JPH01153785A - Regenerating agent - Google Patents
Regenerating agentInfo
- Publication number
- JPH01153785A JPH01153785A JP62312578A JP31257887A JPH01153785A JP H01153785 A JPH01153785 A JP H01153785A JP 62312578 A JP62312578 A JP 62312578A JP 31257887 A JP31257887 A JP 31257887A JP H01153785 A JPH01153785 A JP H01153785A
- Authority
- JP
- Japan
- Prior art keywords
- agent
- clathrate
- supercooling
- cold storage
- freon
- 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.)
- Pending
Links
- 230000001172 regenerating effect Effects 0.000 title abstract 4
- 238000004781 supercooling Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011232 storage material Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、蓄冷剤、特にクラスレートを利用した蓄冷剤
であって、クラスレート生成の過冷却現象を防止させ得
る蓄冷剤に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a cold storage agent, particularly a cold storage agent using clathrate, which can prevent the supercooling phenomenon of clathrate formation. .
現在、省エネルギーの観点から蓄冷法の研究が実用化を
目指して行われており、これらの蓄冷法の一つとしてガ
スクラスレートを利用する方法が考えられている。Currently, research on cold storage methods is being carried out with the aim of putting them into practical use from the perspective of energy conservation, and a method using gas clathrates is being considered as one of these cold storage methods.
クラスレートとは、「原子まだは分子が結合してできた
三次元構造の内部に適当な大きさの空孔があってその中
に他の原子まだは分子が入り込んで特定の結晶構造を形
成する物質」とされている。三次元構造の骨組をつくる
物質は。A clathrate is a three-dimensional structure formed by bonding atoms and molecules, with holes of appropriate size inside which other atoms and molecules can enter to form a specific crystal structure. It is said to be a substance that What is the material that makes up the framework of a three-dimensional structure?
ホストと呼ばれ、−船釣には水が用いられ、また、骨組
の中に取り込まれる物質はゲストと呼ばれ、メタン、エ
タン、プロパン等の炭化水素類やフロンＲ１１（ＣＣＡ
ａＦ）、フロンＲ１２（ＣＣｄ２Ｆ２）。-Water is used for boat fishing, and the substances taken into the framework are called guests, including hydrocarbons such as methane, ethane, and propane, and fluorocarbons R11 (CCA).
aF), Freon R12 (CCd2F2).
フロンＲ２１（ＣＨＣ＆Ｆ）等のフロン類が用いられる
。特にゲストがガス状物質であるクラスレートをガスク
ラスレートと呼んでいる。Freon such as Freon R21 (CHC&F) is used. In particular, clathrates whose guests are gaseous substances are called gas clathrates.
ガスクラスレートを蓄冷に利用すると、氷と同程度の蓄
冷容量があること。水とガスクラスレートとの混合物（
スラリー）は、氷より伝熱特性が良いこと等多くのメリ
ットが期待できる。When gas clathrate is used for cold storage, it has a cold storage capacity comparable to that of ice. A mixture of water and gas clathrate (
Slurry) can be expected to have many advantages, including better heat transfer properties than ice.
第５図（５）、 Ｃ１０）に蓄冷槽の概念図の一例を示
す。Figure 5 (5), C10) shows an example of a conceptual diagram of a cold storage tank.
蓄冷時には第５図（５）に示すように蓄冷槽２内の水と
フロンの混合液１を冷熱源あるいは冷凍機８によりクラ
スレートの臨界分解温度以下まで冷却し、クラスレート
１を生成させる。そして、放冷時には第５図（Ｂ）に示
すように、蓄冷槽２内のクラスレート１を冷房用媒体等
４を循環することにより、水とフロン混合液１に分解し
。During cold storage, as shown in FIG. 5 (5), the mixed liquid 1 of water and chlorofluorocarbon in the cold storage tank 2 is cooled down to below the critical decomposition temperature of the clathrate by a cold heat source or the refrigerator 8, and clathrate 1 is generated. Then, during cooling, as shown in FIG. 5(B), the clathrate 1 in the cold storage tank 2 is decomposed into water and a fluorocarbon mixture 1 by circulating a cooling medium or the like 4.
冷熱を取り出す。Remove cold heat.
この方法の場合、蓄冷時にフロンと水の混合液１を臨界
分解温度まで冷却してもクラスレートは生成せず、クラ
スレートを生成させるには。In the case of this method, clathrate is not generated even if the mixed liquid 1 of fluorocarbon and water is cooled to the critical decomposition temperature during cold storage, and clathrate is generated.
臨界分解温度よりかなり低い温度まで冷却する過冷却が
必要であった。この過冷却は、熱効率的に不利であり、
過冷却を防止するだめに過冷却防止剤を添加することが
よく利用されている。Supercooling to a temperature well below the critical decomposition temperature was required. This supercooling is disadvantageous in terms of thermal efficiency;
Adding an anti-supercooling agent is often used to prevent supercooling.
