KR20110105453A - Method for producing hydrogen hydrate and method for stroing hydrogen using gas accelerator - Google Patents

Abstract

The present invention relates to a hydrogen hydrate and a method for preparing the same, wherein the hydrogen hydrate is stored by applying the principle of hydrate formation, and SF ₆ and HFCs are used as hydrate formation accelerators to change thermodynamic equilibrium conditions or reaction conditions required for hydrate formation. To stably store hydrogen.

Description

HYDROGEN HYDROGEN HYDRATE AND METHOD FOR STROING HYDROGEN USING GAS ACCELERATOR}

The present invention relates to a hydrogen hydrate and a method for preparing the same, and more particularly to a hydrogen hydrate and a method for preparing the same using SF ₆ , HFCs as a hydrate formation accelerator.

Hydrogen utilization technology is an environmentally clean and efficient fuel and is an active area of research around the world. Common hydrogen storage technologies include liquefied hydrogen technology, compressed hydrogen technology, hydrogen storage alloy technology and carbon nanotube technology.

Liquefied hydrogen technology is the most widely used to date, and the liquefied hydrogen used in the liquefied hydrogen technology is a high energy-intensive form of transport as a high-density hydrogen. However, there is a disadvantage that approximately 40% of the energy content has to be consumed to liquefy hydrogen having a very low condensation temperature (20K). In order to maintain such a low condensation temperature, a coolant must be provided, which is impractical and inexpensive. As an example, the temperature of liquid nitrogen, which is one of the representative coolants (> 77 K), is higher than the condensation temperature of liquefied hydrogen. Therefore, even when a coolant is provided, continuous evaporation of liquefied hydrogen occurs, which implies the problem of hydrogen storage.

In addition, compressed hydrogen technology generally accommodates hydrogen at around 15 g / l at 35 MPa. Higher pressures can store hydrogen at higher densities, but are limited by problems such as stability. As another storage method to overcome this problem, a method of adsorbing hydrogen molecules on a large surface solid has been developed.

In addition, since hydrogen storage alloy technology or carbon nanotube technology requires the use of a special material, there is a material limitation, which makes it difficult to commercialize.

In order to overcome the problems of the above-described tank storage techniques, a storage technique using hydrogen hydrate has been proposed. Here, hydrogen hydrate refers to a compound in which water molecules are hydrogen-bonded under low temperature and high pressure to form a nano-sized cage structure (host lattice), in which gas molecules / atoms are encapsulated as guests. The storage technique using hydrogen hydrate generally means to store hydrogen molecules in a lattice of an ice form host (main components of water, methane, ammonia, carbon dioxide, etc.). This hydrogen storage technology is a very interesting alternative to the hydrogen storage method in the solid form. Various forms of hydrogen hydrate can be formed under pressure-temperature conditions of various conditions. Hydrogen crystal compounds in water lattice having a bonding structure of H ₂ (H ₂ 0) ₆ are 23 g / at a pressure of 700 bar at 300 K. If the pressure is 2,200 bar, it can store 110g / l of hydrogen.

However, the pressure for storing the above-mentioned hydrogen hydrate is not economical because it is a considerably high pressure, and thus there is a problem that it is difficult to put into practical use.

The present invention is to solve the above-mentioned problems of the prior art, the object of the present invention is to use hydrogen at high temperature and low pressure compared to the existing hydrogen storage temperature and pressure using SF ₆ , HFCs and mixtures thereof as hydrate accelerator It is to provide a hydrogen hydrate capable of transporting and storing and a method for preparing the same.

In addition, it is an object of the present invention to provide a hydrogen hydrate and a method for producing the same, which is easy to store hydrogen in a stable environment, can be used as an environmentally clean and efficient fuel.

It is also an object of the present invention to provide a hydrogen hydrate having a large weight and bulk density and a method for producing the same, which can be extended to the energy and industrial fields by a technology corresponding to the Climate Change Convention (CSLF, Kyoto Protocol).

In addition, an object of the present invention is to provide a variety of high-density hydrogen storage technology that can be used for transportation / stationary / portable fuel cell, it is widely used in many fields using fuel cells, such as automotive, power generation, hydrogen station, portable, etc. It is.

It is also an object of the present invention to provide a hydrogen hydrate and a method for producing the same that can be utilized as alternative energy.

