、低温保持時間をさらに延長することがで
きる。 本発明で硫酸塩と組合せるバリウム塩の配合割
合は硫酸塩100gに対して50〜250g配合すること
ができる。 次の表は、硫酸塩とこれに組合せるバリウム塩
との各種組合せと、その際に生ずる溶解熱を示し
たものである。
The present invention relates to improvement of a cryogen, and an object of the present invention is to provide a cryogen that can be used as a cooler with a long cooling time by being sealed in a synthetic resin bag or container and adding water to the bag or container. It is something. Regarding cryogens that utilize the heat of dissolution of chemical agents,
Various types are known. For example, a cryogen in which ammonium chloride, sodium thiosulfate pentahydrate, and potassium sulfate are dissolved in water (Japanese Patent Publication No. 1712/1982), anhydrous ammonium nitrate, and a cryogen that has a negative heat of solution and retains crystal water. A cryogen (Japanese Patent Publication No. 27908/1983) which is a mixture of both substances is known. Both of the above two inventions are cryogens that are used for endothermic reactions when chemical agents are dissolved in water, and a low temperature of -5 to -6°C is obtained several minutes after the chemical agents are dissolved in water. However, the products described in the above-mentioned publications have difficulty in maintaining low temperatures for long periods of time, and are not necessarily suitable for products that require long-term cold storage. The present inventors have conducted various studies on improving this seed cold agent, and found that by adopting the structure described in the claims, a low temperature of 0°C or less can be obtained in a short time,
In addition, we were able to obtain a cryogen that can be kept at low temperatures for a longer time than before. That is, the present invention uses barium chloride, barium sulfate, or barium bromide for a sulfate consisting of sodium sulfate (hereinafter referred to as mirabilite), ammonium sulfate (hereinafter referred to as ammonium sulfate), or potassium alum [KA1 (SO 4 ).12H 2 O]. a mixture of one type of barium salt selected from It is a cooling agent characterized by the presence of Glauber's salt [Na 2 SO 4
10H 2 O], ammonium sulfate [(NH 4 ) 2 SO 4 ], or potash alum [KAl(SO 4 ) 2.12H 2 O] are all easily soluble in water, and sulfuric acid generates a negative heat of solution when dissolved. It's salt. On the other hand, the barium salt to be combined with this is a barium salt such as barium chloride, barium sulfate, or barium bromide, which, when dissolved in water, can react with the sulfate to form barium sulfate, which is sparingly soluble in water. things are used. Of the above combinations, however, the combination of Glauber's salt and barium chloride is the most convenient in terms of availability and price. Conventionally, with cryogens that generate negative heat of solution when dissolved in water, when the dissolution of the salt reaches saturated solubility in water, the further dissolution of the salt stops, and the generation of cold heat stops until the solution temperature rises. cannot be avoided. In order to improve the above-mentioned drawbacks, the present invention allows a portion of the dissolved salt to be precipitated and removed from the solution system, thereby allowing continued dissolution. For example, if the reaction mechanism is explained using mirabilite and barium chloride, mirabilite and barium chloride dissolved in water react as shown in the following formula to form barium sulfate, which is sparingly soluble in water. Na 2 SO 4・10H 2 O+BaCl 2・2H 2 O →2NaCl+BaSO 4 ↓+12H 2 O In this way, as a result of precipitating barium sulfate, which is sparingly soluble in water, mirabilite and barium chloride can continue to dissolve in water, and Therefore, it takes a long time for these salts to reach solubility equilibrium, and the cooling time can be extended. The drawings show the cryogen of the present invention [(glauber's salt:
This graph shows the temperature change over time for a mixture of 246 g of Na 2 SO 4 10H 2 O) and 188 g of BaCl 2.2H 2 O, with 202 g of water added, and a conventional cryogen (170 g of water added to 380 g of NH 4 NO 3 ). However, in the present invention, the temperature reaches 3°C within about 20 minutes, and the temperature gradually changes to about 4°C after 60 minutes, about 7°C after 120 minutes, and about 10°C after 200 minutes, and the cooling time can be extended. is recognized. In contrast, conventional cryogens reach -4℃ in a short period of time, but after 60 minutes it reaches about 4℃ and after 120 minutes it reaches about 10℃.
, and the low temperature holding time is extremely short. In this case, if large-sized crystals (lumps with a diameter of about 3 to 6 mm) are used, the low-temperature holding time can be further extended. In the present invention, the barium salt to be combined with the sulfate can be blended in an amount of 50 to 250 g per 100 g of the sulfate. The following table shows various combinations of sulfates and barium salts and the heats of solution generated.

