KR20160044708A - Material for adsorbing and storaging carbon dioxide and method for adsorbing and storaging carbon dioxide using the same - Google Patents

Abstract

Provided are a material for collecting and storing carbon dioxide, and a method for collecting and storing carbon dioxide using the same. The material for collecting and storing carbon dioxide comprises porphyrin minimally including chemical formula 1, or a derivative thereof. In addition, the material for collecting and storing carbon dioxide easily separates carbon dioxide stored at normal pressure and room temperature.

Description

TECHNICAL FIELD The present invention relates to a carbon dioxide capture and storage material, and a carbon dioxide capture and storage method using the carbon dioxide capture and storage material. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a carbon dioxide capture and storage material, and a carbon dioxide capture and storage method using the carbon dioxide capture and storage material.

Global warming is becoming a global issue, and as the Kyoto Protocol has begun to reduce greenhouse gas emissions, it is necessary to develop a carbon dioxide storage material that can capture and store carbon dioxide. As a conventional carbon dioxide capture and storage material, a wet substance including a dry substance such as zeolite, a monoethanolamine or calcium carbonate aqueous solution, and the like can be used. However, there is a problem that dry CO2 capture and storage materials have a low carbon dioxide storage capacity and low selectivity to carbon dioxide. Wet carbon dioxide capture and storage materials have a problem of high selectivity for carbon dioxide but high corrosiveness and unstable at high temperature . In addition, both dry and wet carbon dioxide capture and storage materials can store carbon dioxide at high temperatures and pressures, so that conditions such as high temperatures and high pressures must be met when capturing and storing carbon dioxide, and certain conditions must be met when separating captured carbon dioxide . The background art of the present invention is disclosed in Korean Patent No. 10-1351114.

A problem to be solved by the present invention is to provide a carbon dioxide capture and storage material having excellent capture and storage capacity of carbon dioxide at normal pressure and room temperature.

Another problem to be solved by the present invention is to provide a carbon dioxide capture and storage material which is easy to separate stored carbon dioxide at normal pressure and at room temperature.

The carbon dioxide capture and storage material of the present invention may comprise a complex of a metal ion with a porphyrin or a derivative thereof represented by at least the following formula 1:

≪ Formula 1 >

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _11, R _{12 and} M in the general formula Lt; / RTI >

The carbon dioxide capture and storage method of the present invention may include using the carbon dioxide capture and storage material.

The present invention provides a carbon dioxide capture and storage material having excellent capture and storage capacity of carbon dioxide at normal pressure and room temperature. The present invention provides a carbon dioxide capture and storage material that facilitates the separation of stored carbon dioxide at normal pressure and room temperature.

FIG. 1 shows the capacity and occupation number of the complex according to the trapping temperature in the capture of carbon dioxide in the complex of porphyrin and scandium ion.
Fig. 2 shows the trapping capacity and occupancy of the complex according to the trapping temperature at the time of trapping the carbon dioxide of the complex of porphyrin and titanium ion
3 shows the trapping capacity and occupancy of the complex according to the trapping temperature in capturing carbon dioxide in a complex of porphyrin and vanadium ions.
4 is a schematic diagram of carbon dioxide capture of a carbon dioxide capture and storage material according to an embodiment of the present invention.
5 is another schematic diagram of carbon dioxide capture of carbon dioxide capture and storage materials in one embodiment of the present invention.
6 is another schematic diagram of carbon dioxide capture of carbon dioxide capture and storage materials of one embodiment of the present invention.

The carbon dioxide capture and storage material of the present invention may comprise a complex of a metal ion with a porphyrin or derivative thereof,

≪ Formula 1 >

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _{11 and} R ₁₂ each independently represent hydrogen, unsubstituted An alkyl group having 1 to 10 carbon atoms, an unsubstituted alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a carboxylic acid group (COOH), and M is a metal ion.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _{11 and} R ₁₂ each independently represent hydrogen, a methyl group, a vinyl group, Lt; / RTI > group.

