JP3111667B2 - Manufacturing method of chemical heat storage material - Google Patents
Manufacturing method of chemical heat storage materialInfo
- Publication number
- JP3111667B2 JP3111667B2 JP04210915A JP21091592A JP3111667B2 JP 3111667 B2 JP3111667 B2 JP 3111667B2 JP 04210915 A JP04210915 A JP 04210915A JP 21091592 A JP21091592 A JP 21091592A JP 3111667 B2 JP3111667 B2 JP 3111667B2
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- chemical heat
- storage material
- ammonia
- calcium
- 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 - Fee Related
Links
Landscapes
- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Sorption Type Refrigeration Machines (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、化学蓄熱材の製造法に
関する。更に詳しくは、反応温度の制御が可能なアンモ
ニア錯体系化学蓄熱材の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chemical heat storage material. More specifically, the present invention relates to a method for producing an ammonia complex-based chemical heat storage material capable of controlling the reaction temperature.
【0002】[0002]
【従来の技術】CaCl2・nNH3(n=2,4,8)やCaBr2・nNH
3(n=2,6,8)などのアンモニア錯体は、それらのアンモ
ニア付加数の変化に伴う反応熱が非常に大きいことか
ら、熱の貯蔵やケミカルヒートポンプなどの化学蓄熱材
としての利用が図られている。2. Description of the Related Art CaCl 2 ·nNH 3 (n=2, 4, 8) and CaBr 2 ·nNH
Ammonia complexes such as 3 (n = 2, 6, 8) are expected to be used as chemical heat storage materials such as heat storage and chemical heat pumps because the heat of reaction associated with the change in the number of ammonia additions is very large. It is
【0003】 しかしながら、これらの化学蓄熱材のア
ンモニア付加数が変化する反応温度は、化学蓄熱材の種
類、雰囲気中のアンモニアガス分圧などによって支配さ
れるため、ケミカルヒートポンプなどを構成する際、そ
の作動温度や圧力の仕様に対して適した反応特性を有す
る化学蓄熱材が存在しない場合がある。[0003]However, since the reaction temperature at which the ammonia addition number of these chemical heat storage materials changes is governed by the type of chemical heat storage material, the partial pressure of ammonia gas in the atmosphere, etc., when constructing a chemical heat pump or the like, There may be no chemical heat storage material with suitable reaction characteristics for operating temperature and pressure specifications.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、反応
温度の制御が可能なアンモニア錯体系化学蓄熱材の製造
法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an ammonia complex-based chemical heat storage material in which the reaction temperature can be controlled.
【0005】[0005]
【課題を解決するための手段】かかる本発明の目的は、
塩化カルシウムおよび臭化カルシウムを溶解させた水溶
液を濃縮、乾燥させて得られたカルシウム塩混合物無水
物にアンモニアを付加させて化学蓄熱材を製造すること
によって達成される。DISCLOSURE OF THE INVENTION The object of the present invention is to:
This is achieved by adding ammonia to an anhydrous calcium salt mixture obtained by concentrating and drying an aqueous solution in which calcium chloride and calcium bromide are dissolved to produce a chemical heat storage material.
【0006】塩化カルシウム、臭化カルシウム共、無水
物、水和物のいずれをも使用することができる。本発明
方法においては、まず所定量の塩化カルシウムと臭化カ
ルシウムとを水に完全に溶解させた後、この水溶液を徐
々に加熱減圧下で濃縮し、溶解しているカルシウム塩混
合物を再び析出させ、析出残渣に水気がみられなくなっ
たところで、200℃前後の真空乾燥器内で24時間程度乾
燥させることが行われる。Both calcium chloride and calcium bromide, anhydrides and hydrates can be used. In the method of the present invention, first, predetermined amounts of calcium chloride and calcium bromide are completely dissolved in water, and then this aqueous solution is gradually heated and concentrated under reduced pressure to reprecipitate the dissolved calcium salt mixture. , When the precipitation residue is no longer moist, it is dried in a vacuum dryer at around 200°C for about 24 hours.
【0007】得られたカルシウム塩混合物無水物に、ア
ンモニアガス圧約0.5〜2気圧、温度約-30〜20℃の条件
下でアンモニアを付加させると、どの混合比の場合に
も、CaCl2、CaBr2にそれぞれ8NH3が付加したものに相当
するカルシウム塩混合物アンモニア錯体が得られた。[0007] When ammonia is added to the resulting anhydrous calcium salt mixture under conditions of ammonia gas pressure of about 0.5 to 2 atm and temperature of about -30 to 20°C, CaCl 2 and CaBr are produced at any mixing ratio. Calcium salt mixture ammonium complexes corresponding to the addition of 8NH3 to 2 respectively were obtained.
