JPH11264681A - Cold storage method, cold storage system, and cold storage agent using clathrate hydrate - Google Patents
Cold storage method, cold storage system, and cold storage agent using clathrate hydrateInfo
- Publication number
- JPH11264681A JPH11264681A JP10068901A JP6890198A JPH11264681A JP H11264681 A JPH11264681 A JP H11264681A JP 10068901 A JP10068901 A JP 10068901A JP 6890198 A JP6890198 A JP 6890198A JP H11264681 A JPH11264681 A JP H11264681A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- clathrate hydrate
- concentration
- melting point
- hydrate
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Landscapes
- Other Air-Conditioning Systems (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、冷房などの空調設
備や、食品等の冷却装置などに用いられる冷熱体の蓄冷
方法、蓄冷システム、蓄冷剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold storage method, a cold storage system, and a cold storage agent for a cold body used for air conditioning equipment such as air conditioners and cooling devices for foods and the like.
【０００２】[0002]
【従来の技術】この種の用途に使用される従来公知の蓄
冷方法として以下のものがある。 （１）冷水の温度差による蓄冷 空調では、冷房用の冷水温度は５〜７℃であり、負荷の
小さい時間に冷凍機により冷水を貯蔵タンク（蓄熱槽）
に貯蔵する。冷水の比熱は１ｋｃａｌ／ｋｇＫであるた
め、利用温度差を７℃とすると、１ｋｇ冷水あたり７ｋ
ｃａｌ／ｋｇと単位重量当りの蓄冷量が少ないという欠
点がある。2. Description of the Related Art There are the following known cold storage methods used for this kind of application. (1) Cold storage due to the difference in temperature of cold water In air conditioning, the temperature of cold water for cooling is 5 to 7 ° C, and cold water is stored in a storage tank (heat storage tank) by a refrigerator during a small load period.
Store in. Since the specific heat of cold water is 1 kcal / kgK, if the temperature difference of use is 7 ° C., 7 k per 1 kg of cold water
There is a drawback that cal / kg and the amount of cold storage per unit weight are small.
【０００３】（２）氷などの凝固・融解潜熱を用いた蓄
冷 氷の融解潜熱は、約８０ｋｃａｌ／ｋｇであるため、氷
水の一部を氷にして蓄冷することで、蓄熱密度は冷水よ
り高くできる。例えば、冷水中の氷の体積割合を２０％
とすると、氷の潜熱及び冷水の顕熱（温度差１２℃の場
合）を含めた蓄熱密度は、約２８ｋｃａｌ／ｋｇとな
る。(2) Cold storage using solidification and melting latent heat of ice, etc. Ice has a latent heat of fusion of about 80 kcal / kg. it can. For example, if the volume ratio of ice in cold water is 20%
Then, the heat storage density including the latent heat of ice and the sensible heat of cold water (when the temperature difference is 12 ° C.) is about 28 kcal / kg.
