JP2009051906A - Raw material for forming clathrate hydrate, method for producing clathrate hydrate or slurry thereof, and method for reducing pressure loss caused when cooling aqueous solution for forming clathrate hydrate - Google Patents

Raw material for forming clathrate hydrate, method for producing clathrate hydrate or slurry thereof, and method for reducing pressure loss caused when cooling aqueous solution for forming clathrate hydrate Download PDF

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JP2009051906A
JP2009051906A JP2007218586A JP2007218586A JP2009051906A JP 2009051906 A JP2009051906 A JP 2009051906A JP 2007218586 A JP2007218586 A JP 2007218586A JP 2007218586 A JP2007218586 A JP 2007218586A JP 2009051906 A JP2009051906 A JP 2009051906A
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clathrate hydrate
hydrate
slurry
raw
clathrate
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JP5125316B2 (en
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Tsuyoshi Mizukami
剛志 水上
Keiji Tomura
啓二 戸村
Hidemasa Ogose
英雅 生越
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Jfe Engineering Kk
Jfeエンジニアリング株式会社
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<P>PROBLEM TO BE SOLVED: To provide a technique by which the increase of the pressure loss in a heat exchanger caused when cooling a raw material for forming a clathrate hydrate released from supercooling can be reduced or prevented. <P>SOLUTION: The raw material for forming the clathrate hydrate contains a quaternary ammonium salt being a guest compound of the clathrate hydrate as a main solute, and a tetra(iso-pentyl)ammonium salt added thereto. The raw material has properties of forming the clathrate hydrate by being cooled, and contains the clathrate hydrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、包接水和物のゲスト化合物を含み、冷却により当該包接水和物を生成させる性質を有する原料(以下「包接水和物生成用原料」という場合がある)であって、包接水和物又はそのスラリを製造する際に生じる圧力損失の増加を抑制又は防止する技術、より詳しくは、包接水和物が含まれる包接水和物生成用原料に予めテトラisoペンチルアンモニウム塩を添加しておき、その水溶液を冷却することにより包接水和物又はそのスラリを製造する際に生じる圧力損失の増加を抑制又は防止することができる技術に関する。   The present invention is a raw material containing a guest compound of clathrate hydrate and having the property of generating the clathrate hydrate by cooling (hereinafter sometimes referred to as “clathrate hydrate production raw material”). , A technique for suppressing or preventing an increase in pressure loss that occurs during the production of clathrate hydrate or a slurry thereof, more specifically, tetraiso is previously added to a clathrate hydrate-producing raw material containing clathrate hydrate. The present invention relates to a technique capable of suppressing or preventing an increase in pressure loss that occurs when a clathrate hydrate or a slurry thereof is produced by adding a pentylammonium salt and cooling the aqueous solution.
なお、本発明において、次に掲げる用語は、別段の説明がなされる場合を除き、以下のとおり解釈されるものとする。
(1) 「包接水和物」には、準包接水和物が含まれる。
(2) 「包接水和物」は「水和物」と略称される場合がある。
(3) 「ゲスト化合物」は「ゲスト」と略称される場合がある。
(4) 「スラリ」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、機械的に攪拌したりすることもあるが、液体中に固体粒子が分散又は懸濁している限り、「スラリ」という。液体中に固体粒子が分散又は懸濁している限り、その分散又は懸濁が不均一なものであっても、「スラリ」という。
(5) 「包接水和物生成用原料」とは、包接水和物を生成する性質を有する水溶液若しくはスラリを「包接水和物生成用原料」という。「包接水和物生成用原料」を略して「原料」という場合がある。包接水和物のゲスト化合物とは別の微量物質が添加されていても、また、包接水和物が分散又は懸濁していても、包接水和物を生成する性質を有する水溶液若しくはスラリである限り、「包接水和物生成用原料」又は「原料」に該当する。
(6) 「水和物生成温度」とは、包接水和物が生成するべき平衡温度をいう。原料中のゲスト化合物の濃度など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。
In the present invention, the following terms shall be interpreted as follows unless otherwise explained.
(1) The “clathrate hydrate” includes quasi clathrate hydrate.
(2) “Clusion clathrate hydrate” is sometimes abbreviated as “hydrate”.
(3) “Guest compound” may be abbreviated as “guest”.
(4) “Slurry” refers to a substance in which solid particles are dispersed or suspended in a liquid or in that state. A surfactant may be added or mechanically stirred to make solid particles that tend to settle, but as long as the solid particles are dispersed or suspended in the liquid, That's it. As long as the solid particles are dispersed or suspended in the liquid, even if the dispersion or suspension is not uniform, it is referred to as “slurry”.
(5) “Cathrate hydrate production raw material” refers to an aqueous solution or slurry having a property of producing clathrate hydrate as “clathrate hydrate production raw material”. The “raw material for clathrate hydrate generation” may be abbreviated as “raw material” in some cases. Even if a trace substance other than the guest compound of the clathrate hydrate is added, or the clathrate hydrate is dispersed or suspended, an aqueous solution having the property of forming the clathrate hydrate or As long as it is a slurry, it corresponds to “a raw material for producing clathrate hydrate” or “a raw material”.
(6) “Hydrate formation temperature” refers to the equilibrium temperature at which clathrate hydrate should be generated. Even when the temperature at which the clathrate compound is generated varies depending on the concentration of the guest compound in the raw material, this is referred to as “hydrate formation temperature”. For convenience, the “hydrate formation temperature” may be referred to as “melting point”.
