KR102187754B1 - Carbon dioxide sorbent including diamine hydrate, and carbon dioxide supplier made therefrom - Google Patents

Abstract

An embodiment of the present invention provides a diamine hydrate. In addition, it provides a carbon dioxide absorbent containing the diamine hydrate. The diamine hydrate includes a diamine compound and a water molecule, and the diamine compound and the water molecule are hydrogen bonded to each other to form a crystal structure and are solid at room temperature.

Description

Carbon dioxide sorbent including diamine hydrate, and carbon dioxide supplier made therefrom

The present invention relates to a carbon dioxide absorbent and a diamine carbonate prepared therefrom, and more particularly, to a carbon dioxide absorbent including a diamine hydrate and a diamine carbonate produced by reacting the diamine hydrate with carbon dioxide.

After the Industrial Revolution, emission of greenhouse gases such as CO ₂ , CH ₄ and NO ₂ increased due to the widespread use of fossil fuels, and these emission of greenhouse gases caused global warming. In particular, the major cause of global warming is carbon dioxide, which accounts for more than 70% of greenhouse gases.

Various studies are being conducted to reduce carbon dioxide, which has been attracting attention as the main culprit of global warming. Specifically, the importance of carbon oxide capture and storage technology (CCS) has been emphasized, and CCS for separating such carbon dioxide includes an absorption method, an adsorption method, a membrane separation method, and a deep cooling method.

Among them, the absorption method is a method of selectively removing carbon dioxide by contacting a solution capable of absorbing carbon dioxide with a gas containing carbon dioxide, of which the wet amine method is a representative method. In the wet amine method, carbon dioxide is generally absorbed by using an aqueous solution of MEA (monoethanolamine).

As described above, in the case of a liquid carbon dioxide absorbent using an aqueous amine solution, it is regenerated under high temperature conditions, so the absorption performance decreases due to evaporation or denaturation of the aqueous amine solution, causing corrosion of the device, and high operating cost due to high renewable energy. There is a problem that can only be used in the process.

Korean Patent Registration No. 10-1571062

The technical object of the present invention is to provide a solid diamine hydrate and a solid carbon dioxide absorbent using the same.

In addition, to provide a diamine carbonate formed by additionally reacting carbon dioxide with the solid diamine hydrate and a carbon dioxide supplying agent using the same.

In addition, it is to provide a fire extinguisher system including the carbon dioxide supply.

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems that are not mentioned can be clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention provides a carbon dioxide absorbent.

At this time, the carbon dioxide absorbent contains a diamine hydrate including a diamine compound represented by the following Formula 1 and a water molecule, and the diamine hydrate forms a crystal structure by hydrogen bonding of the diamine compound and the water molecule to each other and at room temperature. It is characterized by being solid.

In Formula 1, R ₁ , R ₂ , R ₃ are each independently a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms.

In addition, the diamine compound is characterized in that N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA).

In addition, the carbon dioxide absorbent is characterized in that it reacts with carbon dioxide at room temperature to form diamine carbonate.

In order to achieve the above technical problem, another embodiment of the present invention provides a carbon dioxide supplying agent.

In this case, the carbon dioxide supplying agent is characterized in that it includes a diamine carbonate formed by further reacting carbon dioxide to a diamine hydrate formed by the reaction of a diamine compound represented by the following Formula 1 with water.

In Formula 1,

R ₁ , R ₂ , and R ₃ are each independently a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms.

In this case, the diamine compound is protonated and bonded to the carbonate by hydrogen bonding, forming a crystal structure, and being solid at room temperature.

In this case, the diamine compound is N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA).

At this time, the carbon dioxide supplying agent is characterized in that during heat treatment, it melts and releases carbon dioxide at the same time, and crystallizes again at room temperature after the melting is completed.

At this time, the carbon dioxide supply is characterized in that the melting is terminated at 60 °C to 90 °C during heat treatment.

In order to achieve the above technical problem, another embodiment of the present invention provides a fire extinguisher system.