In the carbon dioxide capture and storage material of the present invention, the metal ion (M) is a direct site to which carbon dioxide is bonded. Since the volume of carbon dioxide relative to other gases such as hydrogen or nitrogen is large, . Specifically, the metal ion may have a binding energy to carbon dioxide of from 0.6 eV to 0.8 eV, and the metal ion M may be a mono to trivalent metal ion, for example, a calcium ion (Ca ²⁺ ) , scandium ion (Sc ^+), titanium ions (Ti ^+), vanadium ions (V ^+), cobalt ion (Co ^2+), chromium ion (Cr ^2+), manganese ion (Mn ^2+), iron ions (Fe ^2+), nickel ion (Ni ²⁺⁾ and the like can be and, in particular calcium ions (Ca ^2+), ion scandium (Sc ^+), titanium ions (Ti ^+), vanadium ions (V ^+), manganese ion ( Mn ²⁺ ) is much higher in binding energy to carbon dioxide than nitrogen, methane gas, and hydrogen, so that the capture and storage capacity of carbon dioxide can show selectivity even in gas mixtures containing carbon dioxide.

The carbon dioxide capture and storage material of the present invention comprises porphyrin or a derivative thereof, wherein the metal ion is bonded to nitrogen bonded to carbon constituting porphyrin or a derivative thereof, The carbon dioxide capture and storage capacity is excellent even at normal pressure and / or room temperature. Specifically, the carbon dioxide capture and storage material of the present invention can have a binding energy for carbon dioxide of 0.6 eV to 0.8 eV, and the carbon dioxide capture and storage capacity in the above range can be excellent.

In addition, the carbon dioxide capture and storage material of the present invention may be excellent in carbon dioxide capture and storage effect at atmospheric pressure and / or room temperature in carbon dioxide capture and storage. The normal temperature may be 300K to 400K, and the normal pressure may be 1 to 5 bar. Specifically, the carbon dioxide capture and storage material of the present invention has a carbon dioxide capture capacity of at least 3 mmol / g at room temperature and / or atmospheric pressure, and this value is superior to currently used carbon dioxide capture materials.

FIG. 1 shows the capturing capacity and occupation number of the complex according to the trapping temperature in capturing carbon dioxide of a complex of porphyrin and scandium ion (Sc +). Fig. 2 shows the trapping capacity and occupancy of the complex according to the trapping temperature in capturing carbon dioxide in a complex of porphyrin and titanium ion (Ti +). Fig. 3 shows the trapping capacity and occupancy of the complex according to the trapping temperature in capturing carbon dioxide in the complex of porphyrin and vanadium ion (V +).

In this specification "porphyrin" is R _1, R _2, in Formula _{1 R 3, R 4, R} 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12 are both hydrogen ≪ / RTI > 1 to 3, it can be seen that carbon dioxide can be adsorbed to porphyrin or its derivative even at room temperature. Figures 1 and 3 show that the calculated binding energy was calculated by Gibbs Free Energy. At 200 K, it was confirmed that there were two carbon dioxide and one carbon dioxide at room temperature.

In addition, the conventional wet absorbent such as calcium carbonate, which has been used as a carbon dioxide capture and storage material, chemically reacts with carbon dioxide to collect carbon dioxide, while the carbon dioxide capture and storage material of the present invention is a Dewar-Chatt-Duncanson By interacting with each other, metal ions and carbon dioxide can be reversibly combined to lower the temperature to room temperature or lower the pressure to atmospheric pressure, thereby facilitating the separation of carbon dioxide.

In particular, unlike heterogeneous gases such as hydrogen, carbon dioxide reacts with water and / or water vapor to form carbonic acid (CO ₂ + H ₂ O → H ₂ CO ₃ ), which may not be easily captured and stored. The carbon dioxide capture and storage materials of the present invention can adsorb to metal ions without the above-mentioned problems, and thus can capture and store carbon dioxide with high capacity.

The carbon dioxide capture and storage material of the present invention can capture more than one carbon dioxide and can capture various aspects, and the carbon dioxide can be captured on one side of the carbon dioxide capture and storage material and on the other side opposite thereto.

