JP3517832B2 - Water spray type hydrate manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates to how you industrial production of hydrate.

[0002]

2. Description of the Related Art A hydrate is an ice-like crystal in which a water molecule and a guest molecule such as methane or carbon dioxide are bonded under a low temperature and high pressure environment, and the guest molecule is incorporated into a cage formed by the water molecule. It has a unique structure. The production of hydrate is a useful and important technique from the viewpoint of storage and transportation of a gas compound, in that the gas compound can be easily solidified, can be gasified again when necessary, and is safe.
By the way, when a hydrate is to be generated at the contact interface between a liquid phase (water) and a gas phase (gas that becomes a guest molecule), once the hydrate layer is generated at the gas-liquid interface, the generated hydrate is generated. The layer prevents the mass transfer between gas and liquid, so that the reaction does not proceed any further. Therefore, in the conventional method, the liquid phase and the gas phase are stirred and mixed by rotating a stirrer, an impeller, or the like in the container, or by rotating and vibrating the entire container to generate a hydrate.

[0003]

In the above method, since the liquid phase and the gas phase have to be stirred and mixed, the whole apparatus has to be complicated. Further, in the above method, it took a long time to hydrate the entire liquid phase existing in the container. Furthermore, since the hydrate formed hinders the progress of stirring, after all, only a mixture of hydrate and water could be formed. Accordingly, the present invention aims at providing a way for the production of complete hydrate efficiently and conveniently in a short time.

[0004]

The above-mentioned objects have been achieved by the following inventions. ( 1 ) Compress the gas that becomes the guest molecule of hydrate
The gas pressure inside the reaction vessel to the hydrate formation pressure.
It is sent to the reaction vessel until it reaches
Cool the body to the temperature and pressure that satisfy the conditions for producing hydrate of gas in the reaction vessel, and then add water to the reaction vessel.
The pressure inside and the sum of the pressure loss in the piping and water spray means
And supply it to the water spray means
Then, water fine particles are directed from the water spray means toward the gas in the reaction vessel.
And a gas and water particles are brought into contact with each other to produce a hydrate. ( 2 ) The method for producing a water spray hydrate according to item ( 1 ), wherein water contains a water-soluble organic compound.

[0005]

In the production of hydrates by PREFERRED EMBODIMENTS way that have a above-described configuration, boosts and compressed by pressure intensifier the gas to be guest molecule hydrate, the gas in the reaction vessel Feed into the reaction vessel until the pressure reaches the hydrate formation pressure. At the same time, the cooling device cools the gas in the reactor until it reaches the hydrate formation temperature, so that the temperature and pressure of the gas in the reaction vessel satisfy the hydrate formation condition. Thereafter, the water is pressurized to a pressure value or more determined as the sum of the pressure in the reaction vessel and the pressure loss in the pipe and the water spraying means (for example, nozzle), and is supplied to the water spraying means provided in the reaction vessel. If a large number of water particles are sprayed from the water spraying means toward the gas in the reaction container, and the gas and the water particles are brought into contact with each other, gas molecules are taken into the water particles and become hydrated. As a result, hydrate fine particles are generated.

[0006] The present onset bright Way Method gases that can be applied to, for example methane, ethane, propane, and the like lower aliphatic hydrocarbon compounds such as isobutane. The pressure and temperature in the reaction vessel for producing the hydrate vary depending on the type of gas, but for example, in the case of methane, it is usually 4.3 MPa or more at a temperature of 5 ° C., and 6. at a temperature of 10 ° C.
Hydrate is generated at a pressure of 9 MPa or more. on the other hand,
In ethane, normally, a hydrate is generated at a pressure of 0.76 MPa or more when the temperature is 5 ° C. and at a pressure of 1.36 MPa or more when the temperature is 10 ° C. The particle size of the water particles to be brought into contact with the gas in the reaction vessel is preferably of the same order as that of the hydrate film formed at the gas-liquid interface, and is usually 15 μm or less, preferably 3 μm or less, more preferably 1 μm or less. Is. By spraying such fine particles of water and bringing them into contact with gas, hydrate can be efficiently generated without stirring. Further, in the present invention, the water to be brought into contact with the gas may contain a water-soluble organic compound, if necessary.
The water-soluble organic compound has a function of transitioning the hydrate formation temperature to a higher temperature side and the hydrate formation pressure to a lower pressure side, and can significantly reduce the energy required for hydrate formation. Examples of the water-soluble organic compound having such a function include cyclopentanol, cyclopentanone, tetrahydrofuran, furan, γ-butyrolactone, 1,4-dioxane, acetone, 1,3-dioxolane and the like.