【０００４】しかし、氷を生成させるためには、冷水を
０℃以下に冷却しなければならず、冷水を５℃に冷却す
るよりも冷凍機の動力は大きくなるのが欠点である。 （３）氷以外の固液相変化物質を用いた蓄冷 水や氷以外の冷熱蓄熱材として利用可能な物質として、
ＬｉＣｌＯ2 ・３Ｈ2ＯやＮａ2 ＳＯ4 ・１０Ｈ2 Ｏ＋
ＮＨ4 Ｃｌなどの無機水和塩類や気体水和物が知られて
いる（文献１．川崎、秋谷「基体水和物の冷熱蓄熱材へ
の応用」：ケミカルエンジニアリングvol.27,No.8,603-
608,1982、文献２．日本伝熱学会編「環境と省エネルギ
ーのためのエネルギー新技術体系」ｐ．８０２、参照）
しかし、ＬｉＣｌＯ2 ・３Ｈ2 ＯやＮａ2 ＳＯ4 ・１０
Ｈ2 Ｏ＋ＮＨ4 Ｃｌなどの無機水和塩類は、比較的潜熱
量は大きいものの、調和融点（後述）を持たず、無水塩
の濃度によって水和物が変化する。このため、冷却・加
熱過程で相分離をおこし、所定の蓄熱量が得られなくな
る問題が生ずる。[0004] However, in order to generate ice, it is necessary to cool the cold water to 0 ° C or less, and the drawback is that the power of the refrigerator becomes larger than cooling the cold water to 5 ° C. (3) Cold storage using solid-liquid phase change substances other than ice As substances that can be used as cold heat storage materials other than water and ice,
LiClO 2 .3H 2 O or Na 2 SO 4 .10H 2 O +
Inorganic hydrate salts such as NH 4 Cl and gas hydrates are known (Reference 1. Kawasaki and Akiya “Application of base hydrate to cold heat storage material”: Chemical Engineering vol.27, No.8, 603-)
608, 1982; The Heat Transfer Society of Japan, New Energy System for Environment and Energy Saving, p. 802, see)
However, LiClO 2 · 3H 2 O and Na 2 SO 4 · 10
Inorganic hydrated salts such as H 2 O + NH 4 Cl have a relatively large latent heat, but do not have a harmonic melting point (described later), and the hydrate changes depending on the concentration of the anhydrous salt. For this reason, phase separation occurs in the cooling / heating process, and there is a problem that a predetermined amount of heat cannot be obtained.
【０００５】また、文献１に記載されている気体水和物
は、Ｒ１１やＲ１２などのオゾン破壊係数の大きい物質
であったり、また、大気圧下では気体であるため、加圧
された密閉容器や配管を用いる必要があり、蓄冷装置が
高価なものとなる。The gas hydrate described in Document 1 is a substance having a large ozone depletion coefficient such as R11 or R12, or is a gas under the atmospheric pressure. And the use of pipes, which makes the regenerator expensive.
【０００６】[0006]
【発明が解決しようとする課題】以上のように、今まで
に実用化あるいは提案されてきた蓄冷方法には、それぞ
れ問題点があった。本発明は、これらの課題を解決すべ
くなされたもので、蓄冷材に求められる蓄熱密度（潜熱
量）が大きく、安定した熱特性を有し、経済性、安全性
があり取り扱いが容易である包接水和物を用いた蓄冷方
法、蓄冷システムおよび蓄熱剤を提供することを目的と
する。As described above, each of the cold storage methods which have been put to practical use or proposed so far has a problem. The present invention has been made to solve these problems, and has a large heat storage density (latent heat amount) required for a cold storage material, has stable thermal characteristics, is economical, safe, and easy to handle. An object of the present invention is to provide a cold storage method, a cold storage system and a heat storage agent using clathrate hydrate.
【０００７】[0007]
【課題を解決するための手段】すなわち本発明は、 ( １) 包接水和物生成物質を含み、その濃度が調和融
点を与える濃度に設定された水溶液を用意する工程と、
この水溶液を冷却して包接水和物を生成する工程とを具
備したことを特徴とする包接水和物の蓄冷方法。That is, the present invention provides: (1) a step of preparing an aqueous solution containing a clathrate hydrate-forming substance, the concentration of which is set to a concentration that gives a harmonic melting point;
Cooling the aqueous solution to produce a clathrate hydrate.
【０００８】( ２) 包接水和物生成物質を含み、その
濃度が調和融点を与える水溶液濃度より低い濃度に設定
された水溶液を用意する工程と、この水溶液を冷却して
包接水和物を生成する工程を具備したことを特徴とする
包接水和物の蓄冷方法。(2) A step of preparing an aqueous solution containing a clathrate hydrate-forming substance, the concentration of which is set to a concentration lower than the concentration of an aqueous solution giving a harmonic melting point, and cooling the aqueous solution to form a clathrate hydrate A method for regenerating clathrate hydrates, comprising the step of:
【０００９】( ３) 融点降下剤と包接水和物生成物質
とを含む水溶液を用意する工程と、この水溶液を冷却し
て包接水和物を生成する工程とを具備したことを特徴と
する( １) 又は( ２) に記載の包接水和物の蓄冷方法。(3) The method includes a step of preparing an aqueous solution containing a melting point depressant and a clathrate hydrate-forming substance, and a step of cooling the aqueous solution to form a clathrate hydrate. (1) The method for regenerating clathrate hydrate according to (1) or (2).