At this time, the fire extinguisher system is characterized in that it includes a carbon dioxide supply according to another embodiment of the present invention.

According to an embodiment of the present invention, a solid diamine hydrate and a solid carbon dioxide absorbent using the same can be provided. Since the carbon dioxide absorbent exists as a solid at room temperature, it has the advantage of having lower renewable energy, less risk of evaporation and denaturation, and not causing corrosion of the device compared to the liquid carbon dioxide absorbent. In addition, since it can be manufactured in a variety of forms compared to a liquid carbon dioxide absorbent that requires an absorbent reaction vessel in the form of a liquid reactor, it can be miniaturized and applied to various fields. In addition, a fast reaction rate can be maintained by including a diamine compound having a very high reactivity to carbon dioxide.

According to another embodiment of the present invention, it is possible to provide a diamine carbonate and a carbon dioxide supplying agent using the same. The carbon dioxide supplying agent can completely release carbon dioxide by ending melting at a relatively low temperature in the range of 60 °C to 90 °C, and after the melting is finished, it can be crystallized into a solid again at room temperature.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a diagram showing the bonding relationship between the diamine compound and water molecules contained in a carbon dioxide absorbent according to another embodiment of the present invention.
FIG. 2 is a diagram showing a bonding relationship between a diamine compound and a carbonate included in a carbon dioxide supplying agent according to another embodiment of the present invention.
3 shows a reaction mechanism of an amine compound and carbon dioxide and a product thereof.
4 is a photograph of a carbon dioxide absorbent in powder form prepared according to Preparation Example 1. FIG.
5 is a graph showing the crystal structure of N,N'-di-tert-butylethylenediamine hydrate before and after absorption of carbon dioxide.
6 is a graph measuring heat generated when N,N'-di-tert-butylethylenediamine hydrate is generated according to temperature and molar ratio by a micro-reaction calorimeter.
7 is a thermogravimetric analysis (TGA) result of N,N'-di-tert-butylethylenediamine hydrate and N,N'-di-tert-butylethylenediamine carbonate.
8 is a graph obtained by measuring N,N'-di-tert-butylethylenediamine carbonate by FT-IR spectroscopy.
9 is a graph measured by differential scanning calorimetry (DSC) of heat flow generated during heat treatment of N,N'-di-tert-butylethylenediamine carbonate.
10 is a graph showing the absorption amount of carbon dioxide over time of N,N'-di-tert-butylethylenediamine hydrate.
11 is a graph showing the absorption amount of carbon dioxide by temperature of N,N'-di-tert-butylethylenediamine carbonate.
12 is a graph showing the absorption amount of carbon dioxide according to the partial pressure of carbon dioxide of N,N'-di-tert-butylethylenediamine hydrate in a high-pressure reactor.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, bonded)" with another part, it is not only "directly connected", but also "indirectly connected" with another member in the middle. "Including the case. In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

The terms used in the present specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

A carbon dioxide absorbent according to an embodiment of the present invention will be described.

The carbon dioxide absorbent according to an embodiment of the present invention may contain a diamine compound represented by the following Formula 1 and a diamine hydrate including a water molecule.

In this case, in the diamine hydrate, the diamine compound and the water molecule may be bonded to each other by hydrogen bonding, forming a crystal structure and being solid at room temperature.

In the case of a conventional carbon dioxide absorbent using an aqueous amine solution, the carbonate after absorption of carbon dioxide is present in a solution state and needs to be regenerated with distillation of water under high temperature conditions, so energy consumption is large, and the absorption performance decreases due to the denaturation of the amine at high temperature. There is a problem that causes corrosion.

The carbon dioxide absorbent according to an embodiment of the present invention is present in a solid state at room temperature, thereby compensating for the disadvantages of the carbon dioxide absorbent using the amine aqueous solution, and maintaining a fast reaction rate by including a diamine compound having high reactivity with carbon dioxide.

The diamine hydrate may react with carbon dioxide at room temperature to form a diamine carbonate, and using this property, the diamine hydrate may be used as a carbon dioxide absorbent.

