JPH10259978A - Cold heat transport method and system - Google Patents

Cold heat transport method and system

Info

Publication number
JPH10259978A
JPH10259978A JP9096005A JP9600597A JPH10259978A JP H10259978 A JPH10259978 A JP H10259978A JP 9096005 A JP9096005 A JP 9096005A JP 9600597 A JP9600597 A JP 9600597A JP H10259978 A JPH10259978 A JP H10259978A
Authority
JP
Japan
Prior art keywords
clathrate
liquid
heat
cold
cold heat
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.)
Granted
Application number
JP9096005A
Other languages
Japanese (ja)
Other versions
JP3309760B2 (en
Inventor
Hidemasa Ogose
英雅 生越
Shingo Takao
信吾 高雄
Shinichiro Fukushima
信一郎 福嶋
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.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
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 NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP09600597A priority Critical patent/JP3309760B2/en
Publication of JPH10259978A publication Critical patent/JPH10259978A/en
Priority to US09/406,217 priority patent/US6237346B1/en
Priority claimed from US09/406,217 external-priority patent/US6237346B1/en
Application granted granted Critical
Publication of JP3309760B2 publication Critical patent/JP3309760B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14Thermal energy storage

Abstract

PROBLEM TO BE SOLVED: To eliminate an environmental pollution problem such as destruction of the ozone layer by using as a transport medium of cold heat a quasi-clathrate hydrate (liquid-liquid clathrate) wherein an onium salt having a C4 H9 group, an iso-C5 H11 group is included and crystallized as a guest in a basket-shaped clathrate lattice constituted of water molecules. SOLUTION: Equipment 4 necessitating cold heat cools suction air for reducing compression power and the cold heat required for cooling is supplied from a clathrate supply pipeline 1. A water solution brought about by melting by the heat received in the equipment 4 is recovered by a cooling device 3 through a pipeline 2. Between the equipment 4 and the device 3, a clathrate storage vessel 5 is connected to the pipeline 1 and a water solution storage vessel 6 to the pipeline 2. In this system, a quasi-clathrate hydrate wherein an onium salt having a C4 H9 group, an iso-C5 H11 group is included and crystallized as a guest in a basket-shaped clathrate lattice constituted of water molecules is used as a transport medium of the cold heat. As the quasi-clathrate hydrate, water-tetra-n-butylammonium bromide is used.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は冷熱の輸送方法及び
そのシステムに関するものである。
The present invention relates to a method and a system for transporting cold heat.

【0002】[0002]

【従来の技術】冷熱の輸送媒体として、従来から気体水
和物を用いることが検討されている。この気体水和物
は、包接水和物とも呼ばれ、水分子で構成された籠状の
包接格子の中に、メタン、エタン、プロパン、フロン1
1,フロン12等の気体分子がゲストとして包み込まれ
て結晶化する化合物である。
2. Description of the Related Art The use of gaseous hydrate as a transport medium for cold heat has been studied. This gaseous hydrate is also called clathrate hydrate, and methane, ethane, propane, and chlorofluorocarbon are contained in a cage-like clathrate lattice composed of water molecules.
It is a compound in which gas molecules such as 1, Freon 12 and the like are encapsulated as a guest and crystallized.

【0003】そして、この気体水和物は、結晶析出温度
(臨界分解点温度)が氷点よりも高く、5〜20℃の温
度範囲内にあり、その生成熱も氷の潜熱に近い70〜9
0cal/g にあるので、この気体水和物の特性を生かして
冷熱の蓄熱材あるいは冷熱の輸送媒体として利用するこ
とが検討されている。
The gas hydrate has a crystal precipitation temperature (critical decomposition point temperature) higher than the freezing point and is in a temperature range of 5 to 20 ° C., and its heat of formation is 70 to 9 which is close to the latent heat of ice.
Since it is at 0 cal / g, utilization of the gas hydrate as a cold heat storage material or a cold heat transport medium is being studied.