【００１０】( ４) 包接水和物生成物質は、テトラｎ
−ブチルアンモニウム塩、テトラｉｓｏ−アミルアンモ
ニウム塩、テトラｎ−ブチルフォスフォニウム塩、及び
トリｉｓｏ−アミルサルフォニウム塩の群から選択され
た一種又は二種以上であることを特徴とする( １) 〜(
３) のいずれかに記載の包接水和物の蓄冷方法。(4) The clathrate hydrate-forming substance is tetra-n
Or one or more selected from the group consisting of -butylammonium salt, tetraiso-amylammonium salt, tetra-n-butylphosphonium salt, and triiso-amylsulfonium salt (1) ) ~ (
3) The method for regenerating clathrate hydrate according to any of 3).
【００１１】( ５) 包接水和物生成物質は臭化テトラ
ｎ−ブチルアンモニウムで、設定される水溶液濃度は４
０％以下、４％以上であることを特徴とする( １) 〜(
３) のいずれかに記載の包接水和物の蓄冷方法。(5) The clathrate hydrate-forming substance is tetra-n-butylammonium bromide, and the set aqueous solution concentration is 4
0% or less and 4% or more (1) to (
3) The method for regenerating clathrate hydrate according to any of 3).
【００１２】( ６) 調和融点を与える濃度又はこの濃
度未満に設定された包接水和物生成物質の水溶液を収容
する手段と、この収容手段に収容された水溶液を冷却し
て、包接水和物を生成しスラリー状とする手段とを備え
たことを特徴とする包接水和物の蓄冷システム。(6) A means for containing an aqueous solution of a clathrate hydrate-forming substance set at or below a concentration that gives a harmonic melting point, and cooling the aqueous solution contained in the containing means to form a clathrate A clathrate hydrate regenerative system, comprising: means for producing a hydrate to form a slurry.
【００１３】( ７) 包接水和物生成物質を含む水溶液
からなる蓄冷剤。 ( ８) 包接水和物生成物質を含む水溶液は、調和融点
を与える水溶液濃度に設定されている( ７) に記載の蓄
冷剤。(7) A regenerator comprising an aqueous solution containing a clathrate hydrate-forming substance. (8) The regenerator according to (7), wherein the aqueous solution containing the clathrate hydrate-forming substance is set to an aqueous solution concentration that gives a harmonic melting point.
【００１４】( ９) 包接水和物生成物質を含む水溶液
は、調和融点を与える水溶液濃度よりも低い濃度に設定
されている( ７) に記載の蓄冷剤。 ( １０) 包接水和物生成物質を含む水溶液は、融点降
下剤を混入してなる（７) 〜( ９) のいずれかに記載の
蓄冷剤。(9) The regenerator according to (7), wherein the aqueous solution containing the clathrate hydrate-forming substance is set to a concentration lower than the concentration of the aqueous solution that gives a harmonic melting point. (10) The regenerator according to any one of (7) to (9), wherein the aqueous solution containing the clathrate hydrate-forming substance is mixed with a melting point depressant.
【００１５】( １１) 包接水和物生成物質は臭化テト
ラｎ−ブチルアンモニウムで、設定される水溶液濃度は
４０％以下、４％以上であることを特徴とする( ７) 〜
(９) のいずれか記載の蓄冷剤である。(11) The clathrate hydrate-forming substance is tetra-n-butylammonium bromide, and the set aqueous solution concentration is 40% or less and 4% or more.
(9) The regenerator according to any of (9).
