JP3511086B2 - Method and apparatus for producing methane hydrate - Google Patents
Method and apparatus for producing methane hydrateInfo
- Publication number
- JP3511086B2 JP3511086B2 JP2000051348A JP2000051348A JP3511086B2 JP 3511086 B2 JP3511086 B2 JP 3511086B2 JP 2000051348 A JP2000051348 A JP 2000051348A JP 2000051348 A JP2000051348 A JP 2000051348A JP 3511086 B2 JP3511086 B2 JP 3511086B2
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- JP
- Japan
- Prior art keywords
- gas
- pressure
- temperature
- methane
- water
- 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.)
- Expired - Lifetime
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Description
【発明の属する技術分野】本発明は、メタン水和物を製
造するための方法と装置に関するものである。FIELD OF THE INVENTION The present invention relates to a method and apparatus for producing methane hydrate.
【０００１】[0001]
【従来の技術】特開平１１−１３０７００号公報には、
メタンハイドレート（メタン水和物）の製造方法とし
て、水とメタンの反応容器内に鉛直循環流を形成し、上
昇流部ヘメタンガスを供給する製造方法が示されてい
る。当該製造方法においては、メタン水和物の製造効率
を高める温度、圧力等の条件は開示されていない。特開
平１０−３２４６４６号公報、特開平１０−３２４６４
７号公報には、多孔質材料の細孔内に水和物状物を含む
材料及びその製造方法が開示されている。これらの発明
は、メタン水和物を多孔質材料に担持させる材料及びガ
ス／水の質量比が大きい水和物の製造方法に関するもの
であり、メタン水和物の製造過程を高効率化する条件を
開示したものではない。特開平０４−３０５２４１号公
報には、氷によりメタン水和物等の包接水和物の核形成
を励起する方法が示されている。また、特開平１０−１
９６８９５号公報、特開平１０−２１３２９６号公報及
び特開平１０−２３８９１３号公報には、メタン水和物
の製造方法として、製造容器へ氷粒を供給する方法が示
されている。これらの発明は、メタン水和物の生成を開
始される方法（核形成の励起）に関するものであり、核
形成以後の結晶成長過程を効率化する条件を明示してい
ない。特開昭４８−９２４０１号公報に、日本化学会
誌、１９９３（Ｎｏ．４）、３８７−３９４、１９９
３）には、メタン水和物を利用した天然ガス貯蔵運搬方
法として、脂肪族アミン、テトラヒドロフラン、アセト
ンなどにより水和物の生成圧力を低下させる方法が示さ
れている。これらの文献は、天然ガスの貯蔵運搬条件を
緩和することを示すにすぎず、メタン水和物の製造を高
効率化する条件を開示したものではない。2. Description of the Related Art Japanese Patent Laid-Open No. 11-130700 discloses
As a method for producing methane hydrate (methane hydrate), a production method in which a vertical circulation flow is formed in a reaction vessel of water and methane and methane gas is supplied to an ascending flow portion is shown. The manufacturing method does not disclose conditions such as temperature and pressure for increasing the manufacturing efficiency of methane hydrate. JP-A-10-324646, JP-A-10-32464
Japanese Patent Publication No. 7 discloses a material containing a hydrate in the pores of a porous material and a method for producing the same. These inventions relate to a material for supporting a methane hydrate on a porous material and a method for producing a hydrate having a large gas / water mass ratio, and conditions for increasing the efficiency of the methane hydrate production process. Is not disclosed. Japanese Unexamined Patent Publication No. 04-305241 discloses a method of exciting nucleation of clathrate hydrates such as methane hydrate with ice. In addition, JP-A-10-1
As a method for producing methane hydrate, a method of supplying ice particles to a production container is disclosed in JP-A-96895, JP-A-10-213296 and JP-A-10-238913. These inventions relate to a method of initiating the production of methane hydrate (excitation of nucleation), and do not specify conditions for improving the efficiency of the crystal growth process after nucleation. Japanese Unexamined Patent Publication (Kokai) No. 48-92401, Journal of Chemical Society of Japan, 1993 (No. 4), 387-394, 199.