【0008】得られたカルシウム塩混合物アンモニア錯
体の脱NH3温度は、カルシウム塩の混合割合によっても
異なり、具体的には、アンモニアガス圧1.2気圧、温度-
20℃の条件下でアンモニア付加させたカルシウム塩混合
物アンモニア錯体の場合、次の表に示されるように、Ca
Cl2:CaBr2=50:50の混合モル比のとき、最も高い脱NH
3温度(アンモニアガス圧1気圧)を示している。
(以下余白)
表
混合モル比 8NH3錯体中の 脱NH3重量 脱NH3温度
CaCl2 CaBr2 NH3付加重量(%) (重量%) (℃)
100 0 55.1 27.6 30
(CaCl2・8NH3) (8NH3→4NH3)
90 10 53.2 27.1 34
80 20 51.3 26.3 36
70 30 50.0 26.0 38
60 40 48.1 23.8 39
50 50 46.5 21.1 40
40 60 45.1 17.2 39
30 70 43.9 14.1 37
20 80 42.6 12.1 34
10 90 41.5 10.5 32
0 100 40.5 10.1 26
(CaBr2・8NH3) (8NH3→6NH3)
注)8NH3錯体中のNH3付加重量:NH3付加重量/8NH3錯体
粉末重量
脱NH3重量:反応によって失われるNH3重量/8NH3錯体粉
末重量
脱NH3温度:NH3ガス圧1気圧下での脱NH3反応の反応平衡
温度[0008] The deNH 3 temperature of the obtained calcium salt mixture ammonia complex also varies depending on the mixing ratio of the calcium salts.
In the case of the calcium salt mixture ammonia complex that was ammoniated under the condition of 20 °C, as shown in the following table, Ca
The highest deNH
3 Temperature (ammonia gas pressure 1 atm) is shown. (Blanks below) Table Mixing molar ratio De - NH3 weight in 8NH3 complex De - NH3 temperature CaCl2CaBr2NH3 addition weight (%) (% by weight) ( °C) ) (8NH 3 →4NH 3 ) 90 10 53.2 27.1 34 80 20 51.3 26.3 36 70 30 50.0 26.0 38 60 40 48.1 23.8 39 50 50 46.5 21.1 40 40 60 45.1 17.2 39 30 70 43.9 14.1 37 20 80 42.6 12.1 34 10 90 41.5 10.5 32 0 100 40.5 10.1 26 (CaBr 2 8NH 3 ) (8NH 3 → 6NH 3 ) Note) NH3 addition weight in 8NH3 complex: NH3 addition weight/ 8NH3 complex powder weight De - NH3 weight: Reaction NH3 weight/ 8NH3 complex powder weight lost by DeNH3 temperature: reaction equilibrium temperature of deNH3 reaction under NH3 gas pressure of 1 atm
【0009】これに対して、CaCl2(無水物)70モル%とCa
Br2(無水物)30モル%の粉末状態でのカルシウム塩混合物
について、アンモニアガス圧1.2気圧、温度-20℃でアン
モニア付加を行い、得られたカルシウム塩混合物アンモ
ニア錯体について、アンモニアガス圧1気圧での脱NH3
温度を測定すると、まず26℃では
CaBr2・8NH3 → CaBr2・6NH3+2NH3
の反応分のNH3が脱離し、次いで30℃では
CaCl2・8NH3 → CaCl2・4NH3+4NH3
の反応分のNH3が脱離した。即ち、粉末混合物をアンモ
ニア付加させたものの反応特性は、CaBr2・8NH3、CaCl2
・8NH3各成分単独の反応特性と何ら変わらない。In contrast, 70 mol % CaCl 2 (anhydrous) and Ca
Br 2 (anhydride) 30 mol % powdery calcium salt mixture was subjected to ammonia addition at an ammonia gas pressure of 1.2 atm and a temperature of -20°C. DeNH3 at
When the temperature was measured, NH3 from the reaction of CaBr2.8NH3 → CaBr2.6NH3 + 2NH3 was first released at 26°C, and then CaCl2.8NH3 → CaCl2.4NH3 + 4NH at 30 °C. The reaction portion of 3 NH 3 was eliminated. That is, the reaction characteristics of the powder mixture added with ammonia are CaBr 2 .8NH 3 , CaCl 2
・The reaction characteristics of 8NH3 are not different from those of each component alone.