【００１６】[0016]
【発明の実施の形態】本発明に係る包接水和物とは、水
分子（ホスト分子）で構成された籠状の包接格子内に以
下の様なゲスト分子が包み込まれて結晶化する化合物を
いう。ゲスト分子として、テトラｎ−ブチルアンモニウ
ム塩、テトラｉｓｏ−アミルアンモニウム塩、テトラｎ
−フォスフォニウム塩、トリｉｓｏ−アミルサルフォニ
ウム塩の例として、テトラｎ−ブチルアンモニウム塩と
してフッ化テトラｎ−ブチルアンモニウム（ｎ−Ｃ4 Ｈ
9 ）4 ＮＦ），塩化テトラｎ−ブチルアンモニウム
（（ｎ−Ｃ4 Ｈ9 ）4 ＮＣｌ），臭化テトラｎ−ブチル
アンモニウム（（ｎ−Ｃ4 Ｈ9 ）4 ＮＢｒ）などがあ
る。BEST MODE FOR CARRYING OUT THE INVENTION The clathrate hydrate according to the present invention is crystallized by encasing the following guest molecules in a cage-shaped clathrate lattice composed of water molecules (host molecules). Refers to a compound. As guest molecules, tetra n-butyl ammonium salt, tetra iso-amyl ammonium salt, tetra n
- phosphonium salt, examples of tri-iso- amyl monkey iodonium salt, fluoride tetra n- butylammonium (n-C 4 H tetracarboxylic n- butylammonium salt
9) 4 NF), chloride tetra n- butylammonium ((n-C 4 H 9 ) 4 NCl), tetra n- butylammonium ((n-C 4 H 9 ) 4 NBr) , and the like.
【００１７】これらＦ，Ｃｌ，Ｂｒの代わりに酢酸（Ｃ
Ｈ3 ＣＯ2 ），重炭酸（ＨＣＯ2 ），クロム酸（ＣｒＯ
4 ），タングステン酸（ＷＯ4 ），シュウ酸（Ｃ2 Ｏ
4 ），リン酸（ＨＰＯ4 ）でもよい。その他の上記塩も
同様である。Acetic acid (C) is used in place of these F, Cl and Br.
H 3 CO 2 ), bicarbonate (HCO 2 ), chromic acid (CrO
4 ), tungstic acid (WO 4 ), oxalic acid (C 2 O)
4 ), phosphoric acid (HPO 4 ) may be used. The same applies to other salts described above.
【００１８】以下、臭化テトラｎ−ブチルアンモニウム
（（ｎ−Ｃ4 Ｈ9 ）4 ＮＢｒ）を例にとり、本発明の蓄
冷システムを説明する。水溶液濃度と融点の関係を図１
に示す。また、包接水和物が生成、分解するときの反応
式を式（１）に示す。[0018] Hereinafter, taking tetra n- butylammonium the ((n-C 4 H 9 ) 4 NBr) in example describes cold energy storage system of the present invention. Figure 1 shows the relationship between aqueous solution concentration and melting point.
Shown in The reaction formula when the clathrate hydrate is formed and decomposed is shown in formula (1).
【００１９】 (n-C4 H 9 ) 4 NBr ＋n ・H 2 O ←→ (n-C4 H 9 ) 4 NBr ・n ・H 2 O …式（１） ここで、ｎは水和数で、その値はおよそ２６で常に一定
である。(NC 4 H 9 ) 4 NBr + n · H 2 O ← → (nC 4 H 9 ) 4 NBr · n · H 2 O Formula (1) where n is the hydration number and the value is It is always constant at about 26.
【００２０】図１に示されるように、この包接水和物生
成物質を含む水溶液は、水溶液濃度約４０ｗｔ％で融点
が極大値、１１．８℃である。この水溶液濃度の融点は
調和融点と呼ばれ、ここでは水溶液中の濃度と包接水和
物中の塩分濃度が等しい。As shown in FIG. 1, the aqueous solution containing this clathrate hydrate-forming substance has a maximum melting point of 11.8 ° C. at an aqueous solution concentration of about 40 wt%. The melting point of this aqueous solution concentration is called the harmonic melting point, where the concentration in the aqueous solution is equal to the salt concentration in the clathrate hydrate.