In 3), as a natural gas storage and transportation method using methane hydrate, a method of lowering the hydrate formation pressure with an aliphatic amine, tetrahydrofuran, acetone or the like is shown. These documents merely show that the storage and transportation conditions of natural gas are relaxed, and do not disclose the conditions that make the production of methane hydrate highly efficient.
【０００２】[0002]
【発明が解決しようとする課題】本発明は、メタン水和
物の製造工程を高効率化し、かつ製造コストを低減する
製造方法と装置を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a manufacturing method and an apparatus for increasing the efficiency of the manufacturing process of methane hydrate and reducing the manufacturing cost.
【０００３】[0003]
【課題が解決するための手段】本発明によれば、以下の
発明が提供される。
（１）メタンガスを、ガス昇圧装置、定圧ガス供給装置
を介して温度調節装置及び圧力調節装置を備えた圧力容
器内の水と接触させることからなり、該水とメタンガス
との接触圧力を２．７７ＭＰａ以上の圧力条件に保持す
るとともに、該水とメタンガスとの接触温度を、該水と
メタンガスとの接触圧力に対するメタン水和物の生成平
衡温度より１℃低い温度でかつ−０．３℃以上の温度に
保持することを特徴とするメタン水和物の製造方法。
（２）メタンガスを昇圧させるガス昇圧装置、該昇圧メ
タンガスを所定圧力で供給する定圧ガス供給装置及び該
メタンガスと水との接触圧力を２．７７ＭＰａ以上の圧
力条件に保持する圧力調整装置と該メタンガスと水との
接触温度を該メタンガスと水との接触圧力に対するメタ
ン水和物の生成平衡温度より１℃低い温度でかつ−０．
３℃以上の温度に保持する温度調節装置を備える圧力容
器からなることを特徴とするメタン水和物の製造装置。According to the present invention, the following inventions are provided. (1) methane gas, a gas booster, constant pressure gas supply device
Pressure control device with temperature control device and pressure control device
Contacting the water in the vessel with the water and methane gas
Keep contact pressure with 2.77 MPa or higher
And the contact temperature between the water and methane gas
To 1 ℃ low have a temperature at and -0.3 ° C. or higher temperature than the product equilibrium temperature of methane hydrate to the contact pressure between methane
A method for producing methane hydrate, which is characterized by holding the methane hydrate. (2) Gas booster for boosting methane gas, the booster
Constant pressure gas supply device for supplying tan gas at a predetermined pressure, and the same
The contact pressure between methane gas and water is 2.77 MPa or more.
Between the methane gas and water
The contact temperature is 1 ° C. lower than the equilibrium temperature of methane hydrate formation with respect to the contact pressure between the methane gas and water , and −0.
Pressure capacity equipped with a temperature control device to keep the temperature above 3 ℃
An apparatus for producing methane hydrate, which comprises a vessel .