[0007]

The present invention will be described below with reference to the drawings. Figure 1,
2 illustrates a preferred embodiment of the water spray hydrate Manufacturing according to the present invention. Example 1 Figure 1 is an explanatory diagram showing the configuration of Example 1. Te you have <br/> 1, the intensifier is connected to the reaction vessel 1 by the high-pressure pipe 6 2
Is used to supply a gas serving as guest molecules of hydrate to the reaction vessel 1 and to pressurize the inside of the reaction vessel 1 to a gas hydrate generation pressure, and a reaction tower by a cooling device 3 and a cooling pipe 9 which are temperature adjusting means. The gas in 1 is cooled until it reaches the hydrate formation temperature. The nozzle 4, which is a means for spraying water attached to the reaction vessel 1, has a high-pressure pipe 7
Is connected to the discharge port of the pressurizing pump 5. Water is pressurized by the pressure pump 5 and supplied to the nozzle 4. The injection port of the nozzle 5 is directed toward the gas inside the reaction container 1, and water is sprayed toward the gas inside the reaction container 1 as a large number of fine particles and brought into contact therewith. As a result, solid hydrate is deposited and deposited in the reaction vessel 1. Te placed <br/> 1, the check valve 8 is provided between the nozzle 4 and the pressure pump 5. A plurality of nozzles may be attached. By attaching a plurality of particles, a large amount of water particles can be generated at one time, and the hydrate production efficiency is improved. A nozzle may be provided above the reaction vessel and sprayed from above,
A nozzle may be provided on the side surface of the reaction container to spray from the side surface. The number and arrangement of the nozzles in the reaction container are appropriately determined according to the size and shape of the reaction container. The cooling pipe 9 of the cooling device 3 is arranged so as to surround the outer periphery of the reaction container 1, and cools the gas inside the reaction container 1 together. The cooling pipe 3 may be provided inside the reaction container 1. The method for adjusting the temperature in the reaction container is not limited to this, and any known method may be used. The hydrate produced and accumulated in the reaction vessel was prepared after the hydrate production was completed.
The solid may be taken out as it is from the gas supply port of the reaction container or the like, or it may be held in the reaction container as it is and dissociated when necessary to return the gas to the original gas state and released from the gas supply port. May be. Further, if necessary, a hydrate or a port for taking out gas and water or a valve may be provided in the reaction vessel.

Second Embodiment FIG. 2 is an explanatory diagram showing the configuration of the second embodiment. 2, the same symbols as those in FIG. 1 indicate the same things. In FIG. 2, reference numeral 10 denotes a tank, in which water is mixed with a water-soluble organic compound and supplied to the suction port of the pressure pump 5. As the water-soluble organic compound, the above-mentioned cyclopentanol or the like can be used. Also In Fig. 2, may be provided, such as outlet such hydrate optionally in the same manner as in Example 1.

[0009] Oite the present onset bright, that the temperature in the reaction vessel, the pressure may be a hydrate formation conditions of the supplied gas, can be contacted efficiently particulates and gaseous water inside If it is, the size and shape of the reaction container are not particularly limited. The material of the reaction vessel is not particularly limited, and SUS304 or the like is used. Since this onset Ming to control temperature, the pressure in the reaction vessel, these measurements has the like means for displaying, and omitted in FIGS.

[0010]

INDUSTRIAL APPLICABILITY In the present invention, the contact area between the liquid phase and the gas phase is dramatically increased by atomizing water and spraying it into a gas, and a hydrate can be produced in a short time. . Further, it is not necessary to mix and stir the liquid phase and the gas phase, and the hydrate can be produced by a simple apparatus having no stirring means. Further, conventionally, the hydrate layer formed at the gas-liquid interface hinders the mass transfer between the gas and the liquid, the reaction does not proceed efficiently, and the product is a mixture of water and hydrate. If so, it is possible to efficiently generate a complete hydrate. According to the present invention, the gas can be easily solidified in this way, and the gas can be taken out from the solid if necessary, and it is safe because water is used, and the gas compound can be stored, It has an excellent effect in transportation.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a configuration of a first embodiment.

FIG. 2 is an explanatory diagram showing a configuration of a second embodiment.

[Explanation of symbols]

1 reaction vessel 2 Booster 3 Cooling device 4 nozzles 5 pressure pump 6,7 High pressure piping 8 Check valve 9 Cooling pipe 10 tanks

Front page continuation (56) References Tokuhyo 6-511500 (JP, A) International Publication 99/019282 (WO, A1) Journal of the Chemical Society of Japan, 1993, No. 4, P 389-394 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 7/20 C07C 5/00 C07C 9/02-9/12

Claims (2)

(57) [Claims] 1. A gas which becomes a guest molecule of hydrate
When compressed, the gas pressure in the reaction vessel creates hydrate
Feed into the reaction vessel until the pressure is reached and simultaneously
The gas inside is cooled, and the hydrate formation conditions are satisfied temperature and pressure of the gas in the reaction vessel, and thereafter, water anti
Pressure in reaction vessel and pressure loss in piping and water spray means
Pressurize more than the pressure value determined as the sum of
The water is sprayed from the water spray means to the gas in the reaction vessel.
A method for producing a water-spraying hydrate, which comprises spraying as particles and bringing gas and water particles into contact with each other to generate hydrate. 2. The method for producing a water spray hydrate according to claim 1 , wherein the water contains a water-soluble organic compound.
Law .