【００２１】従って、調和融点を与える水溶液濃度（こ
の例では常温における塩濃度が４０ｗｔ％）に設定した
水溶液を用いてこれを冷却すると、調和融点（１１．８
℃）で包接水和物が生成しはじめ、水溶液が全て包接水
和物になるまでこの融点で一定になる。分解（融解）時
も同様にこの融点一定で冷熱を放出する。なお、潜熱量
は約４６ｋｃａｌ／ｋｇであり、利用上限温度を１２℃
とすると、水和物の体積割合が５６％で蓄熱密度は２６
ｋｃａｌ／ｋｇとなる。Therefore, when an aqueous solution which is set to a concentration of an aqueous solution giving a harmonic melting point (in this example, the salt concentration at room temperature is 40 wt%) is cooled, the harmonic melting point (11.8) is obtained.
C.), the clathrate hydrate begins to form and this melting point is constant until all aqueous solutions become clathrate hydrate. Similarly, at the time of decomposition (melting), cold heat is released at the same melting point. The amount of latent heat is about 46 kcal / kg, and the maximum use temperature is 12 ° C.
Then, the volume ratio of the hydrate is 56% and the heat storage density is 26
kcal / kg.
【００２２】このようにこの蓄冷剤は、蓄熱密度が大き
く、安定した熱特性を有する。また、従来は触媒として
用いられているので容易に入手可能であり、経済的かつ
安全である。As described above, the regenerator has a large heat storage density and stable thermal characteristics. Further, since it is conventionally used as a catalyst, it is easily available, and is economical and safe.
【００２３】また、調和融点を与える上記水溶液濃度よ
り低い濃度に設定した水溶液（例えば常温で２７．２ｗ
ｔ％の水溶液）を用いて冷却すると、約９．４℃で水和
物が生成しはじめ、次第に水溶液中の塩分濃度が低下し
ていき、それにつれて水和物の生成温度も低下してい
く。すなわち、図１の曲線に沿って包接水和物の生成温
度も下がる。空調に適する１５℃程度の水・空気を作る
ために水溶液を５℃まで冷却すると、水溶液中の塩分濃
度は約１７ｗｔ％になる。このとき、水溶液の４３％が
水和物になる。また蓄熱量は、およそ２６ｋｃａｌ／ｋ
ｇとなる（水和物の比熱を０．５３ｋｃａｌ／ｋｇＫ，
水溶液の比熱を０．９６ｋｃａｌ／ｋｇＫとした）。ま
た、包接水和物の潜熱を利用する場合には常温で濃度４
％以上の濃度にする必要がある。An aqueous solution (for example, 27.2 watts at room temperature) set at a concentration lower than the above aqueous solution concentration that gives a harmonic melting point.
(% aqueous solution), a hydrate starts to form at about 9.4 ° C., and the salt concentration in the aqueous solution gradually decreases, and the hydrate formation temperature decreases accordingly. . That is, the formation temperature of the clathrate hydrate also decreases along the curve in FIG. When the aqueous solution is cooled to 5 ° C. in order to produce water and air at approximately 15 ° C. suitable for air conditioning, the salt concentration in the aqueous solution becomes about 17 wt%. At this time, 43% of the aqueous solution becomes a hydrate. The heat storage amount is approximately 26 kcal / k
g (specific heat of hydrate is 0.53 kcal / kgK,
The specific heat of the aqueous solution was 0.96 kcal / kgK). When the latent heat of clathrate hydrate is used, the concentration is 4 at room temperature.
%.
【００２４】このように、調和融点を与える上記水溶液
濃度より低い濃度に設定した水溶液を用いると、更に以
下の利点を備える。 （１）融点（生成温度）が低温側に変化するため、低い
温度の冷熱を蓄冷でき、その結果、所望の低い温度で取
出することができる。As described above, the use of an aqueous solution set at a concentration lower than the above-mentioned aqueous solution concentration that gives a harmonic melting point has the following advantages. (1) Since the melting point (generation temperature) changes to a lower temperature side, low-temperature cold heat can be stored, and as a result, it can be extracted at a desired low temperature.