In order to achieve the above object, the present invention provides a hydrogen hydrate characterized in that it comprises one selected from the group consisting of SF ₆ , HFCs and mixtures thereof as water, hydrogen and hydrate promoters.

The present invention also provides a hydrogen hydrate, characterized in that the hydrate promoter is included in a volume of more than 0 and less than 7 with respect to 100 volumes of hydrogen.

In addition, the present invention is to form a hydrogen hydrate by leaving one selected from the group consisting of SF ₆ , HFCs and mixtures thereof with water, hydrogen and hydrate accelerators at a temperature of 273K to 303K, pressure of 40bar to 50bar It provides a method for producing a hydrogen hydrate characterized in that.

In addition, the present invention provides a method for producing a hydrogen hydrate, characterized in that further comprising stirring one selected from the group consisting of SF ₆ , HFCs and mixtures thereof with the water, hydrogen and hydrate promoter.

The hydrogen hydrate of the present invention includes SF ₆ , HFCs, and mixtures thereof as hydrate accelerators, thereby storing and transporting hydrogen at a higher temperature and a lower pressure than the conventional hydrogen hydrate. In addition, the hydrogen hydrate of the present invention is easy to store hydrogen in a stable environment, can be used as an environmentally clean and efficient fuel. In addition, the hydrogen hydrate of the present invention can be extended to energy and industrial fields as a technology corresponding to the Climate Change Convention (CSLF, Kyoto Protocol). Hydrogen hydrate of the present invention provides a high-density hydrogen storage technology that can be used for transportation, stop, and portable fuel cells, and is widely used in many fields using fuel cells such as fuel cell vehicles, power generation, hydrogen stations, and portable devices. can do. In addition, the hydrogen hydrate of the present invention can be utilized as an alternative energy.

1 is a schematic diagram schematically showing a hydrogen hydrate forming apparatus using an inert gas as a hydrate accelerator according to the present invention.
FIG. 2 is a graph showing the pressure of the gas supply chamber with time when generating Example 1. FIG.
Figure 3 is a graph of the gas generated by dissociating the hydrogen hydrate produced in Example 1 at a temperature of 25 ℃, pressure 1bar by GC.
4 is a graph analyzing pure H ₂ gas using GC.
5 is a graph analyzing pure SF ₆ gas using GC.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Ⅰ. Hydrogen hydrate

The hydrogen hydrate of the present invention includes one selected from the group consisting of SF ₆ , HFCs and mixtures thereof as water, hydrogen and hydrate promoters. Since the hydrogen hydrate includes a hydrate accelerator, the hydrogen hydrate is easily generated at a higher temperature than the pressure and a lower pressure than the conventional hydrogen hydrate including water and hydrogen only. This is an effect that occurs because the hydrate promoter stabilizes the pores in the hydrogen hydrate to induce hydrogen to fill the pores well.

Among the hydrate promoters, HFCs mean hydro fluorocarbons. The hydrate promoter is preferably included in the hydrogen hydrate of the present invention in a volume of more than 0 and less than 7 compared to 100 of the hydrogen. If the above range is satisfied, hydrogen hydrate having a stable structure can be produced at a relatively low cost and under a high temperature and a low pressure.

II. Method of preparing hydrogen hydrate

In the method of preparing the hydrogen hydrate of the present invention, the hydrogen hydrate is prepared by leaving one selected from the group consisting of SF ₆ , HFCs, and mixtures thereof as water, hydrogen, and hydrate accelerators at a temperature of 273 K to 303 K and a pressure of 40 bar to 50 bar. Forming. In the above temperature and pressure range, the hydrogen and the hydrate promoter are dissolved in water, thereby forming a hydrogen hydrate. In addition, since the hydrogen hydrate of the present invention can be produced at the above-described temperature and pressure range, the hydrogen hydrate of the present invention has a high temperature compared to the pressure and a low pressure compared to the temperature as compared with the conventional hydrogen hydrate produced at a temperature of 300 K and a pressure of 700 bar. It can be seen that it can be easily produced. This is because the hydrate promoter stabilizes the pores in the hydrogen hydrate, leading to hydrogen filling well. On the other hand, the water for producing the hydrogen hydrate of the present invention is preferably tertiary distilled water.