1 is a diagram showing the bonding relationship between the diamine compound and water molecules contained in a carbon dioxide absorbent according to an embodiment of the present invention.

Referring to FIG. 1, a water molecule may be located between molecules of a diamine compound, wherein a hydrogen bond is formed between H bonded to a nitrogen atom of the diamine compound and O of the water molecule, and a nitrogen atom of another diamine compound Hydrogen bonds can be formed between H and H of water molecules. In addition, the arrangement of the diamine compound and the water molecule may be periodically repeated to form a crystal structure.

At this time, the number of carbon atoms of the R ₁ alkyl group connecting the nitrogen atom in the diamine compound maintains an appropriate distance between the nitrogen atoms to form a hydrogen bond between H bonded to the nitrogen atom and O of the water molecule, and the diamine compound and water It would suffice if the molecular arrangement could be repeated periodically to form a crystal structure.

In addition, it will be sufficient if the number of carbon atoms of the R ₂ , R ₃ alkyl group located at the terminal of the diamine compound causes an appropriate steric hindrance so that the water molecule is stably positioned between the diamine compound molecules.

For example, when the number of carbon atoms in the R ₂ , R ₃ alkyl group is too small, the steric hindrance caused is small, and it is difficult for the water molecule to be stably located between the diamine compound molecules, which is not preferable in the practice of the present invention. When the number of carbon atoms in the R ₂ , R ₃ alkyl group is too large, the steric hindrance caused is too large, so that a crystal structure in which the diamine compound and water molecules are periodically arranged cannot be achieved.

In this respect, the number of carbon atoms in the R ₁ , R ₂ , R ₃ alkyl group may each independently be 2 to 10, preferably 2 to 8, and more preferably 2 to 5.

For example, the diamine compound is characterized in that it is N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA).

The carbon dioxide absorbent according to an embodiment of the present invention may exist in a solid state at room temperature.

In addition, the carbon dioxide absorbent according to an embodiment of the present invention may react with carbon dioxide at room temperature to form diamine carbonate.

In the case of a conventional liquid carbon dioxide absorbent using an aqueous amine solution, since carbon dioxide is released by boiling water at a high temperature of 100 ^o C or higher, the absorption performance decreases due to evaporation or denaturation of the amine aqueous solution, causing corrosion of the device, and high There is a problem that can be used only in large-scale processes due to high operating costs due to renewable energy. On the other hand, in the case of the solid carbon dioxide absorbent, compared to the liquid carbon dioxide absorbent, renewable energy is low, the risk of evaporation and denaturation is low, and there is an advantage of not causing corrosion of the device. In addition, since the size and shape of the reaction vessel can be selected in a wider range than a liquid carbon dioxide absorbent that requires a liquid reactor type absorbent reaction vessel, it can be applied to various fields.

The carbon dioxide absorbent according to another embodiment of the present invention is characterized in that it forms a crystal structure by forming hydrogen bonds between a diamine compound and a water molecule, and exists as a solid at room temperature.

In this case, the carbon dioxide absorbent is present as a solid at room temperature and has the above advantages of the solid absorbent, and reacts with carbon dioxide and is converted into a more stable diamine carbonate, so that a fast reaction rate can be maintained when absorbing carbon dioxide.

The carbon dioxide absorbent according to an embodiment of the present invention is characterized in that it is a hydrate crystal in which the molar ratio of the diamine compound to the water molecule is 1, and even when the molar ratio of the diamine compound to the water molecule is 0.5 to 2, the diamine hydrate crystal in the solid state is It is characterized by being created.

When the molar ratio of the diamine compound to the water molecule is less than 0.5, a solid diamine hydrate is not dissolved in water and is dispersed, and a solid diamine hydrate can be obtained by filtering. When the molar ratio of the diamine compound to the water molecule exceeds 2, it is not preferable because the hydrate crystal cannot be formed due to insufficient water forming a hydrate crystal by hydrogen bonding with the diamine.

Hereinafter, a carbon dioxide supplying agent according to another embodiment of the present invention will be described.