【００２５】（２）融点（生成温度）が低温側に変化し
ていくため、水和物と水又は空気と熱交換させる場合、
その温度差がほぼ一定でしかも大きい。このため熱交換
効率が高く、熱交換器をコンパクトとすることができ
る。即ち、熱交換器で２０℃の水または空気を冷却して
１５℃とするに際し、図２のａに示す調和融点濃度の場
合、水又は空気の出側（蓄冷剤の入り側）の蓄冷剤の温
度が１１．８℃であり、その温度差が３．８℃しかない
が、図２のｂに示す調和融点濃度より低い場合、例えば
水又は空気の出側（蓄冷剤の入り側）の蓄冷剤の温度が
５℃であり、その温度差を１０℃とすることができる。(2) Since the melting point (generation temperature) changes to a lower temperature side, when heat exchange is performed between the hydrate and water or air,
The temperature difference is almost constant and large. Therefore, the heat exchange efficiency is high, and the heat exchanger can be made compact. That is, when the water or the air at 20 ° C. is cooled to 15 ° C. by the heat exchanger and the harmonic melting point concentration shown in FIG. 2A is reached, the regenerator on the outlet side of the water or air (the inlet side of the regenerator). Is 11.8 ° C., and the temperature difference is only 3.8 ° C., but is lower than the harmonic melting point concentration shown in FIG. 2b, for example, at the outlet of water or air (the inlet of the regenerator). The temperature of the regenerator is 5 ° C., and the temperature difference can be 10 ° C.
【００２６】（３）ほぼ同じ利用上限温度で蓄熱密度が
同じ場合、水溶液中の塩分濃度を低くできるため、その
分低コストになる。 （４）ほぼ同じ利用上限温度で蓄熱密度が同じ場合、水
和物の体積割合は小さくてすむため、水和物スラリの輸
送や貯蔵のハンドリングが容易となる。顕熱分が大きく
なる。即ち、蓄熱量は「潜熱」＋「顕熱」で示される
が、蓄熱量を同じとした場合、調和融点より低い濃度の
方が顕熱分が大きいため、水和物の体積割合が小さくて
すむ。この試算を表１に示す。(3) In the case where the heat storage density is the same at substantially the same upper limit use temperature, the salt concentration in the aqueous solution can be lowered, and the cost is accordingly reduced. (4) When the heat storage density is the same at substantially the same use upper limit temperature, the volume ratio of the hydrate may be small, and the handling of the transport and storage of the hydrate slurry becomes easy. Sensible heat increases. That is, the heat storage amount is represented by “latent heat” + “sensible heat”. When the heat storage amount is the same, the concentration of the hydrate is smaller at a concentration lower than the harmonic melting point because the sensible heat component is larger. Yes. This calculation is shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】次に本発明では、水溶液に水よりも凝固点
の小さい物質を混入させて、包接水和物の生成温度（融
点）を低下させることができる。臭化テトラｎ−ブチル
アンモニウム（（ｎ−Ｃ4 Ｈ9 ）4 ＮＢｒ）を例に取る
と、その調和融点は、１１．８℃であり、水溶液濃度と
融点の関係は上述したように図１のようになる。Next, in the present invention, the formation temperature (melting point) of clathrate hydrate can be lowered by mixing a substance having a smaller freezing point than water into the aqueous solution. Taking tetra n- butylammonium the ((n-C 4 H 9 ) 4 NBr) as an example, the harmonic melting point is 11.8 ° C., so that the relationship of solution concentration and melting point above 1 become that way.