【0004】[0004]

【発明が解決しようとする課題】しかし、上記の気体水
和物の主流を占めるフロン系水和物には、周知のように
オゾン層破壊などの環境汚染の問題があり、また、気体
水和物の臨界分解点の圧力は極めて高いものや、また真
空圧力が必要なものであり、実用化には問題がある。本
発明は、上記のような問題点を解消できる冷熱の輸送媒
体を用いた冷熱輸送方法を提供することを課題とするも
のである。
However, the above-mentioned CFC-based hydrate, which occupies the main stream of the gas hydrate, has a problem of environmental pollution such as depletion of the ozone layer. Since the pressure at the critical decomposition point of a substance is extremely high or requires a vacuum pressure, there is a problem in practical use. An object of the present invention is to provide a cold transport method using a cold transport medium that can solve the above-described problems.

【0005】[0005]

【課題を解決するための手段】本発明の冷熱輸送方法
は、冷熱の輸送媒体として、水分子で構成された籠状の
包接格子内にC49 基、iso - C511基を持つオニ
ウム塩がゲストとして包み込まれて結晶化する準包接水
和物(液液クラスレート)を使用することを特徴とする
ものである。
According to the cold transport method of the present invention, as a cold transport medium, a C 4 H 9 group and an iso-C 5 H 11 group are contained in a cage-shaped inclusion lattice composed of water molecules. Characterized in that a quasi-clathrate hydrate (liquid-liquid clathrate) is used in which an onium salt having the following formula is encapsulated as a guest and crystallized.

【0006】ここで、オニウム塩とは、アンモニウム塩
(ammonium),フォスフォニウム塩(phosphonium ),
サルフォニウム塩(sulfonium )等であり、また準包接
水和物(液液クラスレート、液液包接水和物とも呼ばれ
ている)は、ゲストが気体ではないため、その水和物の
結晶構造は気体水和物よりも複雑である。
Here, onium salts include ammonium salts (ammonium), phosphonium salts (phosphonium),
Sulfonium salts, etc., and quasi-clathrate hydrates (also called liquid-liquid clathrates and liquid-liquid clathrate hydrates) are crystals of the hydrate because the guest is not a gas The structure is more complex than gas hydrate.

【0007】そして、準包接水和物はゲストが臭化テト
n ブチルアンモニウム([CH3(CH234
Br:略称;TBAB)であることを特徴とするもので
ある。なお、臭素(Br)の代わりにF,Cl,CHO
4 、CH3 C02 、HCO3、OH、NO3 、CrO
3 、WO4 などのテトラn ブチルアンモニウム塩でも良
い。
In the semi-clathrate hydrate, the guest is tetra- n -butylammonium bromide ([CH 3 (CH 2 ) 3 ] 4 N)
Br: Abbreviation: TBAB). F, Cl, CHO instead of bromine (Br)
4, CH 3 C0 2, HCO 3, OH, NO 3, CrO
3, WO 4 may be tetra-n-butylammonium salt such.

【0008】また冷熱輸送システムは、準包接水和物を
熱交換器が設けられた冷熱を必要とする複数の設備に供
給する管路と、熱を吸収して一部あるいは全てが液体と
なった媒体を複数のクラスレート生成装置に回収する管
路と、から構成されている。
[0008] Further, the cold transport system comprises a pipeline for supplying the quasi-clathrate hydrate to a plurality of facilities requiring cold heat provided with a heat exchanger, and a pipe that absorbs heat and partially or entirely becomes liquid. And a pipeline for collecting the changed medium into a plurality of clathrate generation devices.

【0009】そして、液液クラスレートを供給する管路
及びクラスレート生成装置に回収する管路のそれぞれに
貯蔵容器が接続されている。なお、冷熱を必要とする設
備での使用熱量に応じてゲストの濃度を調整することに
より、液液クラスレートの融点が変更できるようになっ
ている。
[0009] A storage container is connected to each of a pipe for supplying the liquid-liquid clathrate and a pipe for collecting the liquid-liquid clathrate. The melting point of the liquid-liquid clathrate can be changed by adjusting the concentration of the guest according to the amount of heat used in equipment that requires cold heat.