本発明者らは、特願昭５９−２６６２７０ 、特願昭５
９−２６６２７１にて過冷却防止剤として、微粒ゼオラ
イト、スラグ、フライアッシュ、けい酸カルシウム、炭
酸カルシウムを提案している。The inventors of the present invention have filed Japanese Patent Application No. 59-266270, Japanese Patent Application No. 5
No. 9-266271 proposes fine zeolite, slag, fly ash, calcium silicate, and calcium carbonate as supercooling inhibitors.
しかし、前記した過冷却防止剤では、過冷却の大きさは
あまり改善されることなく更に過冷却を小さくする必要
があった。However, with the above-mentioned supercooling inhibitor, the magnitude of supercooling is not significantly improved, and it is necessary to further reduce the supercooling.
本発明では、前記の物質以外の過冷却防止剤を探索し、
クラスレートの生成を熱効率上有利に行なわせ得る蓄冷
剤を提案するものである。In the present invention, we search for supercooling inhibitors other than the above-mentioned substances,
This paper proposes a cold storage agent that can generate clathrates advantageously in terms of thermal efficiency.
本発明は前記した問題点を解決するため、ゲスト剤とホ
スト剤とからなり、冷却することによりクラスレートを
生成する蓄冷剤において。In order to solve the above-mentioned problems, the present invention provides a cold storage agent that includes a guest agent and a host agent and generates clathrate when cooled.
過冷却防止剤として第２族の金属元素を混入したことを
特徴とするものである。It is characterized in that a Group 2 metal element is mixed as a supercooling inhibitor.
水とフロンの混合液に過冷却防止剤としての第２族の金
属元素９例えばＦｅ 、 Ｚｎ、 Ｃｕのうち少なくと
も１種を混入することにより、過冷却を極めて小さくす
ることが可能となり、クラスレートの生成を熱効率的に
有利に行なわせ得ることができた。By mixing at least one of Group 2 metal elements 9, such as Fe, Zn, and Cu, as a supercooling inhibitor into the mixture of water and CFC, supercooling can be made extremely small, and the clathrate can be reduced. could be produced thermally efficiently.
以下に本発明の詳細な説明する。 The present invention will be explained in detail below.
■ｌの耐圧ガラス製の晶析槽本体にイオン交換水７００
ｇ所定量の種晶を採取し、槽内を減圧。■700 liters of ion-exchanged water in the crystallizer body made of pressure-resistant glass
g Collect a predetermined amount of seed crystals and reduce the pressure inside the tank.
脱気後、フロン１２を所定量（１５〜１６ｇ）液状で加
え９００ ｒｐｍで攪拌しながら６０ｍ１ｎ８０°Ｃに
保持した。次いで、このフロン−水混合溶液を攪拌しな
がら冷却し、クラスレートを生成させた。After degassing, a predetermined amount (15 to 16 g) of Freon 12 was added in liquid form, and the mixture was maintained at 60 ml at 80°C while stirring at 900 rpm. Next, this Freon-water mixed solution was cooled while stirring to generate clathrate.
次に混合溶液の温度を上げてクラスレートを分解した後
、フロン１２クラスレートの臨界分解温度（Ｔｅ ＝
１２．０７°Ｃ）より高い温度Ｔｄに混合溶液を６９
ｍｉｎ保持した後、前記と同様にして冷却し。Next, after increasing the temperature of the mixed solution to decompose the clathrate, the critical decomposition temperature of Freon-12 clathrate (Te =
The mixed solution is heated to a temperature Td higher than 69°C (12.07°C).
After holding the temperature for 20 minutes, it was cooled in the same manner as above.
クラスレートの生成−分解を繰り返した。この時の典型
的な温度経時変化を第２図に示す。The generation and decomposition of clathrates was repeated. A typical temperature change over time at this time is shown in FIG.
第１図に種晶を４ｇ添加し、７°Ｃ／ｈで冷却した時の
クラスレートの生成温度Ｔｆを示す。第１図中でＮｏｎ
ｅと示したものは２種晶を添加しない系である。この系
では、クラスレートが生成する前に０°Ｃ以下にまで過
冷却し、氷が先に生成した後、クラスレートが生成した
。Figure 1 shows the clathrate formation temperature Tf when 4g of seed crystals were added and cooled at 7°C/h. Non in Figure 1
The system indicated as e is a system in which no two seed crystals are added. In this system, supercooling was performed to below 0°C before clathrate was formed, and ice was formed first, followed by clathrate.
種晶がＡ Ｉ ＋ Ｎｉｒ Ｍｎでは２種晶を添加して
いない系と同様に先に氷が生成したが９種晶がＦｅ。When the seed crystals were A I + Nir Mn, ice was formed first as in the system without the addition of two seed crystals, but the nine seed crystals were Fe.