【０００４】[0004]
【発明の実施の形態】メタン水和物の生成速度と温度、
圧力の関係を明らかにした実施例を以下に示す。メタン
水和物生成装置としては、ガス昇圧装置、定圧ガス供給
装置及び圧力容器により構成されたものを用いた。メタ
ンガスは、ガス昇圧装置に装備された圧縮空気駆動のガ
スブースターにより加圧された後、定圧ガス供給装置に
流入する。定圧ガス供給装置は、圧力容器からのフィー
ドバック信号により電子圧力調整器をＰＩＤ制御して、
圧力容器へ供給される試料ガスを定圧に保持する。ま
た、定圧ガス供給装置から圧力容器へ送られる試料ガス
の質量は、質量流量計により測定される。このガス流量
は、メタン水和物の生成により消費された容器内のメタ
ンガス量に等しいので、メタン水和物の成長速度を示す
と考えられる。圧力容器は、内容積１．２×１０
-3ｍ2、設計圧力１９．６２ＭＰａのステンレス製であ
り、温度制御用の内部熱交換器とジャケット、観察用耐
圧ガラス（有効直径２０ｍｍ）、攪拌機、シース熱電
対、圧力変換器及び過飽和を解除するための冷却用銅棒
を備えている。攪拌機の中空のシャフトには、メタンガ
スと水の接触を促進するために、スパージャ型翼が取り
付けられた。スパージャ翼により、気相部から吸引され
たガスを液相部へ微細気泡として噴出させることが可能
である。これにより、メタンガスと水の気液接触を促進
することが可能である。生成温度は、低温恒温槽より、
内部熱交換器とジャケットへ、温度調整された不凍液を
循環して制御された。温度、圧力及びメタンガスの質量
流量は、インテリジェントレコーダーにアナログ記録さ
れるとともに、サンプリング間隔１〜３０秒でデジタル
記録された。BEST MODE FOR CARRYING OUT THE INVENTION
An example in which the relationship of pressure is clarified will be shown below. As the methane hydrate producing device, a device comprising a gas pressurizing device, a constant pressure gas supply device and a pressure vessel was used. The methane gas is pressurized by a compressed air-driven gas booster installed in the gas pressure booster and then flows into the constant pressure gas supply device. The constant pressure gas supply device PID-controls the electronic pressure regulator by the feedback signal from the pressure vessel,
The sample gas supplied to the pressure vessel is maintained at a constant pressure. Further, the mass of the sample gas sent from the constant pressure gas supply device to the pressure vessel is measured by a mass flow meter. Since this gas flow rate is equal to the amount of methane gas in the container consumed by the production of methane hydrate, it is considered to indicate the growth rate of methane hydrate. The pressure vessel has an internal volume of 1.2 x 10
-3 m 2 , made of stainless steel with a design pressure of 19.62 MPa, internal heat exchanger and jacket for temperature control, pressure resistant glass for observation (effective diameter 20 mm), stirrer, sheath thermocouple, pressure converter and release of supersaturation It is equipped with a copper rod for cooling. The hollow shaft of the stirrer was fitted with sparger-type blades to promote contact between methane gas and water. With the sparger blade, the gas sucked from the gas phase portion can be ejected to the liquid phase portion as fine bubbles. Thereby, it is possible to promote the gas-liquid contact of methane gas and water. The generation temperature is from a low temperature bath
A temperature-controlled antifreeze was circulated and controlled to the internal heat exchanger and jacket. The temperature, the pressure and the mass flow rate of methane gas were recorded on the intelligent recorder in an analog manner and digitally at a sampling interval of 1 to 30 seconds.
【０００５】メタン水和物の生成には、イオン交換水と
メタンガス（純度９９．５％以上）が使われた。メタン
ガスの初期充填は、メタン水和物の生成温度以上の温度
で行なわれて、攪拌により溶解が促進された。溶解が終
了した後、試料は、実験温度まで冷却された。冷却時の
溶解度増大にともなうガス流入が終了した後に、過飽和
解除用冷却棒を液体窒素で冷却することにより、メタン
水和物の生成が開始された。Ion-exchanged water and methane gas (purity 99.5% or more) were used for the production of methane hydrate. Initial filling of the methane is performed by generating temperature above the temperature of the methane hydrate, dissolution was promoted by stirring. After dissolution was complete, the sample was cooled to the experimental temperature. After the gas inflow due to the increase in solubility during cooling was completed, the production of methane hydrate was started by cooling the supersaturation release cooling rod with liquid nitrogen.