FIG. 4 is a schematic view showing a state in which carbon dioxide is captured in a carbon dioxide capture and storage material according to an embodiment of the present invention, in which carbon dioxide is trapped in a complex of porphyrin and scandium ions. FIG.

Referring to FIG. 4, carbon dioxide is bonded to a complex of porphyrin and scandium ions in a chair type. In this case, a "chair type" is formed by combining scandium ions and one carbon of carbon dioxide and one oxygen to form scandium ions and carbon dioxide Chairs and so on.

Referring to FIG. 4, carbon dioxide is linearly bonded to a complex of porphyrin and scandium ion. In this case, " linear " means that one carbon of scandium ion and carbon dioxide is combined to form a linear combination of scandium ion and carbon dioxide .

Referring to FIG. 4, carbon dioxide is coupled to a complex of porphyrin and scandium ion in a roof type. In this case, " roof type " means that two carbon atoms of scandium ion and carbon dioxide and one oxygen are combined with scandium ions, This means that carbon dioxide is combined in the form of a roof.

The carbon dioxide capture and storage material of one embodiment of the present invention may capture two or more, preferably two to three, carbon dioxide per metal ion. FIG. 5 is a schematic view of capturing two carbon dioxide in a carbon dioxide capture and storage material according to an embodiment of the present invention, and FIG. 6 is a captured schematic diagram of carbon dioxide capture and storage materials of an embodiment of the present invention combined with three carbon dioxide.

In the carbon dioxide capture and storage material of the present invention, nitrogen is bonded to the carbon constituting the metal ion and the porphyrin to capture carbon dioxide and maintain the mechanical properties. In the carbon dioxide capture and storage material of the present invention, porphyrin is a substance that is linked to carbon and nitrogen as commonly known, and supports the binding of nitrogen and metal ions. Therefore, porphyrin is excellent in physical stability and chemical stability. It is possible to increase the easiness, and as a stable material which does not easily decompose, there may be no problems such as corrosion problem and cracking.

In the carbon dioxide capture and storage material of the present invention, when the carbon dioxide capture and storage material collects carbon dioxide, the distance between the metal ion and the carbon dioxide can be approximately 2 A to 2.5 A, and the carbon dioxide capture and storage capacity .

The carbon dioxide capture and storage material of the present invention may have excellent capture and storage capacity of carbon dioxide within the above range.

In addition, in the carbon dioxide capture and storage material of the present invention, the metal ion is a carbon dioxide capture and storage site, but when contained in an excessive amount of porphyrin, the stability may be deteriorated and the carbon dioxide storage capacity may be lowered. do. Specifically, the metal ion may be contained in the carbon dioxide capture and storage material in an amount of 1 mmol / g to 5 mmol / g, and the capture and storage capacity of carbon dioxide in the above range may be excellent.

The carbon dioxide capture and storage material of the present invention may be formed as a single layer as a planar structure in which metal ions are bonded to porphyrin.

The carbon dioxide capture and storage material of the present invention can be prepared by a method of complex binding of porphyrin and a metal ion. Specifically, it can be produced by binding a compound providing a metal ion with porphyrin under predetermined conditions, and binding the porphyrin or a derivative thereof to the metal ion. Specifically, a compound which provides a metal ion and porphyrin or a derivative thereof can be prepared by reacting a pyrrole with an aldehyde. The porphyrin derivatives may be prepared by chemical methods, but are not limited thereto.

The carbon dioxide capture and storage material of the present invention may comprise using the carbon dioxide capture and storage material of the present invention. In particular, the carbon dioxide capture and storage material of the present invention may comprise contacting the carbon dioxide capture and storage material with a gas mixture comprising carbon dioxide.