包接水和物のゲスト化合物を主たる溶質とする水溶液を水和物生成温度以下に冷却すると、その水溶液から当該包接水和物が生成することがよく知られており、ゲスト化合物が第4級アンモニウム塩である場合もその例外ではない(特許文献1)。
また、かくして生成した包接水和物が当該水溶液に分散又は懸濁してスラリになることや、包接水和物が生成する過程で潜熱相当の熱エネルギーを蓄積することから、生成した包接水和物のみにならずそのスラリも潜熱蓄熱剤の組成物として用いられることも知られている(特許文献1〜3)。
It is well known that when an aqueous solution containing a guest compound of clathrate hydrate as a main solute is cooled below the hydrate formation temperature, the clathrate hydrate is produced from the aqueous solution. The case of a quaternary ammonium salt is no exception (Patent Document 1).
In addition, the clathrate hydrate thus generated is dispersed or suspended in the aqueous solution to become a slurry, and heat energy equivalent to latent heat is accumulated in the process of clathrate hydrate formation, so that the generated clathrate is generated. It is also known that not only the hydrate but also the slurry is used as a composition of the latent heat storage agent (Patent Documents 1 to 3).
包接水和物が生成する性質を有する水溶液を冷却して包接水和物又はそのスラリを製造する場合には、その水溶液を水和物生成温度以下に冷却しても水和物が生成せず水溶液状態を維持している過冷却状態になることを解除する必要がある。過冷却を解除して包接水和物又はそのスラリを製造する技術は種々検討されているが(例えば特許文献4及び5参照)、その一例として、包接水和物が生成する性質を有する水溶液を、その流通の過程で、過冷却状態になるまで冷却し、その後過冷却解除手段により当該過冷却状態を解除し、引き続き冷却することにより包接水和物又はそのスラリを製造する技術が知られている(特許文献6)。
特公昭57−35224号公報 特許3641362号公報 特許3555481号公報 特開2003−126676号公報 特開2000−233101号公報 特開2004−3718号公報
When an clathrate hydrate or slurry thereof is produced by cooling an aqueous solution having the property of forming clathrate hydrate, the hydrate is produced even if the aqueous solution is cooled below the hydrate formation temperature. Therefore, it is necessary to cancel the supercooling state in which the aqueous solution state is maintained. Various techniques for producing clathrate hydrate or its slurry by releasing supercooling have been studied (see, for example, Patent Documents 4 and 5). As an example, clathrate hydrate has the property of forming. A technique for producing clathrate hydrate or its slurry by cooling an aqueous solution in the course of its circulation until it becomes supercooled, then releasing the supercooled state by means of a supercooling release means and subsequently cooling. Known (Patent Document 6).
Japanese Patent Publication No.57-35224 Japanese Patent No. 3641362 Japanese Patent No. 3555481 JP 2003-126676 A JP 2000-233101 A Japanese Patent Laid-Open No. 2004-3718
ここで、包接水和物が生成する性質を有する水溶液を冷却することで包接水和物又はそのスラリを製造する際には、過冷却を解除することだけが重要という訳ではない。現実問題として、過冷却が解除された後の包接水和物生成用原料を冷却してより多くの包接水和物又はそのスラリを製造することも重要になってくる。   Here, when the clathrate hydrate or its slurry is produced by cooling an aqueous solution having the property of forming the clathrate hydrate, it is not necessarily important to release the supercooling. As a practical problem, it is also important to produce more clathrate hydrate or its slurry by cooling the clathrate hydrate-forming raw material after the supercooling is released.
しかし、そのような冷却が、過冷却が解除された包接水和物生成用原料を流通させる熱交換器の伝熱面により行われる場合には、熱交換器の伝熱面に包接水和物が付着して流路を狭めることなどの理由で、該熱交換器内での圧力損失が増加する事態を招来し易くなる。このような圧力損失の増加は、包接水和物生成用原料を流通させるポンプの負荷を増大させたり、所望の流量で流通させることができなくなったりするなどの問題が生じ、熱交換器内の伝熱面に付着して圧力損失の原因となっている包接水和物を融解する運転が必要になるなど、包接水和物又はそのスラリを長時間に亘って安定製造することの妨げとなる。
それ故、過冷却が解除された包接水和物生成用原料を冷却してより多くの包接水和物又はそのスラリを製造しようとする場合には、上記の圧力損失の増加を抑制又は防止する工夫が必要になる。
However, when such cooling is performed by the heat transfer surface of the heat exchanger that circulates the clathrate hydrate generating raw material from which supercooling is released, the inclusion water is added to the heat transfer surface of the heat exchanger. It becomes easy to cause a situation in which the pressure loss in the heat exchanger increases due to reasons such as attachment of a Japanese product and narrowing of the flow path. Such an increase in pressure loss causes problems such as an increase in the load on the pump through which the clathrate hydrate raw material is circulated and the inability to circulate at the desired flow rate. It is necessary to stably manufacture clathrate hydrate or its slurry over a long period of time, such as the need to melt the clathrate hydrate that adheres to the heat transfer surface and causes pressure loss. Hinder.
Therefore, when the clathrate hydrate-producing raw material from which supercooling has been released is cooled to produce more clathrate hydrate or a slurry thereof, the increase in the pressure loss is suppressed or Ingenuity to prevent is necessary.