【００２９】この水溶液に、エチレングリコール、プロ
ピレングリコールなど融点降下剤（水よりも融点の低い
物質）を混入させると、水溶液の融点は、この物質の混
入量によって低下する。そこで、用途により利用温度幅
を下げる必要がある場合、これら物質を適量混入させる
ことにより、任意の融点を持つ蓄冷剤を作ることができ
る。When a melting point depressant (a substance having a lower melting point than water) such as ethylene glycol or propylene glycol is mixed into the aqueous solution, the melting point of the aqueous solution is reduced by the amount of the substance. Therefore, when it is necessary to lower the use temperature range depending on the use, a regenerator having an arbitrary melting point can be produced by mixing these substances in an appropriate amount.
【００３０】[0030]
【発明の効果】このように、本発明に係る蓄冷剤を用い
れば、蓄熱密度が大きく、安定した熱特性を有する。ま
た、従来は触媒として用いられており、容易に入手可能
であり、経済的かつ安全である。特に、調和融点を与え
る上記水溶液濃度より低い濃度に設定した水溶液を用い
ると、所望の低い温度範囲で冷熱を蓄冷でき、その結
果、低い温度で取出せる。そして、熱交換効率が高いの
で、熱交換器をコンパクトにでき、さらに、コストも安
く、水和物スラリの輸送や貯蔵のハンドリングが容易と
なる。As described above, when the regenerator according to the present invention is used, the heat storage density is large and stable heat characteristics are obtained. It has been conventionally used as a catalyst, is easily available, is economical and safe. In particular, when an aqueous solution set to a concentration lower than the above aqueous solution concentration that gives a harmonic melting point is used, cold heat can be stored in a desired low temperature range, and as a result, can be taken out at a low temperature. Since the heat exchange efficiency is high, the heat exchanger can be made compact, the cost is low, and the handling of hydrate slurry transportation and storage becomes easy.
【００３１】さらに、水より融点の低い物質を混入させ
ることによって、同じ塩を用いた水溶液で任意の融点を
持つ蓄冷剤を作ることができるため、汎用性が高く、コ
スト安にもなる。Further, by mixing a substance having a lower melting point than water, a regenerator having an arbitrary melting point can be produced from an aqueous solution using the same salt, so that the versatility is high and the cost is low.
【図１】包接水和物生成物質を含む水溶液濃度と融点と
の関係を示す図。FIG. 1 is a diagram showing the relationship between the concentration of an aqueous solution containing a clathrate hydrate-forming substance and the melting point.
【図２】包接水和物生成物質を含む水溶液を蓄冷剤とし
て用いた場合の熱交換器内の温度変化を示す説明図で、
ａは調和融点濃度の包接水和物生成物質を含む水溶液を
蓄冷剤として用いた場合、ｂは調和融点濃度より低い包
接水和物を含む水溶液を蓄冷剤として用いた場合をそれ
ぞれ示す。FIG. 2 is an explanatory diagram showing a temperature change in a heat exchanger when an aqueous solution containing a clathrate hydrate-forming substance is used as a regenerator;
a shows the case where an aqueous solution containing a clathrate hydrate-forming substance having a harmonic melting point concentration was used as a regenerator, and b shows the case where an aqueous solution containing a clathrate hydrate having a lower harmonic melting point concentration was used as a regenerator.
Claims (11)
調和融点を与える濃度に設定された水溶液を用意する工
程と、この水溶液を冷却して包接水和物を生成する工程
とを具備したことを特徴とする包接水和物の蓄冷方法。1. A step of preparing an aqueous solution containing a clathrate hydrate-forming substance, the concentration of which is set to give a harmonic melting point, and a step of cooling the aqueous solution to form a clathrate hydrate. A method for regenerating clathrate hydrates, comprising:
調和融点を与える水溶液濃度より低い濃度に設定された
水溶液を用意する工程と、この水溶液を冷却して包接水
和物を生成する工程を具備したことを特徴とする包接水
和物の蓄冷方法。2. A step of preparing an aqueous solution containing a clathrate hydrate-forming substance, the concentration of which is set to a concentration lower than that of an aqueous solution giving a harmonic melting point, and cooling the aqueous solution to form an clathrate hydrate. A method for regenerating clathrate hydrate, comprising a step of producing.