【0010】また、前記クラスレート生成装置の少なく
とも1つが蒸気吸収式冷凍機であり、中温ないし低温の
蒸気を冷凍機の熱源としている。また、空気の吸収式除
湿システムと併設された冷熱輸送システムであって、前
記蒸気吸収式冷凍機からの排熱を前記吸収式除湿システ
ムの吸収液の再生熱源としている。
[0010] At least one of the clathrate generating devices is a steam absorption refrigerator, and uses medium to low temperature steam as a heat source of the refrigerator. Further, in the cold heat transport system provided in parallel with the air absorption type dehumidification system, exhaust heat from the vapor absorption type refrigerator is used as a heat source for regenerating the absorbent in the absorption type dehumidification system.

【0011】[0011]

【発明の実施の形態】本発明方法を製鉄所に適用した場
合を例にして説明する。この場合の設備の一例を図1に
より説明する。ここで使用する冷熱輸送媒体としての液
液クラスレートは水ー臭化テトラn ブチルアンモニウム
(水−TBAB系)であり、大気圧下で容易に生成でき
るという特徴を持っている。
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An example in which the method of the present invention is applied to a steel mill will be described. An example of the equipment in this case will be described with reference to FIG. The liquid-liquid clathrate used as the cold transport medium used here is water-tetra- n -butylammonium bromide (water-TBAB system), which has a feature that it can be easily produced at atmospheric pressure.

【0012】そして、このクラスレート融点は、濃度が
40%程度の場合11.5℃で、融解熱は40〜50kc
al/kgである。なお、融点は、濃度を調整することによ
り、ほぼ0℃〜12℃の範囲で変えることができる。
The clathrate has a melting point of 11.5 ° C. when the concentration is about 40%, and a heat of fusion of 40 to 50 kc.
al / kg. The melting point can be changed in a range of approximately 0 ° C. to 12 ° C. by adjusting the concentration.

【0013】図1で、符号4は、冷熱を必要とする設
備、例えば空気圧縮機で、ここでは圧縮動力を低減させ
るために、吸気を冷却しており、冷却のために冷熱が必
要である。ここで必要とされる冷熱はクラスレート供給
管路1から供給される。
In FIG. 1, reference numeral 4 denotes equipment requiring cold heat, for example, an air compressor, which cools the intake air in order to reduce the compression power, and requires cold heat for cooling. . The cold required here is supplied from the clathrate supply line 1.

【0014】そして、設備4で冷熱を供給し、溶けた水
溶液は管路2を介してクラスレートを製造する冷却装置
3に回収される。ここでの、冷却装置は、例えば、電気
を利用した機械式冷凍機や、蒸気や温水を利用した吸収
式冷凍機である。この蒸気や温水のための熱源として
は、例えば加熱炉排ガスから熱回収された熱源等、従来
余り活用されていなかった低質の熱源が活用・利用され
る。
[0014] Cooling heat is supplied by the facility 4, and the dissolved aqueous solution is recovered through the pipe 2 to the cooling device 3 for producing a clathrate. The cooling device here is, for example, a mechanical refrigerator using electricity or an absorption refrigerator using steam or hot water. As a heat source for the steam or the hot water, a low-quality heat source, which has not been used so far, such as a heat source recovered from exhaust gas from a heating furnace, is used and used.

【0015】なお、冷熱を必要とする設備としては上記
の空気圧縮機での空気冷却装置の他に、空調装置での空
気冷却装置等がある。なお、設備4と装置3との間で、
利用流量に時間的なずれが生ずる場合を考慮して、管路
1にクラスレート貯蔵容器5が、管路2に水溶液貯蔵容
器6が接続されている。
As equipment requiring cold heat, there are an air cooling apparatus for an air conditioner and the like in addition to the air cooling apparatus for the air compressor. In addition, between equipment 4 and apparatus 3,
The clathrate storage container 5 is connected to the pipeline 1 and the aqueous solution storage container 6 is connected to the pipeline 2 in consideration of a case where a time lag occurs in the use flow rate.

【0016】すなわち、低質の熱が多量に発生する時
は、その熱を利用して水溶液を冷却し、クラスレートを
製造してクラスレートを貯蔵容器5に貯蔵する。そし
て、クラスレートを多量に必要とする時は、貯蔵容器5
に貯蔵されたクラスレートを使用する。
That is, when a large amount of low-quality heat is generated, the aqueous solution is cooled by using the heat, a clathrate is produced, and the clathrate is stored in the storage container 5. When a large amount of clathrate is required, the storage container 5
Use the stored clathrate.

【0017】一方、低質の熱が少量しか発生せず、しか
も多量のクラスレートが必要な時は、多量の水溶液が発
生する。この発生した水溶液は貯蔵容器6に貯蔵され
る。そして、クラスレートの供給管路1と、溶けた水溶
液の回収管路2とは、冷熱を必要とする設備4とクラス
レートを製造する冷却装置3とを介して接続されてい
る。
On the other hand, when only a small amount of low-quality heat is generated and a large amount of clathrate is required, a large amount of aqueous solution is generated. The generated aqueous solution is stored in the storage container 6. The supply line 1 for the clathrate and the recovery line 2 for the dissolved aqueous solution are connected via a facility 4 that requires cold heat and a cooling device 3 that manufactures the clathrate.

【0018】こうして、クラスレートの供給管路と溶け
た水溶液の回収管路を並行して、対象地域に循環して付
設することによって、広い場所であっても設備間の距離
は短く、一巡回路で全ての冷熱を必要とする設備を網羅
することができる。
In this way, the supply line for the clathrate and the recovery line for the dissolved aqueous solution are circulated and provided in parallel in the target area, so that the distance between the facilities is short even in a wide place, and Roads can cover all equipment that requires cooling.

【0019】このため、少ない設備投資で広範な地域に
散在する冷熱を必要とする設備に冷熱を供給することが
できる。なお、本発明で利用されるクラスレートは、ゲ
スト(TBAB)の濃度を調整することにより、その融
点を0〜12℃の範囲で変えることができるため、冷熱
を必要とする設備において、既設、時間でその利用熱量
が変化する場合でも、その利用熱量に合わせて最適な融
点にすることができる。
[0019] Therefore, it is possible to supply cold heat to equipment that needs cold heat scattered in a wide area with a small capital investment. The melting point of the clathrate used in the present invention can be changed in the range of 0 to 12 ° C. by adjusting the concentration of the guest (TBAB). Even when the amount of heat used changes with time, an optimum melting point can be obtained in accordance with the amount of heat used.

【0020】従って、夏期と冬期で利用熱量が異なる場
合や、昼間と夜間で利用熱量が異なる場合においても、
同一の冷熱媒体で濃度を調整するだけで良いためシステ
ムの簡素化及び冷熱製造費用の低減化が図れる。表1
に、水溶液温度が20℃の場合について、クラスレート
の濃度と利用可能熱量の関係を示す。
Therefore, even when the amount of heat used differs between summer and winter, or when the amount of heat used differs between daytime and nighttime,
Since it is only necessary to adjust the concentration with the same cooling medium, the system can be simplified and the cost of cold manufacturing can be reduced. Table 1
Fig. 6 shows the relationship between the concentration of clathrate and the amount of available heat when the temperature of the aqueous solution is 20C.

【0021】[0021]

【表1】 [Table 1]

【0022】クラスレート供給管路が一定で、その流量
が一定であっても、約1:2の範囲で供給熱量を変える
ことができることを示している。一般に冷熱体の製造・
消費・輸送設備は一定流量の時に最大の能率点に設定す
ることができ、最適な運転条件を具現できる。
This shows that even if the clathrate supply line is constant and its flow rate is constant, the amount of heat supplied can be changed within a range of about 1: 2. In general, the production of cold bodies
Consumption / transportation equipment can be set at the maximum efficiency point at a constant flow rate, and can realize optimal operating conditions.

【0023】そのため、エネルギー使用量に合わせて、
濃度調整することにより、最適条件を保ったままの運転
が可能となる。なお、図1において、符号7は他のクラ
スレートの供給管路及び溶けた水溶液の回収管路であ
る。
Therefore, according to the energy consumption,
By adjusting the concentration, it is possible to operate while maintaining the optimum conditions. In FIG. 1, reference numeral 7 denotes a supply line of another clathrate and a collection line of a dissolved aqueous solution.

【0024】次に、図2により、クラスレートを製造す
る冷却装置が蒸気吸収式冷凍機であり、また、空気の吸
収式除湿システムが冷熱輸送システムに併設されている
場合について説明する。
Next, a case will be described with reference to FIG. 2 where a cooling device for producing a clathrate is a vapor absorption refrigerator and an air absorption dehumidification system is provided in addition to a cold heat transport system.

【0025】ここで、液液クラスレートの供給管路及び
溶けた水溶液の回収管路並びにクラスレート及び水溶液
の貯蔵容器等については、図面の同一箇所に図1と同じ
符号を付して説明を省略する。
Here, the supply line for the liquid-liquid clathrate, the recovery line for the dissolved aqueous solution, the storage container for the clathrate and the aqueous solution, and the like are denoted by the same reference numerals in FIG. Omitted.

【0026】この場合のクラスレートを製造する冷却装
置3aは、蒸気吸収式の冷凍機であり、冷凍機の熱源と
しては、例えば製鉄所で、従来余り利用されていなかっ
た中温ないし低温の蒸気を利用する。
The cooling device 3a for producing the clathrate in this case is a refrigerator of a steam absorption type. As a heat source of the refrigerator, for example, a medium- or low-temperature steam, which has not been used so far in steel works, is used. Use.

【0027】そして、符号14で示す設備は、冷熱を必
要とすると共に、除湿システムの熱源を必要とする設備
である。例えば、空気を圧縮する圧縮機を有する設備
で、この設備では圧縮動力の低減を意図して吸気を冷却
するための冷熱を必要とすると共に、冷却された空気か
らドレンが発生して圧縮機に悪影響を及ぼさないように
するために湿分を除去する吸収式除湿システムを備えて
おり、吸収液の再生のための熱源を必要とする設備であ
る。
The equipment indicated by reference numeral 14 is equipment that requires cold heat and a heat source of the dehumidification system. For example, in a facility that has a compressor that compresses air, this facility requires cold heat to cool intake air with the intention of reducing compression power, and drain is generated from the cooled air to the compressor. This equipment is equipped with an absorption dehumidification system that removes moisture so as not to have any adverse effects, and requires a heat source for regeneration of the absorbent.

【0028】ここで使用する、空気中の湿分を吸収する
吸収液は塩化リチウムやエチレングリコールなどの吸湿
性の高い水溶液である。これら水溶液は、高濃度で水分
を吸収し、水分を吸収して低濃度になった溶液は熱を加
えることにより水分をとって高濃度溶液に再生して、再
び吸収液として利用できる。
The absorbing liquid used for absorbing moisture in the air used here is an aqueous solution having high hygroscopicity, such as lithium chloride and ethylene glycol. These aqueous solutions absorb water at a high concentration, and the solution that has absorbed the water to a low concentration can be regenerated into a high-concentration solution by applying heat to remove the water and reused as an absorbing solution.

【0029】符号11は上記の高濃度吸収液の供給管
路、符号12は低濃度になった溶液の回収管路である。
設備14には、これら管路11,12が接続され、高濃
度吸収液を供給すると共に低濃度になった溶液を回収す
るようになっている。なお、設備14には、同時に管路
1から液液クラスレートが供給され、溶けた水溶液が管
路2を介して回収されるようになっている。
Reference numeral 11 denotes a supply line for the above-mentioned high-concentration absorbent, and reference numeral 12 denotes a recovery line for the solution having a low concentration.
The pipes 11 and 12 are connected to the facility 14 so that a high-concentration absorbing solution is supplied and a low-concentration solution is recovered. In addition, the liquid-liquid clathrate is supplied to the equipment 14 from the pipe 1 at the same time, and the dissolved aqueous solution is recovered through the pipe 2.

【0030】なお、設備14aは、除湿装置のみを有す
る設備で、これには管路11、12のみが接続されてい
る。低濃度になった溶液は、再生装置22において,蒸
気吸収式の冷凍機3aからの配管23を介して送給され
る排熱あるいは低圧の蒸気を熱源として高濃度に再生さ
れるようになっている。また、再生装置21で、工場か
らの100℃以下の排熱源から回収した温水により再生
されるようになっている。
The facility 14a is a facility having only a dehumidifier, to which only the pipelines 11 and 12 are connected. The low-concentration solution is regenerated to a high concentration in the regenerating device 22 using exhaust heat or low-pressure steam supplied through a pipe 23 from the vapor absorption refrigerator 3a as a heat source. I have. Further, the regenerating apparatus 21 is configured to regenerate the hot water recovered from a waste heat source of 100 ° C. or less from the factory.

【0031】なお、管路11,12には、管路1,2の
場合と同様に利用流量に時間的なずれが生ずる場合を考
慮して、高濃度吸収液及び低濃度になった溶液の貯蔵容
器15,16が接続されている。
The pipes 11 and 12 are provided with a high-concentration absorbing solution and a low-concentration solution in consideration of a case where a time lag occurs in the use flow rate as in the case of the pipes 1 and 2. Storage containers 15 and 16 are connected.

【0032】また、符号17はクラスレートの供給、回
収管路及び湿分吸収高濃度溶液及び低濃度溶液の管路を
含む他の設備である。そして、クラスレートの供給管路
1と溶けた水溶液の回収管路2並びに高濃度吸収液の供
給管路11及び低濃度吸収液の回収管路12とが、冷熱
を必要とすると共に除湿システムの熱源を必要とする設
備14、クラスレートを製造する冷却装置3a及び湿分
吸収液の再生装置22を介して接続されている。
Reference numeral 17 denotes other equipment including a clathrate supply / recovery line and a line for a moisture-absorbing high-concentration solution and a low-concentration solution. The supply line 1 for the clathrate, the recovery line 2 for the dissolved aqueous solution, the supply line 11 for the high-concentration absorbing solution, and the recovery line 12 for the low-concentration absorbing solution require both cooling and heating and a dehumidifying system. It is connected via a facility 14 requiring a heat source, a cooling device 3a for producing a clathrate, and a moisture absorbing liquid regenerating device 22.

【0033】こうして、クラスレートの供給管路と溶け
た水溶液の回収管路並びに湿分吸収高濃度溶液及び低濃
度溶液の管路を並行して、対象地域に循環して付設する
ことによって、広い場所であっても設備間の距離は短
く、一巡回路で全ての冷熱を必要とする設備及び除湿吸
収液を必要とする設備を網羅することができる。
In this way, the clathrate supply line, the dissolved aqueous solution collection line, and the moisture absorption high concentration solution and low concentration solution lines are circulated in parallel to the target area, thereby providing a wide area. Even in a place, the distance between the equipments is short, and it is possible to cover all the equipment that requires cooling and heating and the equipment that requires the dehumidifying absorbent in a single circuit.

【0034】このため、少ない設備投資で広範な地域に
散在する冷熱を必要とする設備に冷熱を供給すると共
に、除湿吸収液を必要とする設備に吸収液を供給するこ
とができる。
[0034] Therefore, it is possible to supply cold heat to equipment that requires cold heat scattered over a wide area with a small capital investment and supply the absorbing liquid to equipment that requires a dehumidifying absorbent.