本発明は以上の背景からなされたものであり、過冷却が解除された包接水和物生成用原料を冷却する際、その熱交換器内での圧力損失の増加を抑制又は防止することができる技術を提供することを目的とする。   The present invention has been made from the above background, and when cooling a clathrate hydrate generating raw material from which supercooling has been released, it is possible to suppress or prevent an increase in pressure loss in the heat exchanger. It aims at providing the technology that can be done.
上記目的を達成するための、本発明の第1の形態に係る包接水和物生成用原料は、包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、テトラisoペンチルアンモニウム塩が添加されており、冷却により前記包接水和物を生成させる性質を有し、包接水和物が含まれていることを特徴とするとするものである。   In order to achieve the above object, the clathrate hydrate-producing raw material according to the first embodiment of the present invention comprises a quaternary ammonium salt other than a tetraisopentylammonium salt that is a guest compound of the clathrate hydrate. In addition, tetraisopentylammonium salt is added, and the clathrate hydrate is generated by cooling, and the clathrate hydrate is contained.
本発明の第2の形態に係る包接水和物又はそのスラリを製造する方法は、第1の形態に係る包接水和物生成用原料を流通させる工程と、その流通の過程で当該包接水和物生成用原料を冷却する工程とを有することを特徴とするものである。   The method for producing the clathrate hydrate or slurry thereof according to the second aspect of the present invention comprises the steps of circulating the clathrate hydrate-producing raw material according to the first aspect, and And a step of cooling the raw material for producing the wet hydrate.
本発明の第3の形態に係る包接水和物又はそのスラリを製造する方法は、包接水和物又はそのスラリを製造する方法であって、包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、テトラisoペンチルアンモニウム塩が添加されており、冷却により前記包接水和物を生成させる性質を有する包接水和物生成用原料を用意する工程と、前記包接水和物生成用原料を冷却することで生じる過冷却を解除させ包接水和物を生成させる工程と、包接水和物を含む前記包接水和物生成用原料を流通させる工程と、その流通の過程で前記包接水和物生成用原料を冷却する工程とを有することを特徴とするものである。   The method for producing clathrate hydrate or its slurry according to the third aspect of the present invention is a method for producing clathrate hydrate or its slurry, which is a tetra compound that serves as a guest compound of clathrate hydrate. A clathrate hydrate-producing raw material is prepared which contains a quaternary ammonium salt other than isopentylammonium salt, has tetraisopentylammonium salt added, and has the property of producing the clathrate hydrate upon cooling. A step of releasing a supercooling caused by cooling the clathrate hydrate generating raw material to generate a clathrate hydrate, and the clathrate hydrate generating raw material containing the clathrate hydrate And a step of cooling the clathrate hydrate generating raw material in the course of the distribution.
本発明の第4の形態に係る包接水和物生成用水溶液を冷却する際に生じる圧力損失を低減する方法は、過冷却が解除され包接水和物を含む包接水和物生成用原料を熱交換器により冷却する際、前記熱交換器内で生じる圧力損失を低減する方法であって、前記水溶液に予めテトラisoペンチルアンモニウム塩を添加しておく工程を有することを特徴とするものである。   The method for reducing the pressure loss generated when the aqueous solution for clathrate hydrate production according to the fourth aspect of the present invention is cooled is for producing clathrate hydrate containing clathrate hydrate after the supercooling is released. A method for reducing pressure loss generated in the heat exchanger when the raw material is cooled by a heat exchanger, the method comprising a step of adding a tetraisopentylammonium salt to the aqueous solution in advance It is.
後述のとおり、包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、冷却により前記包接水和物を生成させる性質を有し、過冷却が解除されている包接水和物生成用原料に予めテトラisoペンチルアンモニウム塩を添加しておくと、その水溶液を冷却して包接水和物又はそのスラリを製造する際、生成する包接水和物が熱交換器の伝熱面に付着したり、流路の狭い箇所に堆積したりすることが生じ難いので、熱交換器内で生じる圧力損失の増加が抑制又は防止される。
それ故、本発明によれば、過冷却が解除された包接水和物生成用原料を冷却することにより包接水和物又はそのスラリを製造する際、熱交換器内の伝熱面に付着して圧力損失の原因となっている包接水和物を融解する運転が不要にまたは頻度が少なくなり、包接水和物又はそのスラリの製造を長時間に亘り安定的に行うことが可能になる。
As will be described later, it contains a quaternary ammonium salt other than the tetraisopentylammonium salt which is a guest compound of the clathrate hydrate, and has the property of generating the clathrate hydrate by cooling, and the supercooling is released. The clathrate hydrate produced when a clathrate hydrate or a slurry thereof is produced by cooling the aqueous solution by previously adding a tetraisopentylammonium salt to the clathrate hydrate production raw material. Is less likely to adhere to the heat transfer surface of the heat exchanger or deposit in a narrow portion of the flow path, so that an increase in pressure loss occurring in the heat exchanger is suppressed or prevented.
Therefore, according to the present invention, when the clathrate hydrate or the slurry thereof is produced by cooling the clathrate hydrate generating raw material whose supercooling is released, the heat transfer surface in the heat exchanger is provided. The operation of melting the clathrate hydrate that adheres and causes pressure loss is unnecessary or less frequent, and the clathrate hydrate or its slurry can be stably manufactured for a long time. It becomes possible.