【0010】[0010]
【発明の効果】アンモニアガス圧1気圧における反応温
度は、
CaCl2・8NH3 ⇔ CaCl2・4NH3+4NH3 30℃
CaBr2・8NH3 ⇔ CaBr2・6NH3+2NH3 27℃
であるのに対し、水溶液状態を経て混合された塩化カル
シウム-臭化カルシウム混合物のアンモニア錯体は、そ
の脱NH3温度を混合比に応じて32〜40℃と高温側に最大1
0℃迄変化させることができ、反応温度の制御を可能と
させる。[Effect of the Invention] The reaction temperature at an ammonia gas pressure of 1 atm is CaCl2.8NH3 ⇔ CaCl2.4NH3 + 4NH3 30 °C CaBr2.8NH3 ⇔ CaBr2.6NH3 + 2NH3 27°C. On the other hand, the ammonia complex of the calcium chloride-calcium bromide mixture mixed through the aqueous solution state has a deNH
It can be varied down to 0°C, making it possible to control the reaction temperature.
フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C09K 5/16 F28D 20/00 F25B 17/08 CA(STN)Continued from front page (58) Investigated field (Int.Cl. 7 , DB name) C09K 5/16 F28D 20/00 F25B 17/08 CA (STN)
Claims (2)
溶解させた水溶液を濃縮、乾燥させて得られたカルシウ
ム塩混合物無水物にアンモニアを付加させることを特徴
とする化学蓄熱材の製造法。1. A method for producing a chemical heat storage material, comprising adding ammonia to a calcium salt mixture anhydride obtained by concentrating and drying an aqueous solution in which calcium chloride and calcium bromide are dissolved.
ム塩混合物アンモニア錯体。2. A calcium salt mixture ammonia complex obtained by the method of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04210915A JP3111667B2 (en) | 1992-07-15 | 1992-07-15 | Manufacturing method of chemical heat storage material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04210915A JP3111667B2 (en) | 1992-07-15 | 1992-07-15 | Manufacturing method of chemical heat storage material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06136357A JPH06136357A (en) | 1994-05-17 |
JP3111667B2 true JP3111667B2 (en) | 2000-11-27 |
Family
ID=16597174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04210915A Expired - Fee Related JP3111667B2 (en) | 1992-07-15 | 1992-07-15 | Manufacturing method of chemical heat storage material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3111667B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013027778A1 (en) | 2011-08-23 | 2013-02-28 | 株式会社豊田中央研究所 | Chemical heat storage material, manufacturing method therefor and chemical heat storage structure |
EP2918653A1 (en) | 2014-03-14 | 2015-09-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of manufacturing composite metal halide and chemical heat storage material |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4745299B2 (en) * | 2007-06-25 | 2011-08-10 | Jfeエンジニアリング株式会社 | Adsorption / desorption material of ammonia using a combination of specific metal halides, separation method and storage method |
JP5712549B2 (en) * | 2010-10-08 | 2015-05-07 | 株式会社豊田中央研究所 | Chemical heat storage body and method for producing the same |
JP5765346B2 (en) | 2011-02-10 | 2015-08-19 | 株式会社豊田中央研究所 | Chemical heat storage body and method for producing the same |
JP2014159497A (en) * | 2013-02-19 | 2014-09-04 | Toyota Central R&D Labs Inc | Chemical heat storage material, method of producing the same and chemical heat storage structure |
US9914645B2 (en) | 2013-11-07 | 2018-03-13 | Regents Of The University Of Minnesota | Process for making ammonia |
WO2016059982A1 (en) * | 2014-10-14 | 2016-04-21 | 株式会社豊田自動織機 | Chemical heat storage device |
AT520368B1 (en) * | 2017-08-29 | 2022-12-15 | Univ Wien Tech | Process for thermochemical energy storage |
-
1992
- 1992-07-15 JP JP04210915A patent/JP3111667B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013027778A1 (en) | 2011-08-23 | 2013-02-28 | 株式会社豊田中央研究所 | Chemical heat storage material, manufacturing method therefor and chemical heat storage structure |
EP2918653A1 (en) | 2014-03-14 | 2015-09-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of manufacturing composite metal halide and chemical heat storage material |
Also Published As
Publication number | Publication date |
---|---|
JPH06136357A (en) | 1994-05-17 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |