JP2008230988A - Method for promoting phase separation of clathrate compound or its guest molecule in solution - Google Patents

Method for promoting phase separation of clathrate compound or its guest molecule in solution Download PDF

Info

Publication number
JP2008230988A
JP2008230988A JP2007069822A JP2007069822A JP2008230988A JP 2008230988 A JP2008230988 A JP 2008230988A JP 2007069822 A JP2007069822 A JP 2007069822A JP 2007069822 A JP2007069822 A JP 2007069822A JP 2008230988 A JP2008230988 A JP 2008230988A
Authority
JP
Japan
Prior art keywords
solution
raw
region
concentration
clathrate
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
JP2007069822A
Other languages
Japanese (ja)
Other versions
JP4984132B2 (en
Inventor
Shigenori Matsumoto
繁則 松本
Kanetoshi Hayashi
謙年 林
Shingo Takao
信吾 高雄
Original Assignee
Jfe Engineering Kk
Jfeエンジニアリング株式会社
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 Jfe Engineering Kk, Jfeエンジニアリング株式会社 filed Critical Jfe Engineering Kk
Priority to JP2007069822A priority Critical patent/JP4984132B2/en
Publication of JP2008230988A publication Critical patent/JP2008230988A/en
Application granted granted Critical
Publication of JP4984132B2 publication Critical patent/JP4984132B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

<P>PROBLEM TO BE SOLVED: To provide a method for promoting the phase separation of a raw material solution in a storage tank. <P>SOLUTION: This method for promoting and speeding up a phase separation phenomenon for separating a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute into a region where the presence rate of the clathrate compound or the concentration of the guest molecule in the solution is relatively high or a region where the presence rate of the clathrate compound or the concentration of the guest molecule in the solution is relatively low, is characterized by having a first process for producing the clathrate compound L1 on the outer surface of a heat exchanger 2 disposed in the solution L to grow into a massive product, a second process for fusing a part of the massive product from the outer surface of the heat exchanger 2 to release the un-fused portion of the massive product from the outer surface, and a third process for repeating the first process and the second process at least once more to unevenly distribute the un-fused portion in a specific region in the solution on the basis of a density difference between the clathrate compound L1 and the solution L, thereby relatively enhancing the presence rate of the clathrate compound or the concentration of the guest molecule in the specific region. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、包接化合物のホスト分子を溶媒としゲスト分子を溶質として含む溶液を、前記包接化合物の存在比率又は前記ゲスト分子の濃度が相対的に高い領域と低い領域とに相分離する現象を促進又は迅速化させる技術に関する。   The present invention provides a phenomenon in which a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute is phase-separated into a region where the abundance ratio of the clathrate compound or the concentration of the guest molecule is relatively high and a low region. It is related with the technique which promotes or speeds up.
なお、次に掲げる用語又は表現の意味又は解釈は、以下のとおりとする。   In addition, the meaning or interpretation of the following terms or expressions are as follows.
(1)「原料溶液」とは、包接化合物のホスト分子を溶媒としゲスト分子を溶質として含む溶液をいう。包接化合物のホスト分子を溶媒としゲスト分子を溶質として含むとともに包接化合物が分散又は懸濁している溶液も「原料溶液」に該当する。   (1) “Raw material solution” refers to a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute. A solution containing a host molecule of the inclusion compound as a solvent and a guest molecule as a solute and in which the inclusion compound is dispersed or suspended is also a “raw material solution”.
(2)「包接化合物」とは、複数の分子が適当な条件下で組み合わさって結晶ができるとき、一方の分子(ホスト分子)が籠状、トンネル形、層状または網状構造をつくり、その隙間に他の分子(ゲスト分子)が入りこんだ構造の化合物の意味であり、包接水和物を除くこととする狭義の包接化合物のみならず、この包接水和物(特許文献1、2参照)を含む、言わば広義の包接化合物も「包接化合物」に該当する。言うまでもなく、水が凝固してできる氷はこれに該当しない。   (2) “Clusion compound” means that when a plurality of molecules are combined under appropriate conditions to form a crystal, one molecule (host molecule) forms a cage, tunnel, layer, or network structure. This means a compound having a structure in which another molecule (guest molecule) enters the gap, and not only the clathrate compound in a narrow sense to exclude the clathrate hydrate but also this clathrate hydrate (Patent Document 1, In other words, the clathrate compound in a broad sense including 2) also corresponds to the “clathrate compound”. Needless to say, this is not the case with ice formed by water solidification.
(3)「熱交換器」とは、熱源又は熱媒体との熱交換を可能にする外表面を備える伝熱物体を意味し、中実であるか否か、断面形状、寸法、材質等は問わない。プレート式や多管式といった型式も問わない。ヒートパイプも「熱交換器」の一種である。本発明の具体的な説明を行う際に、熱輸送媒体が流通する空洞を有する伝熱管を「熱交換器」として本発明の具体的な説明を行う場合があるとしても、それは「熱交換器」をかかる伝熱管に限定する意図ではない。   (3) “Heat exchanger” means a heat transfer object having an outer surface that enables heat exchange with a heat source or a heat medium, and whether it is solid, cross-sectional shape, dimensions, material, etc. It doesn't matter. A plate type or a multi-tube type may be used. A heat pipe is also a kind of “heat exchanger”. In the specific description of the present invention, even if the specific description of the present invention is sometimes made using a heat transfer tube having a cavity through which a heat transport medium flows as a “heat exchanger”, the “heat exchanger” Is not intended to be limited to such heat transfer tubes.
(4)熱交換器の「外表面」とは、熱交換器の熱交換面(伝熱面)及びその熱交換の効果が及ぶ当該熱交換面の近傍領域をいう。   (4) The “outer surface” of the heat exchanger refers to a heat exchange surface (heat transfer surface) of the heat exchanger and a region near the heat exchange surface where the effect of the heat exchange extends.
(5)「下方」及び「上方」とは、それぞれ、重力が働く方向及びその反対の方向をいう。   (5) “Lower” and “upper” refer to the direction in which gravity works and the opposite direction, respectively.
(6)「塊状体」とは、一つの集合体としての外形を有する物体をいい、周囲のものと視覚的に区別できる外形であれば、その形状に限定はなく、特に明記する場合を除き、内部の構造、強度、硬度、粘性、密度、組成等は問わない。なお、「包接化合物の塊状体」とは、包接化合物が生成を重ねて塊状をなし、塊状体と肉眼で認定できる状態になるに至ったものをいう。   (6) “Block” refers to an object having an outer shape as one aggregate, and there is no limitation on the shape as long as it is visually distinguishable from surrounding objects, unless otherwise specified. The internal structure, strength, hardness, viscosity, density, composition, etc. are not limited. The “clumps of clathrate compound” refers to those in which the clathrate compound is repeatedly formed to form a clump and can be recognized as a lump and the naked eye.
(7)「スラリー」とは、液体中に固体粒子が分散又は懸濁した状態又はその状態にある物質をいう。沈降しがちな固体粒子を浮遊状態とするために界面活性剤を添加したり、機械的に攪拌することもあるが、その場合にも「スラリー」という。特に包接化合物又はその塊状体について「スラリー」という場合には、界面物性剤の添加や機械的攪拌の有無に拘らず、包接化合物のホスト分子を溶媒としゲスト分子を溶質として含む溶液の中に当該包接化合物が分散又は懸濁した状態又はその状態にある物質をいうが、分散や懸濁が均質であることまで必要とされない。例えば、包接化合物の塊状体の一部(特に溶液に接している部分)が前記溶液中に分散又は懸濁しているが残部は前記溶液中で塊状体のままである場合には、その分散又は懸濁しているものは「スラリー」であり、包接化合物の塊状体と前記溶液中で並存している状態にあるといえる。   (7) “Slurry” refers to a substance in which solid particles are dispersed or suspended in a liquid or a substance in that state. In order to make solid particles that tend to settle into a suspended state, a surfactant may be added or mechanically stirred. In particular, when a clathrate or a mass thereof is referred to as a “slurry”, the inclusion compound includes a host molecule of the clathrate compound as a solvent and a guest molecule as a solute, regardless of the presence or absence of an interfacial physical agent. The clathrate is dispersed or suspended, or a substance in that state, but is not required until the dispersion or suspension is homogeneous. For example, when a part of the clathrate of the clathrate compound (particularly the part in contact with the solution) is dispersed or suspended in the solution but the rest remains agglomerate in the solution, the dispersion Or what is suspended is a "slurry", and it can be said that it exists in the state coexisting in the said lump of inclusion compound and the said solution.
(8)「相分離」とは、原料溶液の中で包接化合物の存在比率又はそのゲスト分子の濃度が相対的に高い領域と低い領域とに分離する現象、即ち固相が多い領域と液相が多い領域とに分離する現象をいう。   (8) “Phase separation” refers to a phenomenon in which the abundance ratio of an inclusion compound or the concentration of guest molecules in a raw material solution is separated into a relatively high region and a low region, that is, a region having a large solid phase and a liquid. This refers to the phenomenon of separation into regions with many phases.
(9)「水和物生成温度」とは、原料溶液を冷却したとき、包接水和物が生成するべき平衡温度をいう。原料溶液のゲスト化合物の濃度により包接化合物が生成する温度が変動する場合であっても、これを「水和物生成温度」という。なお、簡便のため、「水和物生成温度」を「融点」という場合がある。   (9) “Hydrate formation temperature” refers to an equilibrium temperature at which clathrate hydrate should be generated when the raw material solution is cooled. Even when the temperature at which the clathrate compound is generated varies depending on the concentration of the guest compound in the raw material solution, this is referred to as “hydrate formation temperature”. For convenience, the “hydrate formation temperature” may be referred to as “melting point”.
(10)「調和融点」とは、原料溶液の液相から包接水和物が生成する際、原料溶液中のゲスト分子の濃度と包接水和物中のゲスト分子の濃度とが等しく、包接水和物の生成の前後において当該液相の組成が変わらない場合の温度をいう。なお、縦軸を水和物生成温度、横軸を原料溶液の液相のゲスト化合物の濃度とした状態図では極大点が「調和融点」となる。また、調和融点を与える原料溶液中のゲスト分子の濃度を「調和融点濃度」という。調和融点濃度未満の濃度の原料溶液から包接水和物を生成する場合には、包接水和物の生成につれて原料溶液のゲスト分子の濃度が低下し、その濃度に対する水和物生成温度が低下する。   (10) “Harmonic melting point” means that when clathrate hydrate is produced from the liquid phase of the raw material solution, the concentration of the guest molecule in the raw material solution is equal to the concentration of the guest molecule in the clathrate hydrate, The temperature at which the composition of the liquid phase does not change before and after the clathrate hydrate is formed. In the state diagram in which the vertical axis represents the hydrate formation temperature and the horizontal axis represents the concentration of the guest compound in the liquid phase of the raw material solution, the maximum point is the “harmonic melting point”. The concentration of guest molecules in the raw material solution that gives a harmonic melting point is called “harmonic melting point concentration”. When clathrate hydrate is produced from a raw material solution having a concentration lower than the harmonic melting point, the concentration of guest molecules in the raw material solution decreases as the clathrate hydrate is produced, and the hydrate formation temperature relative to that concentration is reduced. descend.
(11)包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域を「高濃度領域」という場合があり、前記包接化合物の存在比率又はゲスト分子の濃度が相対的に低い領域を「低濃度領域」という場合がある。尤も、「高濃度領域」以外のすべての領域が「低濃度領域」に該当するという意味ではなく、「低濃度領域」以外のすべての領域が「高濃度領域」に該当するという意味でもない。   (11) A region where the inclusion ratio of the inclusion compound or the concentration of the guest molecule is relatively high may be referred to as a “high concentration region”, and a region where the inclusion ratio of the inclusion compound or the concentration of the guest molecule is relatively low Sometimes referred to as a “low density region”. However, it does not mean that all the regions other than the “high concentration region” correspond to the “low concentration region”, and it does not mean that all the regions other than the “low concentration region” correspond to the “high concentration region”.
包接化合物は、その生成時に潜熱として熱エネルギーを蓄積し、融解時にその熱エネルギーを放出する性質を有することから、これを、例えば蓄熱材の主成分又は組成物として利用するための研究開発が行われている(特許文献1及び2)。   Since the clathrate compound has the property of accumulating thermal energy as latent heat when it is generated and releasing the thermal energy when it is melted, research and development for using it as a main component or composition of a heat storage material has been conducted. (Patent Documents 1 and 2).
ここで、容器内の原料溶液中に配置された熱交換器を介した熱媒体との熱交換により、その原料溶液の中に包接化合物を生成させる場合、包接化合物と原料溶液との間に密度差があると、その密度差に起因して包接化合物が原料溶液の中で浮揚又は沈降して上方又は下方に偏在することになり、原料溶液の中で包接化合物の存在比率又はそのゲスト分子の濃度が相対的に高い領域(高濃度領域)と相対的に低い領域(低濃度領域)とに分離する現象、あるいは固相が多い領域と液相が多い領域とに分離する現象、即ち相分離現象が生じる。   Here, when the clathrate compound is generated in the raw material solution by heat exchange with the heat medium via the heat exchanger arranged in the raw material solution in the container, If there is a difference in density, the clathrate compound floats or settles in the raw material solution due to the density difference and is unevenly distributed upward or downward, and the inclusion ratio of the clathrate compound in the raw material solution or Phenomenon that separates into a region where the concentration of the guest molecule is relatively high (high concentration region) and a region where the concentration is relatively low (low concentration region), or a region where the solid phase is high and the liquid phase is high That is, a phase separation phenomenon occurs.
しかし、前記の特許文献1〜4の例はいずれも、原料溶液を収容している容器(貯留タンクや蓄熱槽)から当該原料溶液を容器外に取り出し、該容器外に設置された熱交換器を介した冷熱又は熱媒体と当該原料溶液との熱交換により包接化合物を生成させ、これをスラリーにして前記容器に戻し、その容器の中で原料溶液と包接化合物のスラリーとを相分離させている。すなわち、容器に収容された原料溶液の中に熱交換器が配置されている構成ではない。   However, in all of the examples of Patent Documents 1 to 4, the raw material solution is taken out from the container (storage tank or heat storage tank) containing the raw material solution, and the heat exchanger is installed outside the container. The clathrate compound is produced by heat exchange between the raw material solution and cold heat or a heat medium through which the slurry is returned to the vessel as a slurry, and the raw material solution and the clathrate slurry are phase-separated in the vessel I am letting. That is, it is not the structure by which the heat exchanger is arrange | positioned in the raw material solution accommodated in the container.
また、前記の特許文献1〜4の例の場合のように、包接化合物が原料溶液中でスラリーになり得る性質を有しているときには、包接化合物の原料溶液への分散性が高く又は原料溶液中での包接化合物の凝集性が低く、相分離現象が速やかに起こり難いことが多く、数時間又はそれ以上の時間が経過しないと相分離現象を肉眼視できない場合すらある。このため、成層型の貯留タンクや蓄熱槽を早期に定常稼動させる必要がある局面では、その定常稼動に耐え得るだけの相分離状態を可及的速やかに実現することが求められてくる。   Moreover, when the clathrate compound has the property of becoming a slurry in the raw material solution as in the case of the above-mentioned Patent Documents 1 to 4, the dispersibility of the clathrate compound in the raw material solution is high or In many cases, the clathrability of the clathrate compound in the raw material solution is low, and the phase separation phenomenon is not likely to occur promptly, and the phase separation phenomenon may not be visually observed until several hours or more have elapsed. For this reason, in a situation where a stratified storage tank or heat storage tank needs to be steadily operated at an early stage, it is required to realize a phase separation state that can withstand the steady operation as quickly as possible.
尤も、包接化合物が原料溶液の中でスラリーになり得る性質を有していても、包接化合物の種類や包接化合物と原料溶液との組み合わせなどによっては、相分離現象が速やかに起こるものもあるかも知れない。しかし、その場合であっても、相分離現象をさらに促進させる必要性は別途あり得る。例えば、相分離現象を促進させて、原料溶液中の特定領域に高濃度領域を形成し、その特定領域又は高濃度領域から原料溶液又は包接化合物若しくはゲスト分子を取り出すことにより、包接化合物のゲスト分子を回収してこれを蓄熱材組成物としての再利用を企図する場合である。逆の場合もあり得る。即ち、相分離現象を促進させて、原料溶液中の特定領域に低濃度領域を形成し、その特定領域又は低濃度領域から原料溶液又は包接化合物若しくはゲスト分子を取り出すことにより、原料溶液中に包接化合物のゲスト分子を濃縮してこれを蓄熱材組成物としての再利用を企図する場合である。   However, even if the clathrate compound has the property of becoming a slurry in the raw material solution, depending on the type of clathrate compound and the combination of the clathrate compound and the raw material solution, the phase separation phenomenon may occur quickly. There may also be. However, even in that case, it may be necessary to further promote the phase separation phenomenon. For example, the phase separation phenomenon is promoted to form a high concentration region in a specific region in the raw material solution, and the raw material solution, the inclusion compound or the guest molecule is taken out from the specific region or the high concentration region. This is a case where a guest molecule is collected and intended to be reused as a heat storage material composition. The reverse is also possible. That is, by promoting the phase separation phenomenon, a low concentration region is formed in a specific region in the raw material solution, and the raw material solution, the inclusion compound or the guest molecule is taken out from the specific region or the low concentration region. This is a case where the guest molecules of the clathrate compound are concentrated and reused as the heat storage material composition.
包接化合物のゲスト分子の濃縮技術の一例が、包接水和物を生成する薬剤(当該包接水和物のゲスト分子)の水溶液から不純物を除去するための水溶液再生技術である(特許文献5)。この水溶液再生技術では、不純物を含む原料溶液とその原料溶液中に配置される熱交換器を備える処理槽を用意し、熱交換器に冷却用熱媒体を流すことで熱交換器の周りに包接水和物の結晶を生成させ、その結晶が生成した後に残った水溶液を処理槽外に排出することで不純物を除去し、次いで熱交換器に加熱用熱媒体を流すことで包接水和物の結晶を融解し、不純物が除去された原料溶液、更にはその原料溶液を加熱・濃縮等してゲスト分子の析出物を得ている。
特公昭57−35224号公報 特許3641362号公報 特開2000−121266号公報 特開2002−333165号公報 特開2002−333168号公報
One example of a technique for concentrating guest molecules of clathrate compounds is an aqueous solution regeneration technique for removing impurities from an aqueous solution of a drug that generates clathrate hydrates (guest molecules of the clathrate hydrate) (Patent Literature). 5). In this aqueous solution regeneration technology, a treatment tank comprising a raw material solution containing impurities and a heat exchanger disposed in the raw material solution is prepared, and a cooling heat medium is passed through the heat exchanger to wrap around the heat exchanger. Impurities are removed by generating crystals of the wet hydrate, draining the aqueous solution remaining after the crystals are formed, and then supplying the heating medium to the heat exchanger for inclusion hydration The crystal of the product is melted, the raw material solution from which impurities are removed, and further, the raw material solution is heated and concentrated to obtain a guest molecule precipitate.
Japanese Patent Publication No.57-35224 Japanese Patent No. 3641362 JP 2000-121266 A JP 2002-333165 A JP 2002-333168 A
しかし、冷却用熱媒体が流れる熱交換器の周りに包接化合物が生成して厚みを増すにつれて伝熱抵抗が大きくなるため、その冷却用熱媒体による冷却の効果が水溶液に及ばなくなってくる。このことは、特許文献5記載の技術において、熱交換器の周りに包接水和物の結晶を生成させても、結晶にならないまま水溶液中にゲスト分子が残り、相分離を行なうことに限界があることを意味している。それ故、特許文献5記載の技術は、これにより包接化合物のゲスト分子の濃縮が可能になるとはいえ、原料溶液の中で、包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに相分離する現象を促進するには、未だ効率的なものとはいえない。また、前記の従来技術では、包接化合物とそのゲスト分子を溶質として含む原料溶液との密度差と、包接化合物の濃縮との関係について、全く考慮されておらず、技術的な示唆も見当たらない。   However, since the heat transfer resistance increases as the clathrate compound is generated around the heat exchanger through which the cooling heat medium flows and the thickness increases, the cooling effect by the cooling heat medium does not reach the aqueous solution. This is because in the technique described in Patent Document 5, even if the clathrate hydrate crystals are generated around the heat exchanger, the guest molecules remain in the aqueous solution without being crystallized, and the phase separation is limited. It means that there is. Therefore, although the technique described in Patent Document 5 enables the concentration of the guest molecule of the clathrate compound by this, the inclusion ratio of the clathrate compound or the concentration of the guest molecule is relatively high in the raw material solution. It is not yet efficient to promote the phenomenon of phase separation into a region and a relatively low region. Further, in the above prior art, the relationship between the density difference between the clathrate compound and the raw material solution containing the guest molecule as a solute and the concentration of the clathrate compound is not taken into consideration at all, and technical suggestions are also found. Absent.
本発明は、以上の問題や事情に鑑みてなされたものであり、原料溶液の中で、包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに相分離する現象を促進又は迅速化若しくは高速化させる技術、加えて、これを効率的に行うことができる技術を提供することを課題とする。   The present invention has been made in view of the above problems and circumstances. In the raw material solution, the inclusion ratio of the clathrate compound or the concentration of the guest molecule is relatively high and low. It is an object of the present invention to provide a technique for promoting, speeding up, or speeding up the phenomenon of separation, and a technique that can efficiently perform this phenomenon.
上記課題を解決するための、本発明の第1の形態に係る相分離の促進又は迅速化方法は、包接化合物のホスト分子を溶媒としゲスト分子を溶質として含む溶液を、前記溶液中で前記包接化合物の存在比率又は前記ゲスト分子の濃度が相対的に高い領域と低い領域とに分離させる方法であって、前記溶液の中に配置された熱交換器の外表面に前記包接化合物を生成させ、塊状体に成長させる第1工程と、前記塊状体の一部を前記外表面の側から融解させることにより、前記塊状体の未融解部を前記外表面から離脱させる第2工程と、前記第1工程及び前記第2工程を少なくとも1回繰り返すことにより、前記包接化合物と前記溶液との密度差にもとづいて前記未融解部を前記溶液の中の特定領域に偏在させ、その特定領域における前記包接化合物の存在比率又は前記ゲスト分子の濃度を相対的に高める第3工程とを有することを特徴とする。   In order to solve the above-described problem, the method for promoting or speeding up phase separation according to the first aspect of the present invention includes a solution containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute in the solution. A method of separating an inclusion compound in an abundance ratio or a guest molecule concentration in a relatively high region and a low region, wherein the inclusion compound is disposed on an outer surface of a heat exchanger disposed in the solution. A first step of generating and growing into a lump, and a second step of detaching an unmelted portion of the lump from the outer surface by melting a part of the lump from the outer surface side; By repeating the first step and the second step at least once, the unmelted portion is unevenly distributed in a specific region in the solution based on the density difference between the inclusion compound and the solution, and the specific region The inclusion compound in And having a third step of relatively increasing the presence ratio or concentration of the guest molecule.
本発明の第2の形態に係る相分離の促進又は迅速化方法は、第1の形態に係る方法において、第2工程の終了後第1工程の開始前又は第1工程の途中に、前記包接化合物の存在比率又は前記ゲスト分子の濃度が相対的に低い領域にある前記溶液を攪拌する攪拌工程を有することを特徴とする。   The method for promoting or accelerating phase separation according to the second aspect of the present invention is the method according to the first aspect, wherein the packaging is performed before the start of the first step or after the first step after the second step. It has a stirring step of stirring the solution in a region where the abundance ratio of the contact compound or the concentration of the guest molecule is relatively low.
本発明の第3の形態に係る相分離の促進又は迅速化方法は、第1又は第2の形態に係る方法において、前記第1工程が、前記包接化合物の潜熱により熱エネルギーを蓄積する工程であり、前記第2工程が、前記熱交換器により前記塊状体の一部から熱エネルギーを取り出す工程であることを特徴とする。   The method for promoting or accelerating phase separation according to the third aspect of the present invention is the method according to the first or second aspect, wherein the first step is a step of storing thermal energy by latent heat of the clathrate compound. The second step is a step of extracting thermal energy from a part of the lump by the heat exchanger.
本発明は、包接化合物が原料溶液と異なる密度と原料溶液中でスラリーになり得る性質を有していることを利用して、原料溶液の中に配置された熱交換器の外表面に包接化合物を生成させ塊状体に成長させる工程と、その塊状体の一部を熱交換器の外表面の側から融解させ、その外表面から未融解部を離脱させる工程とを少なくとも1回繰り返すことにより、包接化合物と原料溶液との密度差に従って未融解部を原料溶液の中の特定領域に偏在させ、その特定領域における包接化合物の存在比率又はゲスト分子の濃度を相対的に高めることを基本構成とする。   The present invention takes advantage of the fact that the clathrate has a density different from that of the raw material solution and the property that it can become a slurry in the raw material solution, so that it is encapsulated on the outer surface of the heat exchanger disposed in the raw material solution. Repeating at least once a step of generating a contact compound and growing it into a lump, and a step of melting a part of the lump from the outer surface side of the heat exchanger and releasing an unmelted portion from the outer surface According to the density difference between the clathrate compound and the raw material solution, the unmelted portion is unevenly distributed in a specific region in the raw material solution, and the inclusion ratio of the clathrate compound or the concentration of the guest molecule in the specific region is relatively increased. Basic configuration.
熱交換器の外表面に生成した包接化合物をその外表面の側から融解させると、融解した部分は原料溶液に戻り外表面から未融解部が離脱し、未融解部は包接化合物と原料溶液との密度差に従って原料溶液の中で浮揚又は沈降し、原料溶液中の特定領域に集まり偏在することになる。この結果、包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに分離することになる。   When the clathrate compound formed on the outer surface of the heat exchanger is melted from the outer surface side, the melted part returns to the raw material solution and the unmelted part is detached from the outer surface, and the unmelted part is the clathrate compound and the raw material. It floats or settles in the raw material solution according to the density difference from the solution, and is concentrated in a specific region in the raw material solution. As a result, the inclusion ratio of the inclusion compound or the concentration of the guest molecule is separated into a relatively high region and a relatively low region.
ここで、未融解部は、包接化合物の塊状体の一部であるので、包接化合物のスラリーと異なり、溶媒への分散性がなく、溶媒の中での凝集性もないので、スラリーよりも迅速に、包接化合物と原料溶液との密度差に従って上方に浮揚又は下方に沈降する。   Here, since the unmelted part is a part of the clathrate of the clathrate compound, unlike the slurry of the clathrate compound, there is no dispersibility in the solvent and no cohesiveness in the solvent. Also rapidly float or sink downward according to the density difference between the inclusion compound and the raw material solution.
それ故、本発明によれば、原料溶液の中で、包接化合物の生成と融解を少なくとも1回繰り返すことにより、高濃度領域と低濃度領域とに相分離する相分離現象を促進させることができる。   Therefore, according to the present invention, the phase separation phenomenon of phase separation into a high concentration region and a low concentration region can be promoted by repeating the generation and melting of the clathrate compound at least once in the raw material solution. it can.
しかも、包接化合物の生成と融解を繰り返すたびに未融解部が特定領域に集まり、当該特定領域に形成される高濃度領域における包接化合物の存在比率又はゲスト分子の濃度は漸増し、当該特定領域又は高濃度領域以外の領域(低濃度領域を含む)の原料溶液における包接化合物の存在比率又はゲスト分子の濃度は平均して漸減することになるが、熱交換器の外表面に原料溶液への伝熱を妨げ伝熱抵抗となる包接化合物が存在しない又は殆ど存在しない状態になるので、原料溶液が熱交換器と直接接触して熱交換器による熱交換の効果(熱伝達性)は高いまま維持され、故にゲスト分子の濃度が低い原料溶液からも引き続き包接化合物が生成する。尤も、ゲスト分子の濃度が低下した分だけ包接化合物の生成量は漸減するが、熱伝達性が低下しないことから包接化合物をより多く生成させることができる、換言すれば、原料溶液の中に残存するゲスト分子の量をより少なくすることができる。   Moreover, each time the generation and melting of the clathrate compound are repeated, the unmelted portion gathers in a specific area, and the inclusion compound concentration or the concentration of guest molecules in the high concentration area formed in the specific area increases gradually. The inclusion ratio of the inclusion compound or the concentration of the guest molecule in the raw material solution in the region other than the region or the high concentration region (including the low concentration region) or the concentration of the guest molecule gradually decreases on average, but the raw material solution on the outer surface of the heat exchanger Since there is no or almost no inclusion compound that prevents heat transfer to the heat transfer resistance, the raw material solution is in direct contact with the heat exchanger and the heat exchange effect (heat transfer) Is maintained at a high level, so that an inclusion compound is continuously formed from a raw material solution having a low concentration of guest molecules. However, the amount of clathrate compound produced gradually decreases as the guest molecule concentration decreases, but the heat transferability does not decrease, so more clathrate compound can be produced, in other words, in the raw material solution. The amount of guest molecules remaining in can be further reduced.
それ故、本発明によれば、原料溶液の中で、包接化合物の生成と融解を複数回繰り返すことにより、原料溶液から包接化合物又はゲスト分子を上方又は下方の特定領域に累積的に偏在させることができ、包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに速やかに、しかも効率的に、またゲスト分子の濃度の高低差がより明確になるように分離させることができる、という基本的な効果を得る。   Therefore, according to the present invention, the clathrate compound or guest molecule is cumulatively unevenly distributed in the upper or lower specific region by repeating the generation and melting of the clathrate compound several times in the raw material solution. The inclusion ratio of the inclusion compound or the concentration of the guest molecule can be quickly and efficiently changed between the region where the concentration of the guest molecule is relatively high and the region where the concentration of the guest molecule is relatively low. The basic effect of being able to be separated is obtained.
また、本発明の各形態が奏する個別的な作用効果は以下のとおりである。   Moreover, the individual effect which each form of this invention show | plays is as follows.
本発明の第1の形態によれば、原料溶液の中で、高濃度領域と低濃度領域とに相分離する現象を促進又は迅速化させる方法を実現できる。特に、原料溶液の中で、包接化合物の生成と融解を複数回繰り返すことにより、相分離を速やかに且つ効率的に行うことができる。なお、包接化合物の生成と融解の繰返し回数を多くすることにより、ゲスト分子の濃度の高低差をより明確にすることができる。   According to the first embodiment of the present invention, it is possible to realize a method for promoting or speeding up the phenomenon of phase separation into a high concentration region and a low concentration region in a raw material solution. In particular, the phase separation can be performed quickly and efficiently by repeating the generation and melting of the clathrate compound a plurality of times in the raw material solution. It should be noted that by increasing the number of repetitions of the generation and melting of the clathrate compound, the difference in the concentration of guest molecules can be made clearer.
この第1の形態において、第1の工程で包接化合物の潜熱により熱エネルギーを蓄積し、第2の工程で熱交換器により熱エネルギーを取り出すという蓄熱・放熱の過程でゲスト分子の相分離現象の促進又は迅速化を実現することができる。このことは、原料溶液を収容する容器(貯留タンクや蓄熱槽)の中に、当該原料溶液の中に没するように熱交換器を配置すれば、この熱交換器により包接化合物の生成と融解を行うことにより、当該容器の中で包接化合物の存在比率又はゲスト分子の濃度が相対的に高い領域と低い領域とに相分離する相分離現象を促進又は迅速化させることができるということをも意味している。   In this first form, the heat energy is accumulated by the latent heat of the clathrate compound in the first step, and the heat energy is taken out by the heat exchanger in the second step. Can be promoted or speeded up. This means that if a heat exchanger is placed in a container (storage tank or heat storage tank) containing the raw material solution so as to be immersed in the raw material solution, the heat exchanger can generate clathrate compounds. By performing melting, it is possible to accelerate or speed up the phase separation phenomenon in which the phase separation phenomenon of the inclusion compound inclusion ratio or the concentration of the guest molecule in the vessel is relatively high and low. Also means.
包接化合物を熱交換器の外表面の側から融解させると、融解した部分は原料溶液に戻る。このとき、熱交換器外表面に近い原料溶液におけるゲスト分子の濃度が相対的に高くなり、熱交換器の外表面から原料溶液に向かって濃度勾配が生じる。このような濃度勾配は熱交換器の外表面における包接水和物の生成を阻害する。他方、熱交換器の外表面に生成し外表面を覆う包接化合物は伝熱抵抗になるので、熱交換器の外表面に包接化合物を生成して、塊状体にまで成長させようとしても、その成長には限界がある。   When the clathrate compound is melted from the outer surface side of the heat exchanger, the melted portion returns to the raw material solution. At this time, the concentration of the guest molecule in the raw material solution close to the outer surface of the heat exchanger becomes relatively high, and a concentration gradient is generated from the outer surface of the heat exchanger toward the raw material solution. Such a concentration gradient inhibits the formation of clathrate hydrate on the outer surface of the heat exchanger. On the other hand, the clathrate compound that is formed on the outer surface of the heat exchanger and covers the outer surface becomes a heat transfer resistance, so even if the clathrate compound is generated on the outer surface of the heat exchanger and is grown to a lump. The growth is limited.
そこで、本発明の第2の形態によれば、第2工程の終了後第1工程の開始前までに、低濃度領域で攪拌されるので、その低濃度領域にある原料溶液が均一化される。また、本発明の第2の形態によれば、第1工程の途中において、未融解部が低濃度領域で攪拌されるので、その低濃度領域にある原料溶液が均一化される。そして、これらの攪拌により、熱交換器の外表面(当該外表面に包接水和物が生成している場合には、原料溶液と接する当該包接水和物の表面)から原料溶液への伝熱性が改善される。   Therefore, according to the second embodiment of the present invention, since the agitation is performed in the low concentration region after the end of the second step and before the start of the first step, the raw material solution in the low concentration region is made uniform. . Moreover, according to the 2nd form of this invention, since an unmelted part is stirred in a low concentration area | region in the middle of a 1st process, the raw material solution in the low concentration area | region is equalized. And by these agitation, from the outer surface of the heat exchanger (the surface of the clathrate hydrate in contact with the raw material solution when clathrate hydrate is formed on the outer surface) to the raw material solution Heat transfer is improved.
これらの結果、低濃度領域における原料溶液からも包接化合物を生成させることができるようになり、原料溶液全体から効率的に包接水和物を塊状体に成長させることができるようになる。それ故、原料溶液からより多くの包接化合物を生成させ、塊状体にまで成長させ、未融解部として原料溶液の中の特定領域に偏在させることができるようになり、延いては、原料溶液の中で、高濃度領域と低濃度領域とに相分離する相分離現象をより効率的に促進させることができる。   As a result, the clathrate compound can be generated from the raw material solution in the low concentration region, and the clathrate hydrate can be efficiently grown into a lump from the whole raw material solution. Therefore, more clathrate compounds can be generated from the raw material solution, can be grown to a lump, and can be unevenly distributed in a specific region in the raw material solution as an unmelted part. Among these, the phase separation phenomenon of phase separation into a high concentration region and a low concentration region can be more efficiently promoted.
本発明の第3の形態においては、記第1工程が、前記包接化合物の潜熱により熱エネルギーを蓄積する工程であり、前記第2工程が、前記熱交換器により前記塊状体の一部から熱エネルギーを取り出す工程となる。これらの工程は、それぞれ、包接水和物を潜熱蓄熱材とする蓄熱方法における蓄熱工程及び放熱工程又は包接水和物を潜熱蓄熱材とする蓄熱装置の蓄熱運転及び放熱運転に対応している。それ故、この第3の形態によれば、包接水和物を潜熱蓄熱材とする既存又は公知の蓄熱方法や蓄熱装置(特に所謂内融式蓄熱装置)を転用することにより、本発明の第1又は第2の形態に係る原料溶液中の包接化合物又はそのゲスト分子の相分離促進方法を容易に実現することができる。これは、使用済みの包接化合物のゲスト分子を回収又は濃縮による再利用を企図する場合において特に有益である。   In the third aspect of the present invention, the first step is a step of accumulating thermal energy by latent heat of the clathrate compound, and the second step is performed from a part of the lump by the heat exchanger. This is a process for extracting thermal energy. These processes correspond to the heat storage operation and heat release process of the heat storage method using the clathrate hydrate as the latent heat storage material, and the heat storage operation and heat release operation of the heat storage device using the clathrate hydrate as the latent heat storage material, respectively. Yes. Therefore, according to this third embodiment, by diverting an existing or known heat storage method or heat storage device (particularly a so-called inner heat storage device) using clathrate hydrate as a latent heat storage material, The method for promoting the phase separation of the clathrate compound or the guest molecule in the raw material solution according to the first or second embodiment can be easily realized. This is particularly beneficial when contemplating recycling of the used clathrate guest molecules by recovery or concentration.
以下、図面にもとづき本発明の実施の形態について説明する。本実施形態では、包接化合物の具体例を包接水和物として説明するが、当該具体例が包接水和物であるからといって、本発明から包接水和物以外の包接化合物が除外されることではなく、包接水和物以外の包接化合物でも本発明を実施できる。また、包接水和物は原料溶液に比べて密度が大きく、未融解の包接化合物の塊状体(未融解部)が原料溶液中を沈降する場合について説明するが、密度が小さい場合は未融解部が原料溶液中を浮上する挙動を示す点で異なるだけであり、基本的な構成は同様になる。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the present embodiment, a specific example of the clathrate compound will be described as a clathrate hydrate. However, just because the specific example is a clathrate hydrate, the clathrate other than the clathrate hydrate is used in the present invention. The present invention can be practiced with inclusion compounds other than inclusion hydrates, not excluding compounds. In addition, the clathrate hydrate has a higher density than the raw material solution, and an explanation will be given of a case where a lump (unmelted portion) of the unmelted clathrate compound settles in the raw material solution. The only difference is that the melting part exhibits the behavior of floating in the raw material solution, and the basic configuration is the same.
図1は、包接水和物を生成、融解して蓄熱、放熱する装置の概要説明図である。この図において、符号1は原料溶液Lが貯留されている貯留槽、符号2は貯留槽1内に配設された熱交換器(伝熱管)である。   FIG. 1 is a schematic explanatory diagram of an apparatus for generating and melting clathrate hydrate to store and release heat. In this figure, reference numeral 1 is a storage tank in which the raw material solution L is stored, and reference numeral 2 is a heat exchanger (heat transfer tube) disposed in the storage tank 1.
熱交換器2は貯留槽1内で水平方向に蛇行し高さ方向に複数段をなしていて、該熱交換器2内を熱媒体が流通している。この熱交換器2は、水平方向の蛇行によらずとも、上下方向に蛇行していてもよい。前記原料溶液Lは、そのゲスト分子の濃度が調和融点を与える濃度(調和融点濃度)であっても、それ未満あるいはそれより高い濃度であってもよい。   The heat exchanger 2 meanders in the horizontal direction in the storage tank 1 and has a plurality of stages in the height direction, and a heat medium circulates in the heat exchanger 2. The heat exchanger 2 may meander in the up-down direction without depending on the meandering in the horizontal direction. The raw material solution L may have a concentration of guest molecules that gives a harmonic melting point (harmonic melting point concentration), or a concentration lower than or higher than that.
図1に示した装置は、蓄熱装置に喩えれば所謂内融式蓄熱装置と実質的に同じである。そしてこの装置において、熱エネルギーを蓄積するための蓄熱工程と蓄積された熱エネルギーを放出する又は取り出すための放熱工程とを実行することにより、換言すれば、蓄熱工程を実現するための蓄熱運転と放熱工程を実現するための放熱運転を行うことにより、包接水和物の存在比率又は前記ゲスト分子の濃度が相対的に高い領域と低い領域とに分離させる。   The apparatus shown in FIG. 1 is substantially the same as a so-called inner-melting type heat storage apparatus when compared to a heat storage apparatus. And in this device, by executing a heat storage step for storing thermal energy and a heat release step for releasing or taking out the stored thermal energy, in other words, a heat storage operation for realizing the heat storage step By performing a heat dissipation operation for realizing the heat dissipation process, the inclusion hydrate content ratio or the concentration of the guest molecule is separated into a relatively high region and a low region.
<蓄熱工程(蓄熱運転)>
熱交換器(伝熱管)2に、包接水和物生成温度より低温の熱媒体が流通され、熱交換器2の外表面で原料溶液Lが熱交換して冷却され包接水和物L1が生成される。包接水和物L1は、図1に見られるように、熱交換器2の外表面に付着し堆積して、該熱交換器2の周囲に包接水和物L1の塊状体が形成される。
<Heat storage process (heat storage operation)>
A heat medium having a temperature lower than the clathrate hydrate formation temperature is circulated through the heat exchanger (heat transfer tube) 2, and the raw material solution L is heat-exchanged and cooled on the outer surface of the heat exchanger 2 to be clathrate hydrate L1. Is generated. As shown in FIG. 1, the clathrate hydrate L1 adheres to and accumulates on the outer surface of the heat exchanger 2, and a mass of the clathrate hydrate L1 is formed around the heat exchanger 2. The
<放熱工程(放熱運転)>
熱交換器2に、包接水和物の融解温度より高温の熱媒体が流通され熱交換器2の外表面で包接水和物L1と熱交換して、熱媒体が冷却されて冷熱エネルギーが取出される。包接水和物L1は熱交換器2の外表面に接している部分から融解し、その融解によりできる原料溶液Lは、その包接水和物L1の融解温度よりも高温で低密度なので貯留槽1の上方に移動し、貯留槽1の上方に偏在する。他方、未融解のまま残る包接水和物L1の塊状体(未融解部)は熱交換器2の表面から離脱し、包接水和物L1と原料溶液Lとの密度差に応じて、従って重力により下方に沈降する。
<Heat dissipation process (heat dissipation operation)>
A heat medium having a temperature higher than the melting temperature of the clathrate hydrate is circulated through the heat exchanger 2 to exchange heat with the clathrate hydrate L1 on the outer surface of the heat exchanger 2, and the heat medium is cooled to cool energy. Is taken out. The clathrate hydrate L1 is melted from the portion in contact with the outer surface of the heat exchanger 2, and the raw material solution L formed by the melting is stored at a higher temperature than the melting temperature of the clathrate hydrate L1 and thus has a low density. It moves above the tank 1 and is unevenly distributed above the storage tank 1. On the other hand, the mass of the clathrate hydrate L1 that remains unmelted (unmelted portion) is detached from the surface of the heat exchanger 2, and according to the density difference between the clathrate hydrate L1 and the raw material solution L, Therefore, it sinks downward by gravity.
この未融解部は、包接水和物の塊状体の一部であるので、包接水和物のスラリーと異なり、溶媒への分散性は比較的小さく、溶媒の中での凝集性も比較的小さいので、スラリーよりも迅速に、包接水和物と原料溶液との密度差に従って下方に沈降してゆく。その過程で未融解部の一部は原料溶液に分散又は懸濁してスラリーとなり、比較的遅い速度で沈降してゆく。こうして未融解部は、塊状体、スラリーといった形態で貯留槽1の下方の領域に偏在することになる。また、貯留槽1の下方の領域に偏在するに至った未融解部が融解すると、上方の原料溶液Lと拡散混合するに足るだけの長時間が経過しない限り又は上方の領域と下方の領域との間で強制的な攪拌を行わない限り、当初の原料溶液Lのゲスト分子濃度より高い濃度の原料溶液となり滞留する。   Since this unmelted part is a part of the clathrate hydrate lump, unlike the clathrate hydrate slurry, the dispersibility in the solvent is relatively small, and the cohesiveness in the solvent is also compared. Therefore, it settles downward according to the density difference between the clathrate hydrate and the raw material solution more rapidly than the slurry. In the process, a part of the unmelted portion is dispersed or suspended in the raw material solution to become a slurry, and settles at a relatively low speed. Thus, the unmelted portion is unevenly distributed in the region below the storage tank 1 in the form of a lump or slurry. Further, when the unmelted portion that has been unevenly distributed in the lower region of the storage tank 1 is melted, as long as a long time sufficient to diffusely mix with the upper raw material solution L has not passed, or the upper region and the lower region Unless the forcible stirring is performed between the two, the raw material solution having a higher concentration than the guest molecule concentration of the original raw material solution L is retained.
かくして、図2のように貯留槽1の上方には低濃度領域が、下方には高濃度領域が形成される。   Thus, as shown in FIG. 2, a low concentration region is formed above the storage tank 1, and a high concentration region is formed below.
<蓄熱工程と放熱工程の繰返し>
原料溶液Lの中に配置された熱交換器2の外表面に包接水和物L1を生成させ塊状体に成長させる工程(蓄熱工程)と、その塊状体の一部を熱交換器2の外表面の側から融解させ、その外表面から未融解部を離脱させる工程(放熱工程)とを少なくとも1回繰り返すと、包接水和物L1と原料溶液Lとの密度差に起因して未融解部を原料溶液の中の特定領域に偏在させることとなり、その特定領域における包接水和物の存在比率が相対的に高まり、また未融解部が融解して現れるゲスト分子の濃度が相対的に高まる。その結果、包接水和物の存在比率又はゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに相分離することになる。
<Repetition of heat storage process and heat dissipation process>
A step of generating clathrate hydrate L1 on the outer surface of the heat exchanger 2 disposed in the raw material solution L and growing it into a lump (heat storage step), and a part of the lump is transferred to the heat exchanger 2 When the process of melting from the outer surface side and detaching the unmelted part from the outer surface (heat dissipation process) is repeated at least once, the density difference between the clathrate hydrate L1 and the raw material solution L is not increased. The melting part is unevenly distributed in a specific region in the raw material solution, the abundance ratio of clathrate hydrate in the specific region is relatively increased, and the concentration of guest molecules that appear when the unmelted part is melted is relatively high. To increase. As a result, phase separation occurs in a relatively high region and a relatively low region in which the clathrate hydrate abundance ratio or guest molecule concentration is relatively high.
ここで、未融解部は、包接水和物の塊状体の一部であるので、包接水和物のスラリーと異なり、溶媒への分散性は比較的小さく、溶媒の中での凝集性も比較的小さいので、スラリーよりも迅速に、包接水和物と原料溶液との密度差に従って下方に沈降する。その過程で未融解部の一部は原料溶液に分散又は懸濁してスラリーとなり、比較的遅い速度で沈降してゆく。こうして未融解部は、塊状体、スラリーといった形態で貯留槽1の下方の領域に偏在することになる。また、貯留槽1の下方の領域に偏在するに至った未融解部が融解すると、例えば上方の原料溶液Lと拡散混合するに足るだけの長時間が経過しない限り又は上方の領域と下方の領域との間で強制的な攪拌を行わない限り、当初の原料溶液Lのゲスト分子濃度より高い濃度の原料溶液となり滞留する。更に、下方の領域に滞留するに至った未融解部分、スラリー及び原料溶液は、蓄熱工程と放熱工程の繰返しの過程で、例えば上方の領域と下方の領域との間で強制的な攪拌を行わない限り、あたかも当該下方の領域に閉じ込められた状態になる。   Here, since the unmelted part is a part of the clathrate hydrate lump, unlike the clathrate hydrate slurry, the dispersibility in the solvent is relatively small, and the cohesiveness in the solvent Is relatively small, and settles down more rapidly than the slurry according to the density difference between the clathrate hydrate and the raw material solution. In the process, a part of the unmelted portion is dispersed or suspended in the raw material solution to become a slurry, and settles at a relatively low speed. Thus, the unmelted portion is unevenly distributed in the region below the storage tank 1 in the form of a lump or slurry. Further, when the unmelted portion that has been unevenly distributed in the lower region of the storage tank 1 is melted, for example, unless a long time sufficient for diffusing and mixing with the upper raw material solution L has passed, or the upper region and the lower region Unless the forcible stirring is performed, the raw material solution having a concentration higher than the initial guest molecule concentration of the raw material solution L is retained. Further, the unmelted portion, slurry and raw material solution that have stayed in the lower region are subjected to forcible agitation between the upper region and the lower region, for example, in the process of repeated heat storage and heat release. As long as there is not, it will be in the state confined to the said lower area | region.
かくして、貯留槽1の上方には低濃度領域が、下方には高濃度領域が形成される。   Thus, a low concentration region is formed above the storage tank 1 and a high concentration region is formed below.
それ故、本発明によれば、原料溶液の中で、包接水和物の生成と融解を少なくとも1回繰り返すことにより、包接水和物の存在比率又はゲスト分子の濃度が相対的に高い領域と低い領域とに分離する相分離現象を促進させることができる。   Therefore, according to the present invention, the inclusion ratio of the clathrate hydrate or the concentration of the guest molecule is relatively high by repeating the generation and melting of the clathrate hydrate at least once in the raw material solution. A phase separation phenomenon that separates into a region and a low region can be promoted.
また、包接水和物の生成と融解を繰り返すと、その繰返しのたびに熱交換器の外表面に付着していた包接水和物が融解するとともに、未融解部が熱交換器の外表面から離脱して行く。すると、未融解部が包接水和物と原料溶液との密度差に起因して原料溶液中の特定領域(包接水和物の方が原料溶液よりも密度が高い場合には、下方の領域)に集まり、包接水和物の存在比率又はゲスト分子の濃度が漸増し、当該特定領域に高濃度領域が形成され、それと同時に、その他の領域の原料溶液における包接水和物の存在比率又はゲスト分子の濃度は漸減する。この結果、熱交換器の外表面の周囲は低濃度領域となり、包接水和物が生成しにくい環境となる。   In addition, when the clathrate hydrate is repeatedly generated and melted, the clathrate hydrate adhering to the outer surface of the heat exchanger is melted each time the clathrate hydrate is repeated, and the unmelted portion is outside the heat exchanger. Get away from the surface. Then, due to the density difference between the clathrate hydrate and the raw material solution, the unmelted part is a specific region in the raw material solution (if the clathrate hydrate has a higher density than the raw material solution, The inclusion ratio of the clathrate hydrate or the concentration of the guest molecule is gradually increased, and a high concentration area is formed in the specific area. At the same time, the presence of the clathrate hydrate in the raw material solution in the other area The ratio or the concentration of guest molecules decreases gradually. As a result, the periphery of the outer surface of the heat exchanger becomes a low-concentration region, and an environment in which clathrate hydrates are difficult to be generated.
ところが、熱交換器の外表面に付着していた包接水和物が融解するとともに、未融解部が熱交換器の外表面から離脱して行くと、その熱交換器の外表面は原料溶液への熱伝熱を妨げる包接水和物が存在しない又は殆ど存在しない状態になるので、熱交換器による熱交換の効果は高いまま維持され、故に低濃度領域の環境下であっても引き続き包接水和物の生成が起こる。勿論、包接水和物の存在比率又はゲスト分子の濃度が漸減すると、熱交換器の外表面に生成する包接水和物の量も漸減するが、熱交換器の外表面の熱伝達性が低下しない分だけより多くの包接水和物が生成し、塊状体となる。   However, when the clathrate hydrate adhering to the outer surface of the heat exchanger is melted and the unmelted part is detached from the outer surface of the heat exchanger, the outer surface of the heat exchanger becomes the raw material solution. Since there is no or almost no clathrate hydrate that hinders heat transfer to the heat exchanger, the heat exchange effect by the heat exchanger remains high, and therefore continues even in the low concentration region environment. Formation of clathrate hydrate occurs. Of course, when the inclusion ratio of the clathrate hydrate or the concentration of the guest molecule decreases gradually, the amount of clathrate hydrate generated on the outer surface of the heat exchanger also decreases, but the heat transferability of the outer surface of the heat exchanger More clathrate hydrates are produced by the amount that does not decrease, resulting in lumps.
かくして、包接水和物の生成と融解を繰り返すことにより、熱交換器の外表面の周囲は低濃度領域となり、包接水和物が生成しにくい環境になっても、原料溶液中の特定領域に高濃度領域が形成され、同時に当該特定領域以外に低濃度領域が形成され、これが繰り返される。   Thus, by repeating the generation and melting of clathrate hydrate, the surroundings of the outer surface of the heat exchanger will be in a low concentration region, and even in an environment where clathrate hydrate is difficult to be generated, it is possible to identify in the raw material solution. A high concentration region is formed in the region, and at the same time, a low concentration region is formed in addition to the specific region, and this is repeated.
それ故、本発明によれば、原料溶液の中で、包接水和物の生成と融解を複数回繰り返しても、原料溶液から包接水和物又はそのゲスト分子を下方の領域に累積的に偏在させることができ、包接水和物の存在比率又はそのゲスト分子の濃度が相対的に高い領域と相対的に低い領域とに速やかに、しかも効率的に、またゲスト分子の濃度の高低差がより明確になるように分離させることができる。   Therefore, according to the present invention, even if the generation and melting of clathrate hydrate are repeated several times in the raw material solution, the clathrate hydrate or its guest molecule is cumulatively accumulated in the lower region from the raw material solution. Can be unevenly distributed, and the inclusion hydrate content ratio or the concentration of the guest molecule can be quickly and efficiently reduced to a relatively high region and a relatively low region. They can be separated so that the difference becomes clearer.
なお、上記のとおり、熱交換器の外表面に付着していた包接水和物が融解するとともに、未融解部が熱交換器の外表面から離脱して行くと、熱交換器による熱交換の効果は高いまま維持され、故に低濃度領域の環境下であっても引き続き包接水和物の生成が起こる。このことは、本発明によれば、ゲスト分子の濃度が低い原料溶液からも当該ゲスト分子を速やかに、効率的に分離することができることを意味している。このような本発明の効果は、使用済みの原料溶液から包接化合物のゲスト分子を回収又は濃縮してこれを蓄熱材組成物としての再利用を企図する場合に特に有益である。   As mentioned above, when the clathrate hydrate adhering to the outer surface of the heat exchanger is melted and the unmelted part is detached from the outer surface of the heat exchanger, heat exchange by the heat exchanger is performed. This effect remains high, so that clathrate hydrate continues to be produced even in a low-concentration environment. This means that according to the present invention, the guest molecules can be quickly and efficiently separated from the raw material solution having a low concentration of guest molecules. Such an effect of the present invention is particularly beneficial when a guest molecule of an inclusion compound is recovered or concentrated from a used raw material solution and intended to be reused as a heat storage material composition.
また、熱交換器2の外表面において融解する包接水和物の量に比べて、その融解の結果当該外表面から離脱して下方に沈降する未融解部における包接水和物の量の方が多いのが普通である。特に、熱交換器が伝熱管の場合には、包接水和物の塊状体は重力の影響を受けて、伝熱管の上方にある包接水和物の塊状体の限られた部分(伝熱管の直上又はその近傍の部分)のみが融解し易くなり、従ってより多くの未融解部が下方に沈降し易くなる。このような場合、特に熱交換器が伝熱管である場合には、包接水和物の存在比率又はゲスト分子の濃度の高低差がより明確になり易くなり、低濃度領域と高濃度領域の形成も効率的且つ迅速に起こり易くなるので、蓄熱工程と放熱工程とを繰り返すと否とに拘らず、本発明の実施形態として好ましい。   In addition, compared to the amount of clathrate hydrate that melts on the outer surface of the heat exchanger 2, the amount of clathrate hydrate in the unmelted part that separates from the outer surface and settles downward as a result of the melting. Usually there are more. In particular, when the heat exchanger is a heat transfer tube, the clathrate hydrate lump is affected by gravity and a limited portion of the clathrate hydrate lump above the heat transfer tube (transfer Only the portion immediately above or in the vicinity of the heat tube is likely to melt, and thus more unmelted portions are likely to settle downward. In such a case, particularly when the heat exchanger is a heat transfer tube, the difference in the clathrate hydrate abundance or the concentration of the guest molecule is more easily clarified, and the low concentration region and the high concentration region Since the formation is likely to occur efficiently and quickly, it is preferable as an embodiment of the present invention regardless of whether the heat storage step and the heat release step are repeated.
図3は、包接水和物のゲスト分子として臭化テトラnブチルアンモニウム(TBAB)の調和融点濃度未満である30wt%の水溶液を原料溶液として、図1に示した装置により、包接水和物の生成と融解を複数回繰り返した後における貯留槽1内の原料溶液中のTBAB濃度の高さ方向の分布を示したものである。ここで横軸は、原料溶液中のTBAB濃度、縦軸は、貯留槽1内の原料溶液の液面高さを1とした高さ比を示している。   FIG. 3 shows clathrate hydration using the apparatus shown in FIG. 1 with a 30 wt% aqueous solution that is less than the harmonic melting point concentration of tetra-n-butylammonium bromide (TBAB) as a guest molecule of the clathrate hydrate. The distribution in the height direction of the TBAB concentration in the raw material solution in the storage tank 1 after the generation and melting of the product are repeated a plurality of times is shown. Here, the horizontal axis indicates the TBAB concentration in the raw material solution, and the vertical axis indicates the height ratio where the liquid surface height of the raw material solution in the storage tank 1 is 1.
図3によると、TBABの包接水和物の密度は原料溶液より大きいが、下部にTBAB濃度の高い領域、上部にTBAB濃度の低い領域として相分離していることが分かる。   According to FIG. 3, the density of the TBAB clathrate hydrate is larger than that of the raw material solution, but it is understood that phase separation is performed as a region having a high TBAB concentration at the bottom and a region having a low TBAB concentration at the top.
本実施形態では、種々の観点から、例えば、以下のごとく、さらに改善を加えることができる。   In the present embodiment, further improvements can be made from various viewpoints, for example, as follows.
(i)放熱工程の効率向上
図2は、図1に示した装置の変形例の概要説明図である。この図に示した装置では、貯留槽1の下部に包接水和物の存在比率が高い領域が形成されている。つまり、図2装置において包接水和物と熱エネルギーを取り出す熱交換器の外表面が接触し効率的に熱交換できる領域を特定できる長所がある。包接水和物を熱交換器の外表面側から融解させると、融解した部分は原料溶液に戻る。この原料溶液の温度は包接水和物の融解温度よりも高温となっているため、交換する熱量を多くとることができ、原料溶液と熱交換器外表面が接触しているよりも、包接水和物と熱交換器外表面が接触している方が効率的に熱エネルギーを取り出すことができる。
(I) Improving Efficiency of Heat Dissipation Process FIG. 2 is a schematic explanatory diagram of a modified example of the apparatus shown in FIG. In the apparatus shown in this figure, a region where the existence ratio of clathrate hydrate is high is formed in the lower part of the storage tank 1. In other words, the clathrate hydrate and the outer surface of the heat exchanger that extracts heat energy in the apparatus shown in FIG. When the clathrate hydrate is melted from the outer surface side of the heat exchanger, the melted portion returns to the raw material solution. Since the temperature of this raw material solution is higher than the melting temperature of the clathrate hydrate, it is possible to take a larger amount of heat to be exchanged, and the encapsulating hydrate is more than the contact between the raw material solution and the outer surface of the heat exchanger. Heat energy can be efficiently extracted when the wetted hydrate and the outer surface of the heat exchanger are in contact with each other.
図2に示した熱交換器は、水平方向に蛇行し高さ方向に連続して複数段を構成している伝熱管であるが、貯留槽1の上部、即ち包接水和物の存在比率が低い領域と、下部、即ち包接水和物の存在比率が高い領域とに別々に熱交換器を設けて、放熱工程では、主に包接水和物の存在比率が高い領域に設けられた熱交換器により熱エネルギーを取り出すようにすれば効率的に、そして包接水和物の存在比率が高い領域に熱エネルギーを取り出すための熱交換器を密に設けるようにすればより効率的に、熱エネルギーを取り出すことができる。   The heat exchanger shown in FIG. 2 is a heat transfer tube meandering in the horizontal direction and continuously forming a plurality of stages in the height direction, but the upper portion of the storage tank 1, that is, the inclusion ratio of clathrate hydrate The heat exchanger is provided separately in the lower area and the lower area, i.e., the area where the clathrate hydrate is high, and in the heat dissipation process, it is mainly provided in the area where the clathrate hydrate is high. It is more efficient if the heat energy is taken out by the heat exchanger, and more efficient if the heat exchanger for taking out the heat energy is densely provided in the region where the clathrate hydrate is present in a high ratio. In addition, heat energy can be taken out.
(ii)相分離の更なる促進
図4は、図1に示した装置の別の変形例の概要説明図である。この図に示した装置は、図2に示した装置に循環手段を設けたものにも相当する。この循環手段は、貯留槽1の上方の領域と下方の領域とを接続する循環用配管と、その循環用配管に取り付けられたポンプ3により構成される。
(Ii) Further Promotion of Phase Separation FIG. 4 is a schematic explanatory diagram of another modification of the apparatus shown in FIG. The apparatus shown in this figure corresponds to the apparatus shown in FIG. 2 provided with a circulating means. This circulation means is constituted by a circulation pipe connecting the upper area and the lower area of the storage tank 1 and a pump 3 attached to the circulation pipe.
この循環手段により、包接水和物の存在比率又はゲスト分子の濃度が低い領域Bからこの領域Bの原料溶液のうち10%程度を抜出し、ポンプ3によって包接水和物の存在比率又はゲスト分子の濃度が高い領域Aへ、低濃度領域Bと高濃度領域Aとが混合しないように低流速で流入させる。これにより、低濃度領域Bから高濃度領域Aに流入したゲスト分子濃度が低い原料溶液の一部からも包接水和物の塊状体を生成することができ、包接水和物の存在比率を高め、ゲスト分子濃度を高めることができるので、包接水和物の存在比率の高い領域と低い領域との相分離をより促進することができる。   By this circulation means, about 10% of the raw material solution in the region B is extracted from the region B where the inclusion hydrate abundance ratio or guest molecule concentration is low, and the inclusion rate of the clathrate hydrate or the guest by the pump 3 The low concentration region B and the high concentration region A are flowed into the region A where the concentration of molecules is high so that the low concentration region B and the high concentration region A do not mix. As a result, a clathrate hydrate mass can be generated from a part of the raw material solution having a low guest molecule concentration flowing from the low concentration region B to the high concentration region A, and the abundance ratio of the clathrate hydrate. And the guest molecule concentration can be increased, so that phase separation between the high and low inclusion clathrate hydrate regions can be promoted.
(iii)低濃度領域における攪拌
包接水和物を熱交換器の外表面の側から融解させると、融解した部分は原料溶液に戻る。このとき、熱交換器外表面に近い原料溶液におけるゲスト分子の濃度が相対的に高くなり、熱交換器の外表面から遠い原料溶液に向かって濃度勾配が生じる。他方、包接水和物の熱伝導性は原料溶液に比べて低く、熱交換器の外表面の熱伝達性はその外表面に包接水和物が生成しこれを覆うにつれて低下するので、熱交換器の外表面に生成した包接水和物を塊状体にまで成長させようとしても、その成長には限界が生じてくる。それ故、効率的に包接水和物を塊状体にまで成長させ、未融解部として原料溶液の中の特定領域に偏在させるためには、包接水和物の存在比率又はゲスト分子の濃度が低い領域にある原料溶液におけるゲスト分子の濃度勾配を解消させ、均一化させ、熱交換器における熱交換を促進するのが好ましい。
(Iii) Agitation in the low concentration region When the clathrate hydrate is melted from the outer surface side of the heat exchanger, the melted portion returns to the raw material solution. At this time, the concentration of guest molecules in the raw material solution close to the outer surface of the heat exchanger becomes relatively high, and a concentration gradient is generated toward the raw material solution far from the outer surface of the heat exchanger. On the other hand, the thermal conductivity of clathrate hydrate is lower than that of the raw material solution, and the heat transferability of the outer surface of the heat exchanger decreases as clathrate hydrate is formed on the outer surface and covered with it, Even if it is going to grow the clathrate hydrate produced | generated on the outer surface of a heat exchanger to a lump, the limit will arise. Therefore, in order to efficiently grow the clathrate hydrate to a lump and unevenly distribute it in a specific region in the raw material solution as an unmelted part, the inclusion ratio of the clathrate hydrate or the concentration of the guest molecule It is preferable to eliminate the concentration gradient of guest molecules in the raw material solution in a low region, to make it uniform, and to promote heat exchange in the heat exchanger.
しかして図5及び図6は、いずれも、図1に示した装置の更に別の変形例の概要説明図である。これらの各図に示した装置は、図2に示した装置に、貯留槽1の低濃度領域Bに攪拌するための循環手段を設けたものにも相当する。図5に示した循環手段は、低濃度領域Bの上方の領域と下方の領域とを接続する循環用配管と、その循環用配管に取り付けられたポンプ4により構成される。また、図6に示す循環手段は、低濃度領域Bにある原料溶液を攪拌する回転翼5を備える攪拌装置である。   5 and 6 are schematic explanatory views of still another modification of the apparatus shown in FIG. The apparatus shown in each of these figures corresponds to the apparatus shown in FIG. 2 provided with a circulation means for stirring in the low concentration region B of the storage tank 1. The circulation means shown in FIG. 5 includes a circulation pipe that connects an upper area and a lower area of the low concentration area B, and a pump 4 attached to the circulation pipe. Moreover, the circulation means shown in FIG. 6 is a stirring device provided with the rotary blade 5 that stirs the raw material solution in the low concentration region B.
特に図5においては、包接水和物の少ない領域Bの原料溶液を、ポンプ4により、低濃度領域Bの上方の領域から抜き出し、低濃度領域Bの下方の領域へ、領域Aの内容物と領域Bの内容物とが混合しないように流入させ、これにより低濃度領域Bの原料溶液を攪拌する。これにより、低濃度領域Bにおいて、熱交換器2の外表面または外表面近傍に包接水和物が存在して熱伝達が低下することを防ぎ、熱交換器2の外表面と原料溶液の熱交換を促進し、包接水和物の生成を促進することができる。   In particular, in FIG. 5, the raw material solution in the region B with low clathrate hydrate is extracted from the region above the low concentration region B by the pump 4, and the contents in the region A are transferred to the region below the low concentration region B. And the contents of region B are mixed so that they do not mix, thereby stirring the raw material solution in low concentration region B. As a result, in the low concentration region B, the clathrate hydrate is present on the outer surface of the heat exchanger 2 or in the vicinity of the outer surface to prevent heat transfer from being reduced, and the outer surface of the heat exchanger 2 and the raw material solution Heat exchange can be promoted and clathrate hydrate formation can be promoted.
なお、図5に示す攪拌手段を設ける際には、原料溶液の吸込部及び吐出部の少なくとも一方を一つ又は複数個設けてもよい。   In addition, when providing the stirring means shown in FIG. 5, you may provide one or more at least one of the suction part and discharge part of a raw material solution.
図5及び図6に示した攪拌手段による低濃度領域Bにおける原料溶液の攪拌により、熱交換器2の外表面から遠い原料溶液に向かって生じていた濃度勾配が解消され、低濃度領域Bにある原料溶液が均一化される。そのため、原料溶液への熱伝達性が維持され、包接水和物の生成と塊状体の成長が円滑に進められる。   By stirring the raw material solution in the low concentration region B by the stirring means shown in FIG. 5 and FIG. 6, the concentration gradient generated toward the raw material solution far from the outer surface of the heat exchanger 2 is eliminated. A certain raw material solution is homogenized. For this reason, heat transfer to the raw material solution is maintained, and the clathrate hydrate generation and the growth of the lump can proceed smoothly.
なお、このような攪拌は、放熱工程の終了後蓄熱工程の開始前までに行うのが好ましい。包接水和物の生成開始前までに、熱交換器2の外表面から遠い原料溶液に向かって生じていた濃度勾配が解消され、低濃度領域Bにある原料溶液が均一化されるからである。   In addition, it is preferable to perform such stirring before completion | finish of the thermal storage process after completion | finish of a thermal radiation process. This is because the concentration gradient generated toward the raw material solution far from the outer surface of the heat exchanger 2 is eliminated before the clathrate hydrate is generated, and the raw material solution in the low concentration region B is made uniform. is there.
また、蓄熱工程の途中において低濃度領域Bを攪拌してもよい。これにより低濃度領域Bにある原料溶液が均一化され、同時に熱交換器2の外表面から原料溶液への伝熱性を改善することができる。   Moreover, you may stir the low concentration area | region B in the middle of a thermal storage process. Thereby, the raw material solution in the low concentration region B is made uniform, and at the same time, the heat transfer from the outer surface of the heat exchanger 2 to the raw material solution can be improved.
本発明の一実施形態に係る装置の概要説明図であり、蓄熱状態を示す。It is a general | schematic explanatory drawing of the apparatus which concerns on one Embodiment of this invention, and shows a thermal storage state. 図1に示した装置の放熱状態を示す。The heat dissipation state of the apparatus shown in FIG. 1 is shown. 原料溶液の相分離の様子を高さ方向に関して示す図である。It is a figure which shows the mode of the phase separation of a raw material solution regarding a height direction. 図1に示した装置の変形例を示す図である。It is a figure which shows the modification of the apparatus shown in FIG. 図1に示した装置の他の変形例を示す図である。It is a figure which shows the other modification of the apparatus shown in FIG. 図1に示した装置のさらに他の変形例を示す図である。It is a figure which shows the further another modification of the apparatus shown in FIG.
符号の説明Explanation of symbols
1 貯留槽
2 熱交換器
3 ポンプ
4 ポンプ
5 回転翼
A 特定領域又は高濃度領域
B 低濃度領域
L 原料溶液
L1 包接化合物(包接水和物)
DESCRIPTION OF SYMBOLS 1 Storage tank 2 Heat exchanger 3 Pump 4 Pump 5 Rotor blade A Specific area or high concentration area B Low concentration area L Raw material solution L1 Inclusion compound (inclusion hydrate)

Claims (2)

  1. 包接化合物のホスト分子を溶媒としゲスト分子を溶質として含む溶液を、前記溶液中で前記包接化合物の存在比率又は前記ゲスト分子の濃度が相対的に高い領域と低い領域とに分離させる、相分離現象の促進又は迅速化方法において、
    前記溶液の中に配置された熱交換器の外表面に前記包接化合物を生成させ、塊状体に成長させる第1工程と、
    前記塊状体の一部を前記外表面の側から融解させることにより、前記塊状体の未融解部を前記外表面から離脱させる第2工程と、
    前記第1工程及び前記第2工程を少なくとも1回繰り返すことにより、前記包接化合物と前記溶液との密度差にもとづいて前記未融解部を前記溶液の中の特定領域に偏在させ、その特定領域における前記包接化合物の存在比率又は前記ゲスト分子の濃度を相対的に高める第3工程とを有することを特徴とする溶液中の包接化合物又はそのゲスト分子の相分離促進方法。
    A phase containing a host molecule of a clathrate compound as a solvent and a guest molecule as a solute is separated into a region where the abundance ratio of the clathrate compound or the concentration of the guest molecule is relatively high and low in the solution. In the method of promoting or speeding up the separation phenomenon,
    A first step of generating the inclusion compound on the outer surface of a heat exchanger disposed in the solution and growing it into a mass;
    A second step of detaching the unmelted portion of the mass from the outer surface by melting a part of the mass from the outer surface side;
    By repeating the first step and the second step at least once, the unmelted portion is unevenly distributed in a specific region in the solution based on the density difference between the inclusion compound and the solution, and the specific region And a third step of relatively increasing the abundance ratio of the clathrate compound or the concentration of the guest molecule in the method for promoting phase separation of the clathrate compound in the solution or the guest molecule.
  2. 第2工程の終了後第1工程の開始前又は第1工程の途中に、前記包接化合物の存在比率又は前記ゲスト分子の濃度が相対的に低い領域にある溶液を攪拌する攪拌工程を有することとする請求項1に記載の溶液中の包接化合物又はそのゲスト分子の相分離促進方法。   After the end of the second step, before the start of the first step or in the middle of the first step, the stirring step of stirring the solution in the region where the abundance ratio of the inclusion compound or the concentration of the guest molecule is relatively low The method for promoting phase separation of an inclusion compound or a guest molecule thereof in a solution according to claim 1.
JP2007069822A 2007-03-19 2007-03-19 Method for promoting phase separation of clathrate compound or guest molecule in solution Expired - Fee Related JP4984132B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007069822A JP4984132B2 (en) 2007-03-19 2007-03-19 Method for promoting phase separation of clathrate compound or guest molecule in solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007069822A JP4984132B2 (en) 2007-03-19 2007-03-19 Method for promoting phase separation of clathrate compound or guest molecule in solution

Publications (2)

Publication Number Publication Date
JP2008230988A true JP2008230988A (en) 2008-10-02
JP4984132B2 JP4984132B2 (en) 2012-07-25

Family

ID=39904227

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2007069822A Expired - Fee Related JP4984132B2 (en) 2007-03-19 2007-03-19 Method for promoting phase separation of clathrate compound or guest molecule in solution

Country Status (1)

Country Link
JP (1) JP4984132B2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008230989A (en) * 2007-03-19 2008-10-02 Jfe Engineering Kk Method for concentrating, method for concentrating and separating, and method for concentrating and recovering guest molecule of clathrate compound, and method for regenerating the guest molecule
JP2012001678A (en) * 2010-06-21 2012-01-05 Jfe Engineering Corp Purification method and regeneration method for cold transfer medium or cold storage material, method for maintaining air conditioning apparatus, purification apparatus and regeneration apparatus for cold transfer medium or cold storage material, and air conditioning system
JP5324692B1 (en) * 2012-10-05 2013-10-23 パナソニック株式会社 Heat storage device and air conditioner equipped with the same
WO2018097183A1 (en) * 2016-11-22 2018-05-31 シャープ株式会社 Heat-storage material, cooling pack, packing container for logistics, and cooling unit

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000146475A (en) * 1998-11-12 2000-05-26 Nkk Corp Manufacturing apparatus for inclusion hydrate
JP2000205775A (en) * 1998-11-12 2000-07-28 Nkk Corp Manufacture of clathrate hydrate slurry
JP2002333166A (en) * 2001-05-09 2002-11-22 Nkk Corp Method for taking out hydrate slurry
JP2002333168A (en) * 2001-05-10 2002-11-22 Nkk Corp Cold storage system and method for regenerating cold medium
JP2007046855A (en) * 2005-08-11 2007-02-22 Jfe Engineering Kk Hydrate slurry thermal storage device and thermal storage method
JP2007182510A (en) * 2006-01-10 2007-07-19 Jfe Engineering Kk Impurity removing method, regeneration method and purification method for cold transfer medium or cold storage material, maintenance method for cold air conditioning apparatus, and impurity removing apparatus, regenerating apparatus and cold air conditioning system for cold transfer medium or storage material
JP2008215655A (en) * 2007-02-28 2008-09-18 Jfe Engineering Kk Heat storage device and its operation method
JP2008230989A (en) * 2007-03-19 2008-10-02 Jfe Engineering Kk Method for concentrating, method for concentrating and separating, and method for concentrating and recovering guest molecule of clathrate compound, and method for regenerating the guest molecule

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000146475A (en) * 1998-11-12 2000-05-26 Nkk Corp Manufacturing apparatus for inclusion hydrate
JP2000205775A (en) * 1998-11-12 2000-07-28 Nkk Corp Manufacture of clathrate hydrate slurry
JP2002333166A (en) * 2001-05-09 2002-11-22 Nkk Corp Method for taking out hydrate slurry
JP2002333168A (en) * 2001-05-10 2002-11-22 Nkk Corp Cold storage system and method for regenerating cold medium
JP2007046855A (en) * 2005-08-11 2007-02-22 Jfe Engineering Kk Hydrate slurry thermal storage device and thermal storage method
JP2007182510A (en) * 2006-01-10 2007-07-19 Jfe Engineering Kk Impurity removing method, regeneration method and purification method for cold transfer medium or cold storage material, maintenance method for cold air conditioning apparatus, and impurity removing apparatus, regenerating apparatus and cold air conditioning system for cold transfer medium or storage material
JP2008215655A (en) * 2007-02-28 2008-09-18 Jfe Engineering Kk Heat storage device and its operation method
JP2008230989A (en) * 2007-03-19 2008-10-02 Jfe Engineering Kk Method for concentrating, method for concentrating and separating, and method for concentrating and recovering guest molecule of clathrate compound, and method for regenerating the guest molecule

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008230989A (en) * 2007-03-19 2008-10-02 Jfe Engineering Kk Method for concentrating, method for concentrating and separating, and method for concentrating and recovering guest molecule of clathrate compound, and method for regenerating the guest molecule
JP2012001678A (en) * 2010-06-21 2012-01-05 Jfe Engineering Corp Purification method and regeneration method for cold transfer medium or cold storage material, method for maintaining air conditioning apparatus, purification apparatus and regeneration apparatus for cold transfer medium or cold storage material, and air conditioning system
JP5324692B1 (en) * 2012-10-05 2013-10-23 パナソニック株式会社 Heat storage device and air conditioner equipped with the same
WO2018097183A1 (en) * 2016-11-22 2018-05-31 シャープ株式会社 Heat-storage material, cooling pack, packing container for logistics, and cooling unit

Also Published As

Publication number Publication date
JP4984132B2 (en) 2012-07-25

Similar Documents

Publication Publication Date Title
JP4984132B2 (en) Method for promoting phase separation of clathrate compound or guest molecule in solution
CN101070571B (en) Method for manufacturing composite material for carbon nano material and metal material
JP5400782B2 (en) Method for treating silicon powder to obtain silicon crystals
JP6621547B2 (en) Method and apparatus for producing semi-solid slurry
JP2000233101A (en) Process and apparatus for manufacturing hydrate slurry
CN101748291A (en) High-purity aluminum purification device based on segregation method
JP4984133B2 (en) Concentration method, concentration separation method, concentration recovery method, and regeneration method of guest molecules of inclusion compounds
CN206262143U (en) A kind of 4-propyl bromide crystallizer
CN106955981A (en) A kind of preparation method of semisolid state slurry thereof
JP2010099665A (en) Method and device for processing release agent
Jiang et al. Progress in the application of fractal porous media theory to property analysis and process simulation in melt crystallization
CN104478693B (en) A kind of preparation method of refining oxalic acid
KR102133660B1 (en) Continuous reaction solidification die casting production method and production system
JP6230847B2 (en) Aluminum melting and holding furnace
JP5769112B2 (en) Gas separation method and apparatus and gas treatment method and apparatus
JP2008215655A (en) Heat storage device and its operation method
CN103442777A (en) Apparatus and method for separating solid particles from a slurry
CN107709633A (en) Method for volume contained by the melted material that maintains material to be depleted and supplement
CN104548647B (en) The reciprocating continuous crystalizer of multiple spot
US20110006014A1 (en) System and Method For Process and Waste Water Filtration
JP2009130032A (en) Substrate treating apparatus
CN205832669U (en) A kind of system of recovered material from crystallization feed liquid
JP2002153859A (en) Freeze-thawing solution separation method by advanced freeze concentration method as well as freeze-thawing solid-liquid separation method for suspension solution and freeze-thawing separator for the same
JP6541240B2 (en) Modular subunit for suspension crystallization system and suspension crystallization method using the modular subunit
JP6322100B2 (en) Gas separation device and gas separation method

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20090804

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20120215

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20120329

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20120411

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20150511

Year of fee payment: 3

LAPS Cancellation because of no payment of annual fees