本発明の各形態が奏する作用効果は、以下のとおりである。
本発明の第1の形態によれば、包接水和物又はそのスラリの製造に供されたとき、冷却されても圧力損失の増加が抑制又は防止される包接水和物生成用原料を実現することができる。それ故、この原料を冷却することにより包接水和物又はそのスラリを製造すれば、その製造を長時間に亘り安定的に行うことが可能になる。
The effect which each form of this invention has is as follows.
According to the first aspect of the present invention, there is provided a clathrate hydrate-producing raw material that suppresses or prevents an increase in pressure loss even when cooled when used for the production of clathrate hydrate or a slurry thereof. Can be realized. Therefore, if the clathrate hydrate or its slurry is produced by cooling this raw material, the production can be carried out stably for a long time.
本発明の第2及び第3の各形態によれば、包接水和物を含む包接水和物生成用原料がその流通の過程で、熱交換器で冷却されてもその熱交換器部分の圧力損失が増加し難くなる包接水和物又はそのスラリの製造方法を実現することができる。それ故、この製造方法によれば、包接水和物又はそのスラリを長時間に亘り安定的に製造することが可能になる。   According to each of the second and third aspects of the present invention, even if the clathrate hydrate-containing raw material containing clathrate hydrate is cooled by a heat exchanger in the course of its circulation, the heat exchanger portion thereof It is possible to realize a clathrate hydrate or a method for producing the slurry in which the pressure loss is less likely to increase. Therefore, according to this production method, the clathrate hydrate or its slurry can be produced stably for a long time.
本発明の第4の形態によれば、包接水和物を含む包接水和物生成用原料がその流通の過程で冷却されても圧力損失の増加を招来し難くなることから、包接水和物又はそのスラリを長時間に亘り安定的に製造することが可能になる。
テトラisoペンチルアンモニウム塩は、その包接水和物の調和融点が30℃程度であり、テトラisoペンチルアンモニウム塩以外の多くの第4級アンモニウム塩の包接水和物の調和融点に比べて高い。このため、テトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含む水溶液を冷却して、当該第4級アンモニウム塩の包接水和物を生成させる際に、テトラisoペンチルアンモニウム塩を添加しておくことにより、冷却過程でテトラisoペンチルアンモニウム塩の包接水和物が先に生成され、当該第4級アンモニウム塩の包接水和物の生成を促進して、その大きさや形態などに影響を及ぼし、包接水和物が熱交換器の伝熱面に付着したり、流路の狭い箇所に堆積したりすることを抑制して、熱交換器内で生じる圧力損失の増加が抑制又は防止される効果を生むと考えられる。
また、テトラisoペンチルアンモニウム塩を非常に低い濃度で添加(例えば1wt%以下)した場合でも、圧力損失の増加が抑制又は防止する効果があることを見出した。
According to the fourth aspect of the present invention, it is difficult to cause an increase in pressure loss even if the clathrate hydrate-containing raw material containing clathrate hydrate is cooled in the course of its circulation. It becomes possible to produce a hydrate or its slurry stably over a long period of time.
Tetraisopentylammonium salt has a harmonic melting point of its clathrate hydrate of about 30 ° C., which is higher than the harmonic melting point of many quaternary ammonium salt clathrate hydrates other than tetraisopentylammonium salt. . Therefore, when the aqueous solution containing a quaternary ammonium salt other than the tetraisopentylammonium salt is cooled to produce an inclusion hydrate of the quaternary ammonium salt, the tetraisopentylammonium salt is added. In this way, the clathrate hydrate of tetraisopentylammonium salt is first produced during the cooling process, which promotes the production of clathrate hydrate of the quaternary ammonium salt and affects its size and form. Suppresses the clathrate hydrate from adhering to the heat transfer surface of the heat exchanger or depositing in a narrow part of the flow path, thereby suppressing an increase in pressure loss generated in the heat exchanger or It is thought to produce a preventive effect.
Further, it has been found that even when tetraisopentylammonium salt is added at a very low concentration (for example, 1 wt% or less), an increase in pressure loss is suppressed or prevented.
このようなテトラisoペンチルアンモニウム塩としては、臭化テトラisoペンチルアンモニウム、フッ化テトラisoペンチルアンモニウム、塩化テトラisoペンチルアンモニウムが挙げられる。また、アニオン部がリン酸、硝酸、硫酸などのテトラisoペンチルアンモニウム塩が挙げられる。
また、本発明において、テトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩の典型例は、テトラnブチルアンモニウム塩である。
Examples of such a tetraisopentylammonium salt include tetraisopentylammonium bromide, tetraisopentylammonium fluoride, and tetraisopentylammonium chloride. Further, tetraisopentylammonium salts having an anion moiety such as phosphoric acid, nitric acid and sulfuric acid can be mentioned.
In the present invention, a typical example of the quaternary ammonium salt other than the tetraisopentylammonium salt is a tetra-n-butylammonium salt.
テトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩の典型例としての臭化テトラnブチルアンモニウム(TBAB)の水溶液に、テトラisoペンチルアンモニウム塩の典型例としての臭化テトラisoペンチルアンモニウム(以下TiPABという)を添加した包接水和物生成用原料を用いて、包接水和物スラリを製造する実験を行なった。   An aqueous solution of tetra-n-butylammonium bromide (TBAB) as a typical example of a quaternary ammonium salt other than the tetraisopentylammonium salt is added to a tetraisopentylammonium bromide (hereinafter referred to as TiPAB) as a typical example of a tetraisopentylammonium salt. The clathrate hydrate slurry was produced using the clathrate hydrate-forming raw material to which (A) was added.
[熱交換器による実験]
プレート式熱交換器(高さ1.6m、幅0.6m、奥行き0.9m、片側の保有水量0.2m、対向流方式)を用いて、包接水和物生成用原料を冷却して包接水和物スラリを製造する実験を行なった。
熱交換器に冷水を流入し、対向して過冷却が解除された包接水和物生成用原料を流入して熱交換させてさらに冷却し、包接水和物スラリを製造する。包接水和物生成用原料の流通速度は一定として、熱交換器の上流側と下流側の圧力を計測し、熱交換器内での圧力損失を計測した。
[Experiment with heat exchanger]
Using a plate-type heat exchanger (height 1.6m, width 0.6m, depth 0.9m, amount of retained water 0.2m 3 on one side, counter-flow system), the clathrate hydrate production raw material is cooled. Experiments were carried out to produce clathrate hydrate slurry.
Chilled water is introduced into the heat exchanger, and the clathrate hydrate generating raw material that has been released from supercooling is introduced into the heat exchanger for heat exchange to further cool the clathrate hydrate slurry. The flow rate of the clathrate hydrate generation raw material was constant, the pressure on the upstream and downstream sides of the heat exchanger was measured, and the pressure loss in the heat exchanger was measured.
包接水和物生成用原料として、14.5wt%濃度のTBAB水溶液のみの場合と、TBAB水溶液にTiPABの添加濃度を変えて添加した場合とを比較した。変えたTiPABの添加濃度は薄い方から順に、0.01、0.025、0.05wt%である。熱交換器での冷却を開始してからの圧力損失増加分の時間変化を図1に示す。図1のグラフは、横軸が経過時間(分)、縦軸が圧力損失増加分(kPa)である。   As a clathrate hydrate generating raw material, a case where only a 14.5 wt% concentration of TBAB aqueous solution was compared with a case where the addition of TiPAB was added to the TBAB aqueous solution at different concentrations. The added concentrations of TiPAB thus changed are 0.01, 0.025, and 0.05 wt% in order from the lowest. FIG. 1 shows the change over time in the amount of increase in pressure loss after the start of cooling in the heat exchanger. In the graph of FIG. 1, the horizontal axis represents elapsed time (minutes), and the vertical axis represents pressure loss increase (kPa).
TiPABを添加しない場合には、約9分で例えば90kPaまで圧力損失増加分が増加した。これに対して、TiPABの添加濃度を変えて添加した場合には、同じ圧力損失増加分に到達するまでの時間は、TiPABの添加濃度が0.01wt%では14分、0.025wt%では24分、0.05wt%では29分と長くなり、TiPABを添加することにより圧力損失の増加を抑制する効果が認められ、添加濃度が増加するに従い、圧力損失の増加が緩やかになる傾向にある。
また、熱交換量、つまり熱交換器を通過する間に単位重量の包接水和物生成用原料が得た冷熱量は、TiPABを添加した場合には、TiPABを添加しない場合に比べて減少することは無かった。むしろ、熱交換量が若干増加する結果であった。
When TiPAB was not added, the pressure loss increase increased to 90 kPa, for example, in about 9 minutes. On the other hand, when the addition concentration of TiPAB is changed, the time to reach the same increase in pressure loss is 14 minutes when the addition concentration of TiPAB is 0.01 wt%, and 24 hours when 0.025 wt% is added. Min., 0.05 wt%, it is as long as 29 minutes, and the effect of suppressing the increase in pressure loss is recognized by adding TiPAB, and the increase in pressure loss tends to be moderate as the addition concentration increases.
In addition, the amount of heat exchange, that is, the amount of cold heat obtained by the raw material for producing clathrate hydrate while passing through the heat exchanger, is reduced when TiPAB is added compared to when TiPAB is not added. There was nothing to do. Rather, the heat exchange amount increased slightly.
以上のように、TBAB水溶液にTiPABを添加した包接水和物生成用原料を冷却することにより、添加しない場合に比べて熱交換器内での圧力損失の増加を抑制することができることが判明した。
また、TiPABの添加濃度が高いほど圧力損失の増加を抑制する効果が高いことが分かった。
As described above, it was found that the increase in pressure loss in the heat exchanger can be suppressed by cooling the clathrate hydrate generating raw material in which TiPAB is added to the TBAB aqueous solution compared to the case where it is not added. did.
Moreover, it turned out that the effect which suppresses the increase in pressure loss is so high that the addition density | concentration of TiPAB is high.
このことは、TiPABを添加することにより、熱交換器内の伝熱面に付着、堆積等した包接水和物を除去することが必要な程度にまで圧力損失が増加するまでの時間を長くすることができることを意味しており、包接水和物または包接水和物スラリを長時間安定して製造することができることを示している。   This means that by adding TiPAB, the time until the pressure loss increases to the extent that it is necessary to remove the clathrate hydrate adhering to and accumulating on the heat transfer surface in the heat exchanger is increased. This means that the clathrate hydrate or clathrate hydrate slurry can be produced stably for a long time.