The carbon dioxide supplying agent may be generated by a reaction of the diamine hydrate and carbon dioxide. In this case, the diamine hydrate may react with a mixed gas including not only pure carbon dioxide but also carbon dioxide and at least one other gas to generate the carbon dioxide supplying agent.

Specifically, the carbon dioxide supplying agent may include a diamine carbonate formed by further reacting carbon dioxide to a diamine hydrate formed by the reaction of a diamine compound represented by the following Formula 1 with water.

At this time, in Formula 1, R ₁ , R ₂ , and R ₃ are each independently a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms.

The diamine carbonate has a crystal structure and is characterized in that it exists as a solid at room temperature.

In addition, the diamine carbonate may be melted during heat treatment and release carbon dioxide at the same time, and may be crystallized into a solid again when cooled to room temperature after the melting is completed. Accordingly, the diamine carbonate may be used as a carbon dioxide supplying agent by using the carbon dioxide emission and recrystallization characteristics.

The diamine compound is characterized in that it is N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA).

2 is a diagram showing a bonding relationship between a diamine compound and a carbonate contained in a carbon dioxide supplying agent according to another embodiment of the present invention.

Referring to FIG. 2, the carbon dioxide supplying agent may include a diamine compound and a carbonate represented by Formula 1, wherein the diamine compound may be protonated and bonded to the carbonate through hydrogen bonding.

In addition, the protonated diamine compound and carbonate may be aligned by hydrogen bonds to form a crystal structure, and the carbon dioxide supplying agent may exist in a solid state at room temperature.

At this time, the number of carbon atoms of the R ₁ alkyl group connecting the nitrogen atom in the diamine compound maintains an appropriate distance between nitrogen atoms to form a hydrogen bond between H bonded to the protonated nitrogen atom in the diamine compound and O of the carbonate, and the It would be sufficient if the arrangement of the protonated diamine compound and carbonate can be repeated periodically to form a crystal structure.

In addition, it would be sufficient if the number of carbon atoms of the R ₂ , R ₃ alkyl group located at the terminal of the diamine compound causes an appropriate steric hindrance so that the carbonate is stably positioned between the protonated diamine compound molecules.

For example, when the number of carbon atoms in the R ₂ , R ₃ alkyl group is too small, the resulting steric hindrance is small, and the carbonate is not stably located between the protonated diamine compound molecules, which is not preferable in the practice of the present invention. When the number of carbon atoms in the R ₂ R ₃ alkyl group is too large, the resulting steric hindrance is too large to form a crystal structure in which the protonated diamine compound and the carbonate are periodically arranged.

In this respect, the number of carbon atoms in the R ₁ , R ₂ , R ₃ alkyl group may each independently be 2 to 10, preferably 2 to 8, and more preferably 2 to 5.

The carbon dioxide supplying agent may dissolve and release carbon dioxide at the same time during heat treatment, and thus may serve as a carbon dioxide supplying agent.

In addition, the carbon dioxide supplying agent is characterized in that it is crystallized into a solid again at room temperature after fusion is terminated by heat treatment.

Figure 3 (A) is a diagram showing the reaction of the primary and secondary amine compounds and carbon dioxide and its products.

Referring to FIG. 3 (A), in the case of the primary and secondary amine compounds, it is possible to produce all of the carbamate salt, carbonate and hydrogen carbonate by reacting with carbon dioxide.

At this time, carbamate salts are stable compared to carbonates and hydrogen carbonates and are difficult to decompose, and they decompose at a high temperature of 100°C or higher to release carbon dioxide.

3(B) is a diagram showing a reaction of a tertiary amine compound or an amine compound having a relatively large hindered effect with carbon dioxide and a product thereof.

Referring to FIG. 3 (B), in the case of a tertiary amine compound or an amine compound having a relatively large steric hindrance, it may react with carbon dioxide and exist in the form of carbonate and hydrogen carbonate.