【表】 前述表から明らかな如く、芒硝と塩化バリウム
又は芒硝と硝酸バリウムとの組合せの場合は冷却
効果が優れているのが認められる。 以上の如く本発明は水に溶解して負の溶解熱を
生じ、かつ、水に溶解して反応して水に難溶性の
硫酸バリウムを形成する芒硝、硫安若しくはカリ
明ばんとバリウム塩とを組合せることによつて、
水に対する飽和溶解度に達する時間を延長するこ
とによつて低温保持時間を長くすることができ、
従つて本発明を適宜合成樹脂製の袋又は容器に収
納しておき、使用に当り該合成樹脂製の袋又は容
器に水を添加することによつて氷枕、冷湿布さら
には携帯用クーラー等の保冷器などとすることが
できるという利点がある。
[Table] As is clear from the above table, it is recognized that the combination of mirabilite and barium chloride or mirabilite and barium nitrate has an excellent cooling effect. As described above, the present invention uses mirabilite, ammonium sulfate, or potassium alum, and barium salt, which generate negative heat of solution when dissolved in water, and which react with water to form barium sulfate, which is sparingly soluble in water. By combining
By extending the time to reach saturated solubility in water, the low temperature retention time can be extended.
Therefore, by storing the present invention in an appropriate synthetic resin bag or container and adding water to the synthetic resin bag or container before use, it can be used as an ice pillow, cold compress, or even a portable cooler. It has the advantage that it can be used as a cooler.

【図面の簡単な説明】[Brief explanation of drawings]

図面は本発明の一実施例と、従来の寒剤との温
度の経時変化を示すグラフである。
The drawing is a graph showing temperature changes over time between an embodiment of the present invention and a conventional cryogen.

Claims (1)

【特許請求の範囲】 1 硫酸ナトリウム、硫酸アンモニウム若しくは
カリ明ばん〔KAl(SO42・12H2O〕からなる硫
酸塩に対し、塩化バリウム、硝酸バリウム若しく
は臭化バリウムから選ばれた1種のバリウム塩と
の混合物からなり、水に溶解して負の溶解熱を生
ずると共に、バリウム塩が前記硫酸塩と反応して
硫酸バリウムの沈澱を形成するように構成されて
いることを特徴とする寒剤。
[Claims] 1. A sulfate consisting of sodium sulfate, ammonium sulfate or potassium alum [KAl(SO 4 ) 2.12H 2 O], and one selected from barium chloride, barium nitrate or barium bromide. A cryogen consisting of a mixture with a barium salt, which is configured to dissolve in water to generate a negative heat of solution, and to react with the barium salt to form a precipitate of barium sulfate. .
JP59048522A 1984-03-14 1984-03-14 Freezing mixture Granted JPS60192783A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59048522A JPS60192783A (en) 1984-03-14 1984-03-14 Freezing mixture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59048522A JPS60192783A (en) 1984-03-14 1984-03-14 Freezing mixture

Publications (2)

Publication Number Publication Date
JPS60192783A JPS60192783A (en) 1985-10-01
JPH0419276B2 true JPH0419276B2 (en) 1992-03-30

Family

ID=12805687

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59048522A Granted JPS60192783A (en) 1984-03-14 1984-03-14 Freezing mixture

Country Status (1)

Country Link
JP (1) JPS60192783A (en)

Also Published As

Publication number Publication date
JPS60192783A (en) 1985-10-01

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