[二段熱交換器による実験]
水和物スラリにより蓄熱を行なうための水和物スラリ製造装置として、特開2004−3718号公報に記載されたものがある。同公報に記載された水和物スラリ製造装置は、水和物のゲスト化合物の水溶液を過冷却する水溶液過冷却熱交換器と、水和物スラリを冷却する水和物スラリ熱交換器を設けている。また、二つの熱交換器間の配管途中に、過冷却を解除する手段として、水和物結晶生成の核となる水和物スラリを過冷却水溶液に注入する手段を設けたものである。
本実験は、上記公報に記載されたものを基に、水溶液の過冷却を解除する手段として二つの熱交換器間にバッファタンクを設け、バッファタンクに流入する過冷却水溶液に水和物結晶生成の核として水和物スラリを注入して、バッファタンクを流通する間に過冷却解除を行なうようにした水和物スラリ製造装置を用いて行なった。
[Experiments with a two-stage heat exchanger]
As a hydrate slurry manufacturing apparatus for storing heat with a hydrate slurry, there is one described in JP-A-2004-3718. The hydrate slurry manufacturing apparatus described in the publication includes an aqueous supercooling heat exchanger for supercooling an aqueous solution of a hydrate guest compound and a hydrate slurry heat exchanger for cooling the hydrate slurry. ing. Further, in the middle of the piping between the two heat exchangers, there is provided means for injecting a hydrate slurry serving as a nucleus of hydrate crystal formation into the supercooled aqueous solution as means for releasing the supercooling.
In this experiment, based on what is described in the above publication, a buffer tank is provided between two heat exchangers as means for releasing supercooling of the aqueous solution, and hydrate crystals are generated in the supercooled aqueous solution flowing into the buffer tank. Hydrate slurry was injected as the core of the hydrate slurry, and this was carried out using a hydrate slurry production apparatus in which supercooling was canceled while flowing through the buffer tank.
図2はこの実験装置の説明図であり、1は水溶液ライン、2は水和物スラリライン、3は水和物スラリを過冷却水溶液に注入するライン、4は原料溶液を冷水との熱交換により冷却して過冷却状態にまで冷却する水溶液冷却熱交換器、5は過冷却解除され包接水和物を含む水和物スラリを冷水との熱交換によりさらに冷却して包接水和物の濃度を高め蓄熱量を高める水和物スラリ冷却熱交換器、6は過冷却状態の原料溶液に包接水和物生成の核となる水和物粒子を添加し、滞留している間に過冷却解除させるバッファタンク、7は冷水ラインを示している。   FIG. 2 is an explanatory view of this experimental apparatus, where 1 is an aqueous solution line, 2 is a hydrate slurry line, 3 is a line for injecting the hydrate slurry into the supercooled aqueous solution, and 4 is a heat exchange of the raw material solution with cold water. Aqueous solution cooling heat exchanger that cools to a supercooled state by cooling with water, and 5 is a clathrate hydrate by further cooling the hydrate slurry containing the clathrate hydrate after being overcooled by heat exchange with cold water Hydrate slurry cooling heat exchanger that increases the concentration of heat and increases the amount of heat storage, 6 adds hydrate particles that are the core of clathrate hydrate formation to the supercooled raw material solution and stays A buffer tank 7 for releasing the supercooling, and a cold water line.
この水和物スラリ製造装置では、水和物スラリ冷却熱交換器5内で包接水和物スラリをさらに冷却して包接水和物を生成して包接水和物の濃度を高めた水和物スラリを製造している。製造を続けていると生成した包接水和物が伝熱面に付着して次第に堆積したり、流路の狭隘箇所に堆積したりして熱交換器内の水和物スラリ流路を狭め、熱交換器内の圧力損失が大きくなる現象が生じる。
そのため、水和物スラリを流送するポンプの負荷が高くなったり、水和物スラリ流量が低下したりするという支障が生じ始める前に、すなわち、熱交換器の圧力損失がある程度大きくなった時点で、熱交換器内の付着、堆積した包接水和物を融解除去して、圧力損失を低下させる融解運転を行なう必要がある。
In this hydrate slurry manufacturing apparatus, the clathrate hydrate slurry is further cooled in the hydrate slurry cooling heat exchanger 5 to produce clathrate hydrate to increase the clathrate hydrate concentration. Manufactures hydrate slurries. As the production continues, the clathrate hydrate produced adheres to the heat transfer surface and gradually accumulates, or accumulates in narrow areas of the flow path, narrowing the hydrate slurry flow path in the heat exchanger. A phenomenon occurs in which the pressure loss in the heat exchanger increases.
Therefore, before the load of the pump that feeds the hydrate slurry increases or the trouble that the flow rate of the hydrate slurry decreases, that is, when the pressure loss of the heat exchanger increases to some extent Therefore, it is necessary to perform a melting operation to reduce pressure loss by melting and removing the adhering and accumulated clathrate hydrate in the heat exchanger.