The water; Hydrogen; And hydrate accelerator SF ₆ , HFCs and one kind selected from the group consisting of a mixture thereof; It is preferable to stir together, the stirring speed is preferably 100 ~ 1000rpm. If the above-mentioned range is satisfied, more uniform hydrogen hydrate can be manufactured.

Hydrogen hydrate of the present invention includes one selected from the group consisting of SF ₆ , HFCs, and mixtures thereof as a hydrate accelerator to store and transport hydrogen at a higher temperature and lower pressure than the existing hydrogen storage temperature and pressure. have. In addition, the hydrogen hydrate of the present invention is easy to store hydrogen in a stable environment, can be used as an environmentally clean and efficient fuel.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example 1 Preparation of Hydrohydrate

An embodiment of the present invention was generated using the apparatus of Korean Patent No. 10-0786812 shown in FIG.

135 ml of tertiary distilled water was stored in a reactor (R) having a volume of 350 cm 3, and SF ₆ was stored so that the internal pressure of the reactor (R) was 3 bar. Meanwhile, hydrogen was stored so that the internal pressure of the gas supply chamber (S) having a volume of 518 cm 3 was 61 bar.

Hydrogen stored in the gas supply chamber was injected into the reactor in which the tertiary distilled water and SF ₆ were stored so that the internal pressure of the reactor was 50 bar, and the internal temperature of the reactor was 283K. Meanwhile, hydrogen was stored again so that the internal pressure of the gas supply chamber was 61 bar.

Hydrogen hydrate was prepared by putting a magnetic bar inside the reactor for efficient agitation inside the reactor in which hydrogen, water and SF ₆ were stored, and stirring at 500 rpm using a magnetic stirrer.

Test Example 1: Confirmation of Hydrogen Hydrate

<Pressure change of gas supply chamber according to manufacturing of hydrogen hydrate>

Figure 2 is a graph showing the pressure of the gas supply chamber with time in the first embodiment.

Here, since the gas supply chamber is connected to the reactor, the pressure change of the gas supply chamber refers to the gas consumption in the reactor.

Referring to FIG. 2, it can be seen that the pressure of the gas supply chamber is changed from approximately 61 bar to 57 bar during 120 minutes during which the hydrogen hydrate is generated, so that the gas is consumed by the pressure of approximately 4 bar. Thus, it can be seen that SF ₆ was consumed 3bar in hydrate form, and 1bar of hydrogen was stored.

<Hydrogen analysis through hydrogen hydrate dissociation>

The hydrogen hydrate produced in Example 1 was dissociated at a temperature of 25 ° C. and a pressure of 1 bar. The gas generated was analyzed by GC and shown in FIG. 3.

Referring to Figure 3, it can be seen that the peak occurs when the residence time is about 2.7 minutes and about 3.5 minutes.

Meanwhile, FIG. 4 is a graph analyzing pure H ₂ gas using GC, and FIG. 5 is a graph analyzing pure SF ₆ gas using GC.

Referring to FIG. 4, the residence time of the H ₂ gas is about 2.6 minutes, and referring to FIG. 5, the residence time of the SF ₆ gas is about 3.5 minutes.

As a result of Figs. 4 and 5, it can be seen that the peaks for the hydrogen and SF ₆ in the 2 minutes and 3 minutes shown in Fig. 3, respectively. For this reason, it can be seen that the hydrogen hydrate of Example 1 according to the present invention is a hydrate including hydrogen and SF ₆ .

Claims (4)

Hydrogen hydrate comprising one selected from the group consisting of SF ₆ , HFCs and mixtures thereof as water, hydrogen and hydrate promoters. The method according to claim 1,
Wherein said hydrate promoter is contained in a volume greater than 0 and less than 7 with respect to 100 volumes of hydrogen. Hydrogen hydrate, characterized in that the water, hydrogen and hydrate accelerator is selected from the group consisting of SF ₆ , HFCs and mixtures thereof at a temperature of 273K to 303K, pressure of 40bar to 50bar to form a hydrogen hydrate Manufacturing method. The method according to claim 3,
Method for producing a hydrogen hydrate, characterized in that further comprising stirring one selected from the group consisting of SF ₆ , HFCs and mixtures thereof as the water, hydrogen and hydrate promoter.

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