【０００６】図１は、成長速度係数と過冷却度の関係を
示す。ここで、成長速度係数は、水単位質量あたりのメ
タン水和物の質量増加速度である。また、過冷却度は、
メタン水和物の生成平衝条件の測定結果から決定された
次式の関係を用いて、生成圧力Ｐに対する生成平衡温度
Ｔと実温度の差として求められた。
ｌｎＰ＝−８０７６／Ｔ＋３０．５１ Ｐ＜１０ＭＰａ，
ｌｎＰ＝−１０１４５／Ｔ＋３７．７８ Ｐ≧１０ＭＰａ．
Ｐ：圧力（ＭＰａ）
Ｔ：絶対温度（Ｋ）FIG. 1 shows the relationship between the growth rate coefficient and the degree of supercooling. Here, the growth rate coefficient is a mass increase rate of methane hydrate per unit mass of water. Also, the degree of supercooling is
It was determined as the difference between the production equilibrium temperature T and the actual temperature with respect to the production pressure P, using the relationship of the following equation determined from the measurement result of the production equilibrium condition of methane hydrate. lnP = -8076 / T + 30.51 P <10 MPa, lnP = -10145 / T + 37.78 P ≧ 10 MPa. P: Pressure (MPa) T: Absolute temperature (K)
【０００７】成長速度係数は、過冷却度１℃以上の範囲
において、有意な値を持った。すなわち、メタン水和物
の成長は、過冷却度１℃以上で加速されることが明らか
となった。メタン水和物の成長速度は、過冷却度に比例
して増大する。しかし、過冷却度が過大であると、製造
工程を冷却するためのコストが増大するために不都合で
ある。一方、過冷却度１℃未満においては、メタン水和
物の成長速度が無視できるほどに遅いために、不都合で
ある。メタン水和物の生成は、温度−０．３℃以下の温
度範囲において、氷の発生を伴なうことが分かった。氷
の発生は、メタン水和物を製造するためには好ましくな
い。以上の製造試験から、メタン水和物を生成させる温
度は、温度−０．３℃以上でかつ生成圧力Ｐにおける生
成平衝温度Ｔより１℃以上低い温度、好ましくは１．５
〜１．５℃以上低い温度であることが明らかとなった。
なお、当該温度条件においてメタン水和物を製造するた
めには、圧力２．７７ＭＰａ以上で操作する必要があ
る。The growth rate coefficient had a significant value in the range of supercooling degree of 1 ° C. or more. That is, it was revealed that the growth of methane hydrate was accelerated at a supercooling degree of 1 ° C. or higher. The growth rate of methane hydrate increases in proportion to the degree of supercooling. However, if the degree of supercooling is excessively large, the cost for cooling the manufacturing process increases, which is disadvantageous. On the other hand, when the supercooling degree is less than 1 ° C., the growth rate of methane hydrate is negligibly slow, which is inconvenient. It was found that the formation of methane hydrate was accompanied by the formation of ice in the temperature range of -0.3 ° C or lower. The generation of ice is not desirable for producing methane hydrate. From the above production test, the temperature at which methane hydrate is produced is a temperature of −0.3 ° C. or higher and a temperature lower than the production equilibrium temperature T at the production pressure P by 1 ° C. or more, preferably 1.5.
It became clear that the temperature was low by ˜1.5 ° C. or more.
In addition, in order to produce methane hydrate under the temperature conditions, it is necessary to operate at a pressure of 2.77 MPa or more.
【０００８】[0008]
【発明の効果】このように、本発明に係わるメタン水和
物の製造方法を用いれば、冷却能力を過大に設定するこ
となく、メタン水和物の生成速度を増大させることが可
能である。公知の製造方法と比較すると、低コストで、
メタン水和物を高効率に製造できる効果がある。As described above, by using the method for producing methane hydrate according to the present invention, the production rate of methane hydrate can be increased without excessively setting the cooling capacity. Compared with known manufacturing methods, at low cost,
There is an effect that methane hydrate can be produced with high efficiency.