【0035】[0035]

【発明の効果】本発明で利用されるクラスレートは、大
気圧下で容易に生成できるので、取り扱いが簡便であ
る。そして、気体クラスレートのような、フロンによる
環境破壊の問題もない。
The clathrate used in the present invention can be easily produced under atmospheric pressure, and is easy to handle. Also, there is no problem of environmental destruction due to chlorofluorocarbon such as gas clathrate.

【0036】また、融解熱が40〜50kcal/kgである
ことから、高密度化により水を用いる場合に比べ、熱輸
送能力が4倍になり、配管径を半分にすることができ
る。また、融点は、濃度により、ほぼ0℃〜12℃の範
囲で可変であり、冷却対象の所望冷却温度によっては、
氷水スラリなどを用いる場合に比べ、冷熱製造費用を安
くすることができる。
Further, since the heat of fusion is 40 to 50 kcal / kg, the heat transfer capacity is quadrupled and the pipe diameter can be halved as compared with the case where water is used due to high density. Further, the melting point is variable in the range of approximately 0 ° C. to 12 ° C. depending on the concentration, and depending on the desired cooling temperature of the object to be cooled,
As compared with the case of using ice water slurry or the like, the cost of cold heat production can be reduced.

【0037】冷熱の製造と吸収液の再生を同じ場所で行
うことにより、冷熱の製造に使われる蒸気エネルギーを
最大限に有効利用できる。こうして、湿分吸収液を利用
した除湿システムと吸収液を元に戻すシステムと、液液
クラスレートの冷熱を製造する装置を配管ネットワーク
により接続することによりに今までにない熱の有効利用
システムを構築することができる。
By performing the cold heat production and the regeneration of the absorbing solution in the same place, the steam energy used for the cold heat production can be effectively utilized to the maximum. In this way, by connecting a dehumidifying system using a moisture absorbing liquid and a system for returning the absorbing liquid to the original liquid, and a device for producing the cold heat of the liquid-liquid clathrate through a piping network, an unprecedented effective heat utilizing system can be achieved. Can be built.

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

【図1】本発明方法を実施するための全体構成の一例を
示す説明図。
FIG. 1 is an explanatory diagram showing an example of an overall configuration for implementing a method of the present invention.

【図2】本発明方法を実施するためのたの設備の全体構
成の一例を示す説明図。
FIG. 2 is an explanatory diagram showing an example of the entire configuration of another facility for carrying out the method of the present invention.

【符号の説明】[Explanation of symbols]

1…液液クラスレート供給管路,2…水溶液の管路、3
…冷却装置、3a…蒸気吸収式の冷凍機、4…冷熱を必
要とする設備,5、6…貯蔵容器、11…高濃度除湿吸
収液供給管路、12…低濃度除湿液の回収管路、14…
冷熱を必要とすると共に除湿システムの熱源を必要とす
る設備、15…高濃度除湿吸収液の貯蔵容器、16…低
濃度除湿吸収液の貯蔵容器、21、22…除湿吸収液の
再生装置。
1 ... liquid-liquid clathrate supply line, 2 ... aqueous solution line, 3
... Cooling device, 3a ... Vapor absorption type refrigerator, 4 ... Equipment requiring cold heat, 5, 6 ... Storage container, 11 ... High concentration dehumidification absorption liquid supply line, 12 ... Low concentration dehumidification liquid collection line , 14 ...
Equipment that requires cold heat and requires a heat source of the dehumidification system, 15: storage container for high-concentration dehumidification / absorption liquid, 16: storage container for low-concentration dehumidification / absorption liquid, 21, 22: regenerating device for dehumidification / absorption liquid.