融解運転の際には水和物スラリ冷却熱交換器5に冷水に替えて温水を供給することなどを行なうが、そうすると水和物スラリを冷却できないため、熱交換器の冷却稼働時間が減少して時間当たりの水和物スラリ製造装置の製造能力が低下してしまう。
このことから、逆に、水和物スラリ冷却熱交換器5内の圧力損失の増加を抑制できれば、圧力損失が増加して融解運転が必要なレベルにまで達するまでの時間を長くでき、時間当たりの水和物スラリ製造能力の低下を抑制できると考えられる。
そこで、水和物スラリ冷却熱交換器5内の圧力損失の増加を抑制して、圧力損失が増加して融解運転が必要なレベルにまで達する時間を長くできることの具体的な効果を調べる実験を行なった。
During the melting operation, hot water is supplied to the hydrate slurry cooling heat exchanger 5 instead of cold water. However, since the hydrate slurry cannot be cooled, the cooling operation time of the heat exchanger decreases. As a result, the production capacity of the hydrate slurry production apparatus per hour is reduced.
On the contrary, if the increase in the pressure loss in the hydrate slurry cooling heat exchanger 5 can be suppressed, the time until the pressure loss increases and the melting operation reaches a necessary level can be increased. It is considered that the decrease in the production capacity of hydrate slurry can be suppressed.
Therefore, an experiment was conducted to examine the specific effect of suppressing the increase in pressure loss in the hydrate slurry cooling heat exchanger 5 and increasing the time until the pressure loss increases and the melting operation reaches a necessary level. I did it.
実験は、水和物スラリ製造運転と、一定の圧力損失に到達したときに実施する融解運転とを繰返して実施した。水和物スラリ冷却熱交換器5での冷却を開始してから圧力損失が融解運転の必要なレベルに達するまでの時間(冷却運転時間という)を求めた。また、水和物スラリ製造運転と融解運転の繰返しを5時間にわたって実施した時の水和物スラリ冷却熱交換器5での冷熱の交換熱量、融解に用いた温熱の交換熱量(融解熱量という)及び冷熱の交換熱量から融解熱量を差し引いた有効交換熱量を求めた。
なお、水和物スラリ冷却熱交換器5での交換熱量は、熱交換器に流入する冷水温度と熱交換器から流出する冷水温度と、冷水流量を計測して求めた。また、水和物スラリ冷却熱交換器5での融解に用いた熱量は、熱交換器に流入する温水温度と熱交換器から流出する温水温度と、温水流量を計測して求めた。
The experiment was repeated with a hydrate slurry manufacturing operation and a melting operation performed when a certain pressure drop was reached. The time from the start of cooling in the hydrate slurry cooling heat exchanger 5 until the pressure loss reached the required level for melting operation (referred to as cooling operation time) was determined. In addition, when the hydrate slurry manufacturing operation and the melting operation are repeated for 5 hours, the heat exchange heat amount of the cold heat in the hydrate slurry cooling heat exchanger 5 and the heat exchange heat amount used for melting (referred to as the heat of fusion) The effective exchange heat quantity obtained by subtracting the heat of fusion from the exchange heat quantity of the cold heat was determined.
The amount of heat exchanged in the hydrate slurry cooling heat exchanger 5 was obtained by measuring the cold water temperature flowing into the heat exchanger, the cold water temperature flowing out from the heat exchanger, and the cold water flow rate. The amount of heat used for melting in the hydrate slurry cooling heat exchanger 5 was determined by measuring the hot water temperature flowing into the heat exchanger, the hot water temperature flowing out from the heat exchanger, and the hot water flow rate.
また、実験においては、包接水和物生成用原料として、14.5wt%濃度のTBAB水溶液のみの場合と、TBAB水溶液にTiPABの添加濃度を0.01、0.025、0.05wt%と変えて添加した場合との比較を行った。実験結果を表1に示す。   In addition, in the experiment, as the clathrate hydrate generation raw material, only the 14.5 wt% TBAB aqueous solution and the addition concentration of TiPAB to the TBAB aqueous solution were 0.01, 0.025, 0.05 wt%. A comparison was made with the case of adding by changing. The experimental results are shown in Table 1.
TBAB水溶液にTiPABを添加した包接水和物生成用原料を用いることにより、水和物スラリ冷却熱交換器5での圧力損失の増加を抑制することができ、融解運転を開始する必要がある圧力損失のレベルに達するまでの時間、すなわち冷却運転時間を長くすることができること、その結果、融解運転の頻度を低減でき、有効交換熱量を高くすることができることが判明した。
また、TiPABの添加濃度が高いほど、圧力損失の増加を抑制する効果が大きいことも分かった。
By using the raw material for clathrate hydrate generation in which TiPAB is added to the TBAB aqueous solution, an increase in pressure loss in the hydrate slurry cooling heat exchanger 5 can be suppressed, and it is necessary to start the melting operation. It has been found that the time to reach the level of pressure loss, that is, the cooling operation time can be increased, and as a result, the frequency of the melting operation can be reduced and the effective heat of exchange can be increased.
It was also found that the higher the TiPAB addition concentration, the greater the effect of suppressing the increase in pressure loss.
このようにTBAB水溶液にTiPABを添加した包接水和物生成用原料を用いることにより、水和物スラリ冷却熱交換器5での圧力損失の増加を抑制することができ、包接水和物または包接水和物スラリを長時間安定して製造することができる。   Thus, by using the clathrate hydrate generation raw material in which TiPAB is added to the TBAB aqueous solution, an increase in pressure loss in the hydrate slurry cooling heat exchanger 5 can be suppressed, and the clathrate hydrate can be suppressed. Alternatively, the clathrate hydrate slurry can be produced stably for a long time.