At this time, the carbonate and hydrogen carbonate are more unstable than the carbamate salt and are easily decomposed, and thus, they may be decomposed at a lower temperature than the carbamate salt to release carbon dioxide.

The carbon dioxide supplying agent according to another embodiment of the present invention may release carbon dioxide at the same time as melting during heat treatment, and the melting is terminated at a temperature in the range of 60 °C to 90 °C.

Specifically, the carbon dioxide supplying agent introduces an alkyl group having a relatively large steric hindrance to the nitrogen atom in the diamine compound represented by Formula 1, so that when reacted with carbon dioxide, carbonates and hydrogen carbonates can be generated as shown in FIG. have. Accordingly, the carbonate and hydrogen carbonate produced in this way may be decomposed at a lower temperature than the carbamate salt formed from the primary and secondary amine compounds of FIG. 3A to release carbon dioxide.

Hereinafter, a fire extinguisher system according to another embodiment of the present invention will be described.

A fire extinguisher system according to another embodiment of the present invention is characterized in that it includes a carbon dioxide supply agent according to another embodiment of the present invention.

Specifically, the carbon dioxide supplying agent releases carbon dioxide at the same time as it melts during heat treatment, and the melting is terminated at a temperature in the range of 60 °C to 90 °C, which is lower than that of the carbon dioxide supplying agent based on primary and secondary amine compounds to completely release carbon dioxide Therefore, when the carbon dioxide supplying agent is applied to a fire extinguisher system, it has the advantage of being able to react quickly to temperature changes. Specifically, it can be applied to a powder fire extinguisher, a portable fire extinguisher, a ceiling fire extinguisher system, an automatic diffusion fire extinguisher system, and the like.

Hereinafter, the present invention will be described in more detail through Preparation Examples and Experimental Examples. However, the present invention is not limited to Preparation Examples and Experimental Examples.

<Preparation Example 1: Preparation of a solid crystalline diamine hydrate and a carbon dioxide absorbent using the same through reaction of a diamine compound and water>

In a flask under nitrogen conditions, N,N'-di-tert-butylethylenediamine (hereinafter referred to as'DBEDA') and water were reacted to produce a solid mixture. At this time, the mixture was mixed so that the molar ratio of DBEDA and water was 1:1. The resulting solid mixture was dissolved and recrystallized at room temperature to prepare DBEDA hydrate. The DBEDA hydrate was ground to prepare a carbon dioxide absorbent in powder form.

4 is a photograph of a carbon dioxide absorbent in powder form prepared according to Preparation Example 1 above.

<Experimental Example 1: Confirmation of the crystal structure of solid crystalline diamine hydrate before/after absorption of carbon dioxide>

An experiment was conducted to confirm the presence or absence of changes in the crystal structure of the solid crystalline diamine hydrate before/after absorption of carbon dioxide. To this end, DBEDA carbonate was prepared by reacting carbon dioxide with DBEDA hydrate prepared according to Preparation Example 1. Thereafter, the crystal structures of the DBEDA hydrate and the DBEDA carbonate were compared through X-ray diffraction analysis (XRD).

5 (A) and (B) are graphs measuring the crystal structure of DBEDA hydrate before and after absorption of carbon dioxide, respectively.

Referring to Figures 5 (A) and (B), it can be determined that both before and after absorption of DBEDA hydrate forms a monoclinic crystal structure.

In addition, as a result of analyzing the peaks of FIGS. 5A and 5B, it can be seen that the crystal volume increased after absorption of carbon dioxide compared to before absorption of carbon dioxide of DBEDA hydrate.

<Experimental Example 2: Confirmation of crystal structure according to temperature conditions and molar ratio>

An experiment was conducted to determine whether solid crystals were formed by the reaction of the diamine compound and water according to the temperature conditions. DBEDA and water were reacted under the conditions of 30°C, 50°C, and 90°C to generate DBEDA hydrate, and the heat generated at this time was measured. In addition, experiments were conducted by varying the molar ratio of DBEDA and water under each temperature condition.

6 is a graph measuring heat generated when generating DBEDA hydrate according to temperature and molar ratio.