Ｚｎでは、氷よりも先にクラスレートが生成し。In Zn, clathrate is formed before ice.
種晶として有効であった。種晶がＣｕでは、生成・分解
を行った溶液を再度冷却した場合に、氷よりも先にクラ
スレートが生成し１種晶として有効であった。It was effective as a seed crystal. When the seed crystal was Cu, when the solution that had been generated and decomposed was cooled again, clathrate was generated before ice, and it was effective as a seed crystal.
第８図及び第４図に種晶としてＦｅ、Ｚｎを用いた時の
種晶添加量の△Ｔｆへの影響を調べた結果を各々示す。FIGS. 8 and 4 show the results of investigating the influence of the amount of seed crystals added on ΔTf when Fe and Zn were used as seed crystals, respectively.
Ｆｅ、Ｚｎのいずれの系においても添加量の多い時に△
Ｔｆは小さくなり２種晶として効果が大きくなることが
わかる。In both Fe and Zn systems, when the amount added is large, △
It can be seen that as Tf becomes smaller, the effect as a two-seed crystal increases.
以上に述べたように９本発明により、クラスレート蓄冷
において、蓄冷剤に第２族の金属元素を混入することに
より過冷却を極めて小さくすることができ、熱効率上有
利に蓄冷することが可能となる。As described above, according to the present invention, in clathrate cold storage, by mixing a group 2 metal element into the cold storage agent, supercooling can be extremely reduced, and cold storage can be advantageously achieved in terms of thermal efficiency. Become.
第１図は種晶を添加したときのクラスレート生成温度Ｔ
ｆを示す図、第２図はクラスレート生成−分解時の温度
経時変化図、第３図及び第４図は種晶としてＦｅ、Ｚｎ
を用いたときめ添加量のクラスレート生成温度への影響
を示す図、第５図（４）、集）は蓄冷剤を用いた蓄冷装
置の概念図である。Figure 1 shows the clathrate formation temperature T when seed crystals are added.
Fig. 2 is a diagram showing temperature change over time during clathrate formation and decomposition, Fig. 3 and Fig. 4 are graphs showing Fe and Zn as seed crystals.
Figure 5 (4), a diagram showing the influence of the amount of grain added on the clathrate formation temperature using a cold storage agent, is a conceptual diagram of a cold storage device using a cold storage agent.
Claims (2)
よりクラスレートを生成する蓄冷剤において、過冷却防
止剤として第２族の金属元素を混入したことを特徴とす
る蓄冷剤。(1) A cold storage agent comprising a guest agent and a host agent and generating clathrate upon cooling, characterized in that a metal element of Group 2 is mixed as an anti-supercooling agent.
ロンＲ２１の少なくとも１種、ホスト剤が水、過冷却防
止剤としての第２族の金属元素がＦｅ、Ｚｎ、又はＣｕ
の少なくとも１種であることを特徴とする特許請求の範
囲（１）項記載の蓄冷剤。(2) The guest agent is at least one type of Freon R11, Freon R12, or Freon R21, the host agent is water, and the Group 2 metal element as a supercooling inhibitor is Fe, Zn, or Cu.
The cold storage agent according to claim (1), characterized in that it is at least one of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62312578A JPH01153785A (en) | 1987-12-10 | 1987-12-10 | Regenerating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62312578A JPH01153785A (en) | 1987-12-10 | 1987-12-10 | Regenerating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01153785A true JPH01153785A (en) | 1989-06-15 |
Family
ID=18030894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62312578A Pending JPH01153785A (en) | 1987-12-10 | 1987-12-10 | Regenerating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01153785A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2927299A2 (en) | 2014-04-02 | 2015-10-07 | Panasonic Intellectual Property Management Co., Ltd. | Heat storage apparatus, method for storing heat, and method for producing heat storage apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184584A (en) * | 1984-03-02 | 1985-09-20 | Mitsubishi Heavy Ind Ltd | Refrigerant |
-
1987
- 1987-12-10 JP JP62312578A patent/JPH01153785A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184584A (en) * | 1984-03-02 | 1985-09-20 | Mitsubishi Heavy Ind Ltd | Refrigerant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2927299A2 (en) | 2014-04-02 | 2015-10-07 | Panasonic Intellectual Property Management Co., Ltd. | Heat storage apparatus, method for storing heat, and method for producing heat storage apparatus |
| US10161688B2 (en) | 2014-04-02 | 2018-12-25 | Panasonic Intellectual Property Management Co., Ltd. | Heat storage apparatus, method for storing heat, and method for producing heat storage apparatus |
| US10921064B2 (en) | 2014-04-02 | 2021-02-16 | Panasonic Intellectual Property Management Co., Ltd. | Heat storage apparatus, method for storing heat, and method for producing heat storage apparatus |
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