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】 冷熱の輸送媒体として、水分子で構成さ
れた籠状の包接格子内にC49 基、iso - C511
を持つオニウム塩がゲストとして包み込まれて結晶化す
る準包接水和物(液液クラスレート)を使用することを
特徴とする冷熱輸送方法。
1. An onium salt having a C 4 H 9 group and an iso-C 5 H 11 group is wrapped as a guest in a cage-shaped inclusion lattice composed of water molecules as a cold and hot transport medium and crystallized. A cold clathrate hydrate (liquid-liquid clathrate).
【請求項2】 準包接水和物は水−臭化テトラn ブチル
アンモニウムである請求項1に記載の冷熱輸送方法。
2. The method according to claim 1, wherein the semi-clathrate hydrate is water-tetra- n -butylammonium bromide.
【請求項3】請求項1または2に記載の準包接水和物を
熱交換器が設けられた冷熱を必要とする複数の設備に供
給する管路と、熱を吸収して一部あるいは全てが液体と
なった媒体を少なくとも1つのクラスレート生成装置に
回収する管路と、から構成される冷熱輸送システム。
3. A pipeline for supplying the quasi-clathrate hydrate according to claim 1 or 2 to a plurality of facilities requiring cold heat provided with a heat exchanger; A conduit for collecting all liquid media into at least one clathrate generator.
【請求項4】 液液クラスレートを供給する管路及びク
ラスレート生成装置に回収する管路のそれぞれに貯蔵容
器が接続されている請求項3に記載の冷熱輸送システ
ム。
4. The cold / hot transport system according to claim 3, wherein storage vessels are connected to each of a pipe for supplying the liquid-liquid clathrate and a pipe for collecting the liquid-liquid clathrate.
【請求項5】 冷熱を必要とする設備での使用熱量に応
じてゲストの濃度を調整することにより、液液クラスレ
ートの融点を変更することを特徴とする請求項1〜4の
いずれかに記載の冷熱輸送方法。
5. The method according to claim 1, wherein the melting point of the liquid-liquid clathrate is changed by adjusting the concentration of the guest in accordance with the amount of heat used in equipment requiring cold heat. The cold transport method as described.
【請求項6】 前記クラスレート生成装置の少なくとも
1つが蒸気吸収式冷凍機であり、中温ないし低温の蒸気
を冷凍機の熱源とすることを特徴とする請求項3に記載
の冷熱輸送システム。
6. The cold heat transport system according to claim 3, wherein at least one of the clathrate generation devices is a steam absorption refrigerator, and medium- or low-temperature steam is used as a heat source of the refrigerator.
【請求項7】 空気の吸収式除湿システムと併設された
冷熱輸送システムであって、前記蒸気吸収式冷凍機から
の排熱を前記吸収式除湿システムの吸収液の再生熱源と
することを特徴とする請求項6に記載の冷熱輸送システ
ム。
7. A cold heat transport system provided in conjunction with an air absorption dehumidification system, wherein exhaust heat from the vapor absorption refrigerator is used as a heat source for regenerating an absorbent in the absorption dehumidification system. The cold transport system according to claim 6.
JP09600597A 1997-01-20 1997-04-14 Cold transport medium, cold transport method, cold transport system and method for changing melting point of semi-clathrate hydrate Expired - Lifetime JP3309760B2 (en)

Priority Applications (2)

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JP09600597A JP3309760B2 (en) 1997-01-20 1997-04-14 Cold transport medium, cold transport method, cold transport system and method for changing melting point of semi-clathrate hydrate
US09/406,217 US6237346B1 (en) 1997-04-14 1999-09-27 Method for transporting cold latent heat and system therefor

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9-7678 1997-01-20
JP767897 1997-01-20
JP09600597A JP3309760B2 (en) 1997-01-20 1997-04-14 Cold transport medium, cold transport method, cold transport system and method for changing melting point of semi-clathrate hydrate
US09/406,217 US6237346B1 (en) 1997-04-14 1999-09-27 Method for transporting cold latent heat and system therefor

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JPH10259978A true JPH10259978A (en) 1998-09-29
JP3309760B2 JP3309760B2 (en) 2002-07-29

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