【図１】メタン水和物の生成速度は、過冷却度１℃以上
の温度条件において加速することを示すグラフを示す。FIG. 1 is a graph showing that the production rate of methane hydrate accelerates at a temperature condition of a supercooling degree of 1 ° C. or higher.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 成田 英夫 北海道札幌市豊平区月寒東２条17丁目２ 番１号 工業技術院北海道工業技術研究 所内 (56)参考文献 特開 平11−130700（ＪＰ，Ａ) 特表 平６−511500（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 5/00 C07C 7/20 C07C 9/04 - 9/08 C10L 3/00 C10L 5/00 C07B 53/02 C07B 61/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideo Narita Hideo Narita 2-17-1, Tsukikanto, Toyohira-ku, Sapporo-shi, Hokkaido, Institute of Industrial Technology Hokkaido Industrial Technology Research Institute (56) , A) Special table HEI 6-511500 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C07C 5/00 C07C 7/20 C07C 9/04-9/08 C10L 3/00 C10L 5/00 C07B 53/02 C07B 61/00
Claims (2)
供給装置を介して温度調節装置及び圧力調節装置を備え
た圧力容器内の水と接触させることからなり、該水とメ
タンガスとの接触圧力を２．７７ＭＰａ以上の圧力条件
に保持するとともに、該水とメタンガスとの接触温度
を、該水とメタンガスとの接触圧力に対するメタン水和
物の生成平衡温度より１℃低い温度でかつ−０．３℃以
上の温度に保持することを特徴とするメタン水和物の製
造方法。 The method according to claim 1 methane gas, a gas booster, pressure gas
Equipped with temperature control device and pressure control device via supply device
Contact with the water in the pressure vessel.
Contact pressure with tan gas is 2.77 MPa or higher
Temperature, and the contact temperature between the water and methane gas
And a 1 ℃ lower have a temperature from generating the equilibrium temperature of the methane hydrate to the contact pressure between the water and methane gas and -0.3 ° C. or less
A method for producing methane hydrate, which is characterized by holding at the above temperature .
該昇圧メタンガスを所定圧力で供給する定圧ガス供給装
置及び該メタンガスと水との接触圧力を２．７７ＭＰａ
以上の圧力条件に保持する圧力調整装置と該メタンガス
と水との接触温度を該メタンガスと水との接触圧力に対
するメタン水和物の生成平衡温度より１℃低い温度でか
つ−０．３℃以上の温度に保持する温度調節装置を備え
る圧力容器からなることを特徴とするメタン水和物の製
造装置。2. A gas booster for boosting methane gas,
Constant pressure gas supply device for supplying the boosted methane gas at a predetermined pressure
And the contact pressure between the methane gas and water is 2.77 MPa.
Pressure adjusting device for maintaining the above pressure conditions and the methane gas
The contact temperature of water with water is 1 ° C lower than the equilibrium temperature of methane hydrate formation with respect to the contact pressure of the methane gas with water .
One apparatus for producing methane hydrate characterized by comprising the pressure vessel including a temperature regulating device to keep the -0.3 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000051348A JP3511086B2 (en) | 2000-02-28 | 2000-02-28 | Method and apparatus for producing methane hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000051348A JP3511086B2 (en) | 2000-02-28 | 2000-02-28 | Method and apparatus for producing methane hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001233801A JP2001233801A (en) | 2001-08-28 |
| JP3511086B2 true JP3511086B2 (en) | 2004-03-29 |
Family
ID=18573010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000051348A Expired - Lifetime JP3511086B2 (en) | 2000-02-28 | 2000-02-28 | Method and apparatus for producing methane hydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3511086B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003227266B2 (en) * | 2002-03-28 | 2008-09-18 | Mitsui Engineering & Shipbuilding Co., Ltd | Gas hydrate and method for production thereof |
| MY134335A (en) * | 2002-09-11 | 2007-12-31 | Jfe Eng Corp | Process for producing gas clathrate and production apparatus |
| JP4514506B2 (en) * | 2004-05-10 | 2010-07-28 | Ｊｆｅエンジニアリング株式会社 | Gas clathrate manufacturing method and apparatus |
| JP4796418B2 (en) * | 2006-03-27 | 2011-10-19 | 三井造船株式会社 | Gas hydrate generating method and generating apparatus |
-
2000
- 2000-02-28 JP JP2000051348A patent/JP3511086B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001233801A (en) | 2001-08-28 |
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