Referring to FIG. 6, it can be seen that the heat generated increases as the molar ratio of water to DBEDA increases under the condition of 30° C. and does not increase any more after the molar ratio of about 1:1. Through this, it can be seen that a solid crystal having a molar ratio of DBEDA:water of about 1:1 is formed.

On the other hand, under the conditions of 50°C and 90°C, the heat generated during the formation of DBEDA hydrate was not measured, and this is because the crystal structure cannot be formed due to a temperature condition higher than the melting point of DBEDA hydrate (47.6°C). Is grasped.

<Experimental Example 3: Confirmation of carbon dioxide absorption capacity of solid crystalline diamine hydrate>

An experiment was conducted to confirm the carbon dioxide absorption capacity of the solid crystalline diamine hydrate. To this end, the mass composition ratio according to the temperature of the DBEDA hydrate according to Preparation Example 1 and the DBEDA carbonate produced by reacting carbon dioxide therewith was measured and shown in FIG. 7.

Referring to FIG. 7, it can be seen that in the case of DBEDA carbonate, the mass composition ratio rapidly decreases in the range of 60 °C to 90 °C during heat treatment. From this, it can be seen that melting ends in the range of 60°C to 90°C and all carbon dioxide is released.

In addition, it can be seen that the mass composition ratio of carbon dioxide emitted due to melting is about 20 wt% of DBEDA carbonate, and from this, it can be seen that the molar ratio of DBEDA: water: carbon dioxide in DBEDA carbonate is 1:1.

<Experimental Example 4: Identification of solid crystalline diamine carbonate produced by reaction of solid crystalline diamine hydrate and water>

An experiment was conducted to produce a solid crystalline diamine carbonate due to the reaction of the solid crystalline diamine hydrate and water. To this end, DBEDA carbonate was produced by reacting DBEDA hydrate prepared according to Preparation Example 1 with carbon dioxide, and the DBEDA carbonate was measured by FT-IR spectroscopy, and the results are shown in FIG. 8.

Referring to Figure 8, the FT-IR peak DBEDA carbonate is CO ₃ ^- to confirm that occurs in the vicinity of 1648 cm ^-1 indicating the C = O bond 1390 cm ^-1, indicating ^- 1375 cm ^-1, HCO ₃ represents the Through this, it can be seen that the DBEDA hydrate reacts with carbon dioxide to form carbonate.

<Experimental Example 5: Confirmation of carbon dioxide emission by heat treatment of solid crystalline diamine carbonate>

An experiment was conducted to confirm the release of carbon dioxide due to melting during heat treatment in the solid crystalline diamine carbonate. To this end, DBEDA carbonate was prepared by reacting carbon dioxide with DBEDA hydrate according to Preparation Example 1. Thereafter, the change occurring during the heat treatment of the DBEDA carbonate was measured by differential scanning calorimetry (DSC), and the results are shown in FIG. 9.

Referring to FIG. 9, it can be seen that peaks occur around 60 °C and around 90 °C. Specifically, it can be seen that the DBEDA carbonate at the peak near 60 °C melts due to heat treatment and loses its crystal structure, and it can be seen that the melting ends by releasing all carbon dioxide at the peak near 90 °C. Considering that the temperature of the peak measured during the differential scanning calorimeter analysis is measured higher than the actual temperature, it can be determined that the DBEDA carbonate begins to melt at a temperature of 60 °C or less and ends at 60 °C to 90 °C. have. In addition, the result of FIG. 9 is a test result for a sealed sample cell, and as a result of confirming using an unsealed cell, carbon dioxide was released at the same time as it was melted, and the result was all released at a temperature of 90 °C or less.

<Experimental Example 6: Confirmation of carbon dioxide absorption rate of solid crystalline diamine hydrate>

An experiment was conducted to confirm the carbon dioxide absorption rate of the solid crystalline diamine hydrate. To this end, carbon dioxide was reacted with the DBEDA hydrate according to Preparation Example 1 under a temperature condition of 30 °C to measure the amount of carbon dioxide absorbed over time.