む水溶液を用意する工程と、この水溶液を冷却して包接
水和物を生成する工程とを具備したことを特徴とする請
求項１又は２に記載の包接水和物の蓄冷方法。3. A method for preparing an aqueous solution containing a melting point depressant and a clathrate hydrate-forming substance, and a step of cooling the aqueous solution to form a clathrate hydrate. The method for regenerating clathrate hydrate according to claim 1 or 2.
ルアンモニウム塩、テトラｉｓｏ−アミルアンモニウム
塩、テトラｎ−ブチルフォスフォニウム塩、及びトリｉ
ｓｏ−アミルサルフォニウム塩の群から選択された一種
又は二種以上であることを特徴とする請求項１〜３のい
ずれかに記載の包接水和物の蓄冷方法。4. The clathrate hydrate-forming substance comprises tetra-n-butylammonium salt, tetra-iso-amylammonium salt, tetra-n-butylphosphonium salt, and tri-i-ammonium salt.
The method for regenerating clathrate hydrate according to any one of claims 1 to 3, wherein the clathrate hydrate is one kind or two or more kinds selected from the group of so-amylsulfonium salts.
チルアンモニウムで、設定される水溶液濃度は４０％以
下、４％以上であることを特徴とする請求項１〜３のい
ずれかに記載の包接水和物の蓄冷方法。5. The clathrate hydrate-forming substance is tetra-n-butylammonium bromide, and the set aqueous solution concentration is 40% or less and 4% or more. 5. The method for regenerating clathrate hydrate according to the above.
に設定された包接水和物生成物質の水溶液を収容する手
段と、この収容手段に収容された水溶液を冷却して、包
接水和物を生成しスラリー状とする手段とを備えたこと
を特徴とする包接水和物の蓄冷システム。6. A means for accommodating an aqueous solution of a clathrate hydrate-forming substance set at or below a concentration giving a harmonic melting point, and cooling the aqueous solution contained in said accommodating means to form a clathrate hydrate. And a means for producing a product and converting the product into a slurry.
る蓄冷剤。7. A regenerator comprising an aqueous solution containing a clathrate hydrate-forming substance.
和融点を与える水溶液濃度に設定されている請求項７に
記載の蓄冷剤。8. The regenerator according to claim 7, wherein the aqueous solution containing the clathrate hydrate-forming substance is set to an aqueous solution concentration that gives a harmonic melting point.
和融点を与える水溶液濃度よりも低い濃度に設定されて
いる請求項７に記載の蓄冷剤。9. The regenerator according to claim 7, wherein the concentration of the aqueous solution containing the clathrate hydrate-forming substance is lower than the concentration of the aqueous solution that gives a harmonic melting point.
融点降下剤を混入してなる請求項７〜９のいずれかに記
載の蓄冷剤。10. The aqueous solution containing the clathrate hydrate-forming substance,
The regenerator according to any one of claims 7 to 9, further comprising a melting point depressant.
ブチルアンモニウムで、設定される水溶液濃度は４０％
以下、４％以上であることを特徴とする請求項７〜９の
いずれかに記載の蓄冷剤。11. The clathrate hydrate-forming substance is tetra-n-bromide
With butyl ammonium, set aqueous solution concentration is 40%
The regenerator according to any one of claims 7 to 9, wherein the content is 4% or more.
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|---|---|---|---|
| JP06890198A JP3641362B2 (en) | 1998-03-18 | 1998-03-18 | Cold storage method using cold clathrate, cold storage system, and cold storage agent |
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|---|---|---|---|
| JP06890198A JP3641362B2 (en) | 1998-03-18 | 1998-03-18 | Cold storage method using cold clathrate, cold storage system, and cold storage agent |
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|---|---|---|---|
| JP2004367878A Division JP4134982B2 (en) | 2004-12-20 | 2004-12-20 | Cold storage method, cold storage system, cold storage agent, and method of extracting cold |
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| Publication Number | Publication Date |
|---|---|
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| JP3641362B2 JP3641362B2 (en) | 2005-04-20 |
Family
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| Country | Link |
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