上記実施の形態では、包接水和物生成用原料のテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩の典型例として臭化テトラnブチルアンモニウム(TBAB)を挙げ、テトラisoペンチルアンモニウム塩の典型例として臭化テトラisoペンチルアンモニウム(TiPAB)を挙げたが、第4級アンモニウム塩としてのリン酸テトラnブチルアンモニウムの水溶液に、テトラisoペンチルアンモニウム塩としてリン酸テトラisoペンチルアンモニウムを添加したものを包接水和物生成用原料とすることによっても、熱交換器での圧力損失の増加を抑制することができ、包接水和物または包接水和物スラリを長時間安定して製造することができる。   In the above embodiment, tetra-n-butylammonium bromide (TBAB) is given as a typical example of the quaternary ammonium salt other than the tetraisopentylammonium salt which is a raw material for clathrate hydrate generation. As an example, tetraisopentylammonium bromide (TiPAB) was mentioned. An aqueous solution of tetra-n-butylammonium phosphate as a quaternary ammonium salt was added with tetraisopentylammonium phosphate as a tetraisopentylammonium salt. Inclusion of clathrate hydrate can also suppress an increase in pressure loss in the heat exchanger and stably produce clathrate hydrate or clathrate hydrate slurry for a long time. be able to.
本発明の実施例1における実験結果を示すグラフである。It is a graph which shows the experimental result in Example 1 of this invention. 本発明の実施例2の実験装置を示すグラフである。It is a graph which shows the experimental apparatus of Example 2 of this invention.
符号の説明Explanation of symbols
1 水溶液ライン
2 スラリライン
3 水和物スラリを過冷却水溶液に注入するライン
4 水溶液冷却熱交換器
5 水和物スラリ冷却熱交換器
6 バッファタンク
7 冷水ライン
DESCRIPTION OF SYMBOLS 1 Aqueous solution line 2 Slurry line 3 Line which injects hydrate slurry into supercooled aqueous solution 4 Aqueous solution cooling heat exchanger 5 Hydrate slurry cooling heat exchanger 6 Buffer tank 7 Cold water line

Claims (4)

  1. 包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、テトラisoペンチルアンモニウム塩が添加されており、冷却により前記包接水和物を生成させる性質を有し、包接水和物が含まれていることを特徴とする包接水和物生成用原料。 It contains a quaternary ammonium salt other than tetraisopentylammonium salt, which is a guest compound of clathrate hydrate, added with tetraisopentylammonium salt, and has the property of forming the clathrate hydrate upon cooling. And a clathrate hydrate-producing raw material containing clathrate hydrate.
  2. 請求項1に記載の包接水和物生成用原料を流通させる工程と、その流通の過程で当該包接水和物生成用原料を冷却する工程とを有することを特徴とする包接水和物又はそのスラリを製造する方法。 A clathrate hydration comprising the steps of circulating the clathrate hydrate generating raw material according to claim 1 and cooling the clathrate hydrate generating raw material in the course of the flow. A method of manufacturing an object or its slurry.
  3. 包接水和物又はそのスラリを製造する方法であって、包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、テトラisoペンチルアンモニウム塩が添加されており、冷却により前記包接水和物を生成させる性質を有する包接水和物生成用原料を用意する工程と、前記包接水和物生成用原料を冷却することで生じる過冷却を解除させ包接水和物を生成させる工程と、包接水和物を含む前記包接水和物生成用原料を流通させる工程と、その流通の過程で前記包接水和物生成用原料を冷却する工程とを有することを特徴とする包接水和物又はそのスラリを製造する方法。 A method for producing an clathrate hydrate or a slurry thereof, comprising a quaternary ammonium salt other than a tetraisopentylammonium salt to be a guest compound of the clathrate hydrate, wherein a tetraisopentylammonium salt is added A step of preparing a clathrate hydrate generating raw material having a property of generating the clathrate hydrate by cooling, and releasing supercooling caused by cooling the clathrate hydrate generating raw material. A step of producing an clathrate hydrate, a step of circulating the clathrate hydrate-producing raw material containing the clathrate hydrate, and cooling the clathrate hydrate-producing raw material in the course of the circulation. A method for producing an inclusion hydrate or a slurry thereof.
  4. 包接水和物のゲスト化合物となるテトラisoペンチルアンモニウム塩以外の第4級アンモニウム塩を含み、過冷却が解除され包接水和物を含む包接水和物生成用原料を熱交換器により冷却する際、前記熱交換器内で生じる圧力損失を低減する方法であって、前記水溶液に予めテトラisoペンチルアンモニウム塩を添加しておく工程を有することを特徴とする圧力損失を低減する方法。 A quaternary ammonium salt other than tetraisopentylammonium salt, which is a guest compound of clathrate hydrate, is released from the supercooling and the clathrate hydrate-containing raw material containing clathrate hydrate is removed by a heat exchanger. A method for reducing pressure loss, which comprises reducing a pressure loss generated in the heat exchanger when cooling, comprising adding a tetraisopentylammonium salt to the aqueous solution in advance.
JP2007218586A 2007-08-24 2007-08-24 Raw material for clathrate hydrate production, method for producing clathrate hydrate or slurry thereof, and method for reducing pressure loss generated when cooling an aqueous solution for clathrate hydrate production Expired - Fee Related JP5125316B2 (en)

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