The gas mixture may include carbon dioxide alone, or conventional gas known as carbon dioxide. As described below, the carbon dioxide capture and storage material of the present invention has remarkably high binding energy to carbon dioxide compared to a heterogeneous gas, Can be selectively collected and stored. The carbon dioxide capture and storage material and the gas mixture may be contacted at room temperature, for example, at 25 to 100 ° C and / or atmospheric pressure, for example, 0.1 to 1 atmosphere, and under the above conditions, the carbon dioxide capture and storage material of the present invention, Can be collected and stored.

The captured carbon dioxide can be recovered from the carbon dioxide capture and storage material by treating the predetermined conditions, for example, by treating at 25 to 100 ° C and / or 0.1 to 1 atmosphere, the carbon dioxide can be recovered.

The method of the present invention may further comprise recycling the carbon dioxide capture and storage material after carbon dioxide recovery. The carbon dioxide capture and storage materials are excellent in physical stability and / or chemical stability as described above and can be easily recovered.

In order to confirm that the carbon dioxide capture and storage material of the present invention is excellent in the carbon dioxide storage capacity even at room temperature and / or atmospheric pressure by using the principle principle density function computation, it is preferable that the metal ion M in the chemical formula 1 is calcium ion, scandium ion, Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _{11 and} R ₁₂ are each hydrogen The structure was modeled, and the binding energy for carbon dioxide and the binding between metal ions and carbon dioxide were calculated at room temperature and / or atmospheric pressure using the computation of the density function function. The results are shown in Table 1 below.

Metal ion type Number of carbon dioxide captured Combined energy (eV) Distance between metal ions and carbon dioxide (Å) Ca ²⁺ Chair type One 0.34 2.57 Ca ²⁺ Linear One 0.34 2.56 Ca ²⁺ Roof type One 0.34 2.56 Sc ⁺ Chair type One 0.69 2.11 Sc ⁺ Linear One 0.49 2.27 Sc ⁺ Roof type One 0.54 2.23 Sc ⁺ Chair type 2 0.53 3.42 Sc ⁺ Linear 2 0.30 2.47 Sc ⁺ Roof type 2 0.21 2.20 Sc ⁺ - Three 0.10, 0.63 - Ti ⁺ Chair type One 1.31 1.97 Ti ⁺ Linear One 0.40 2.17 Ti ⁺ Roof type One 0.45 1.99 Ti ⁺ Chair type 2 0.93 1.95 Ti ⁺ Linear 2 0.05 4.11 Ti ⁺ Roof type 2 0.40 4.11 Ti ⁺ - Three 0.18, 0.53 - V ⁺ Chair type One 0.29 1.96 V ⁺ Linear One 0.21 2.12 V ⁺ Roof type One -0.91 2.14 V ⁺ Chair type 2 0.29 1.96 V ⁺ Linear 2 0.02 3.7 V ⁺ Roof type 2 0.31 1.96 V ⁺ - Three 0.06 Mn ²⁺ Chair type One 0.02 2.99 Mn ²⁺ Linear One 0.02 3.00 Mn ²⁺ Roof type One 0.01 3.74

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

CLAIMS 1. A carbon dioxide capture and storage material,
≪ Formula 1 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen, unsubstituted An alkyl group having 1 to 10 carbon atoms, an unsubstituted alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a carboxylic acid group (COOH)
M is a metal ion). The method of claim 1, wherein the metal ion is a calcium ion (Ca ^2+), ion scandium (Sc ^+), titanium ions (Ti ^+), vanadium ions (V ^+), cobalt ion (Co ^2+), chromium ion ( Carbon dioxide capture and storage material, wherein the carbon dioxide is Cr ²⁺ , Mn ²⁺ , Fe ²⁺ , or Ni ²⁺ . The carbon dioxide capture and storage material of claim 1, wherein the carbon dioxide capture and storage material has a binding energy for carbon dioxide between 0.6 eV and 0.8 eV. The carbon dioxide capture and storage material of claim 1, wherein the metal ion is comprised between 1 mmol / g and 5 mmol / g of the carbon dioxide capture and storage material. A method of collecting and storing carbon dioxide, comprising using the carbon dioxide capture and storage material of any one of claims 1 to 4.

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