10 is a graph showing the absorption of carbon dioxide over time of DBEDA hydrate.

Referring to FIG. 10, it can be seen that about 50% of the maximum absorption capacity of DBEDA hydrate is absorbed within about 10 minutes after the start of the reaction of DBEDA hydrate and carbon dioxide. In addition, it can be seen that about 90% of the maximum absorption capacity of carbon dioxide is absorbed within 1 hour after the start of the reaction.

<Experimental Example 7: Confirmation of the temperature range of carbon dioxide emission of solid crystalline diamine carbonate>

An experiment was conducted to confirm the carbon dioxide emission temperature range of the solid crystalline diamine carbonate. To this end, DBEDA carbonate was produced by reacting carbon dioxide with the DBEDA hydrate according to Preparation Example 1. Subsequently, heat treatment was performed on DBEDA carbonate to measure the number of moles of carbon dioxide compared to DBEDA according to temperature, and shown in FIG. 11.

Referring to FIG. 11, it can be seen that the concentration of carbon dioxide begins to rapidly decrease at a temperature between 50° C. and 60° C., and carbon dioxide is completely released at about 80° C.

<Experimental Example 8: Measurement of carbon dioxide absorption rate of solid crystalline diamine hydrate according to partial pressure of carbon dioxide>

An experiment was conducted to measure the carbon dioxide absorption rate of the solid crystalline diamine hydrate according to the partial pressure of carbon dioxide. To this end, the DBEDA hydrate according to Preparation Example 1 was reacted with a mixed gas consisting of 15 vol% of carbon dioxide and 85 vol% of nitrogen in a high-pressure reactor, and the results are shown in FIG. 12.

Referring to FIG. 12, it can be seen that the amount of carbon dioxide absorbed by DBEDA hydrate from the mixed gas reaches 0.9 mole or more for 1 mole of DBEDA under the condition of partial pressure of carbon dioxide of 1 atm or more. In addition, it can be seen that the carbon dioxide absorption efficiency of DBEDA hydrate maintains a value of around 1 even under a high partial pressure of carbon dioxide of 2 atm or more.

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (9)

It contains a diamine hydrate containing a diamine compound and a water molecule represented by the following formula (1),
The diamine hydrate is characterized in that the diamine compound and the water molecule are bonded to each other by hydrogen bonds to form a crystal structure and are solid at room temperature,
The diamine hydrate is a carbon dioxide absorbent, characterized in that the arrangement of the diamine compound and the water molecule is periodically repeated to form a crystal structure:

In Formula 1,
R ₁ , R ₂ , and R ₃ are each independently a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. The method of claim 1,
The diamine compound is a carbon dioxide absorbent, characterized in that N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA). The method of claim 1,
The carbon dioxide absorbent, characterized in that by reacting with carbon dioxide at room temperature to form a diamine carbonate. It is characterized in that it comprises a diamine carbonate formed by further reacting carbon dioxide to a diamine hydrate formed by the reaction of a diamine compound represented by the following Formula 1 with water,
The diamine hydrate is characterized in that the arrangement of the diamine compound and the water molecule is periodically repeated to form a crystal structure,
The diamine carbonate is a carbon dioxide supplying agent, characterized in that it forms a crystal structure and is solid at room temperature:

In Formula 1,
R ₁ , R ₂ , and R ₃ are each independently a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms. delete The method of claim 4,
The diamine compound is a carbon dioxide supplying agent, characterized in that N,N'-di-tert-butylethylenediamine (N,N'-Di-tert-butylethylenediamine, DBEDA). The method of claim 4,
The carbon dioxide supplying agent, characterized in that the carbon dioxide supplying agent emits carbon dioxide at the same time as it melts during heat treatment, and crystallizes again at room temperature after the melting is completed. The method of claim 4,
The carbon dioxide supplying agent, characterized in that the melting is terminated at 60 °C to 90 °C during heat treatment. A fire extinguisher system comprising the carbon dioxide supplying agent of claim 4.

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