KR102389822B1 - Organic-Inorganic Hybrid nanoporous materials and applications thereof - Google Patents

Abstract

According to an embodiment of the present invention, a central metal ion provided in a crystal lattice having a tetragonal structure; and a ligand linker connecting the crystal lattice containing the central metal ion to the adjacent crystal lattice in a plane, wherein the crystal lattice and the ligand linker are connected in a form including pores on the plane, and within the pores An organic-inorganic hybrid that adsorbs molecules, a plurality of the crystal lattices are connected in a direction penetrating the plane, and the plurality of crystal lattices connected in a direction penetrating the plane are connected in a cis-helix structure A nanoporous body is provided.

Description

Organic-inorganic hybrid nanoporous body and its application {Organic-Inorganic Hybrid nanoporous materials and applications thereof}

The present invention relates to an organic-inorganic hybrid nanoporous body, and the organic-inorganic hybrid nanoporous body according to the present invention has excellent usability and can be used as a moisture adsorbent, an adsorbent for gas separation or storage, and the like.

Organic-inorganic hybrid nanoporous bodies are generally referred to as "porous coordination polymers", or "metal-organic frameworks". Organic-inorganic hybrid nanoporous bodies have recently begun to develop anew by combining molecular coordination and materials science.

The organic-inorganic hybrid nanoporous body has a high surface area and molecular or nano-sized pores, so it is used for adsorbents, gas storage materials, sensors, membranes, functional thin films, drug delivery materials, catalysts and catalyst carriers, etc. Recently, it has been actively studied because it can be used to trap guest molecules or to separate molecules according to their size using pores. In particular, since the organic-inorganic hybrid nanoporous body contains a polar metal ion and a carboxylate oxygen anion in the crystalline backbone, and a non-polar aromatic compound group coexists, it can have both hydrophilicity and hydrophobicity.

One of the application fields of the organic-inorganic hybrid nanoporous body is a cooling and heating device using moisture adsorption and moisture adsorption. For example, heat energy generated or absorbed during moisture adsorption/desorption of an adsorbent installed in an enclosed system can be used as an adsorbent in a moisture adsorption type heat pump used for heating and cooling industrial, medium-large buildings, and households. In addition, if an adsorbent is used in a heating and cooling system, it can absorb moisture from outside at a low temperature during heating and then flow into the room and desorb from the inside of a high temperature room to act as a humidifier. Therefore, it can be detached from the outdoors at a high temperature and sent outdoors, so that a pleasant indoor atmosphere can be obtained.

Another application example of the organic-inorganic hybrid nanoporous body is an adsorbent for separating organic compounds in an oil refining process. Currently, in the oil refining and petrochemical industries, olefin molecules with 2 to 4 carbon atoms such as ethylene, propylene, and butylene are used to produce synthetic resins such as polyethylene, polypropylene, and polybutene, and chemical products such as ethylbenzene, ethylene glycol, and propylene glycol. It is known as one of the most important raw materials in the petrochemical industry as the compound with the highest production volume. In particular, ethylene and propylene monomers are produced annually in the petrochemical and gas chemical industries at an annual scale of 200 million tons, and they are recognized as one of the most important chemical products supporting the modern industrial society. These olefin compounds are produced by various raw materials and processes such as pyrolysis and catalytic cracking of naphtha, ethane cracking, propane dehydrogenation, ethane/propane cracking and dehydrogenation of shale gas, olefin conversion of methanol, and fluidized bed catalytic cracking of heavy oil. is becoming However, in order to be used as a raw material for a synthetic polymer resin, ethylene, propylene, and butylene monomers having a purity of 99.5% or more must be prepared. The currently used olefin separation and purification process is the separation of hydrocarbons by carbon number and olefin/paraffin separation of the same carbon number, and is performed by a multi-step distillation method using the difference in boiling point of each hydrocarbon. The problem with the separation and purification process in the current ethylene and propylene production process is that the boiling points of the ethylene/ethane and propylene/propane molecules to be separated are very similar. am.

As described above, the organic-inorganic hybrid nanoporous body has various application fields. An object of the present invention is to provide an organic-inorganic hybrid nanoporous body having excellent performance that can be applied to the various technical fields described above.

de Lange MF, Verouden KJ, Vlugt TJ, Gascon J, Kapteijn F. Adsorption-Driven Heat Pumps: The Potential of Metal-Organic Frameworks. Chem Rev 115, 12205-12250 (2015)

An object of the present invention is to provide an organic-inorganic hybrid nanoporous body having excellent utility.

In addition, according to the present invention, there is provided an organic-inorganic hybrid nanoporous body that can be used as a moisture adsorbent. Organic/inorganic hybrid nanoporous materials that can be used as moisture adsorbents include air conditioning and dehumidification devices, dehumidifying devices, thermal batteries, and water harvesting devices that produce water by condensing water vapor in the air. It can be used as a seawater desalination device (desalination), etc., and exhibits excellent efficiency.

In addition, according to the present invention, there is provided an organic-inorganic hybrid nanoporous body that can be used as a gaseous compound adsorbent. A gas processing apparatus including a gaseous compound adsorbent may be an apparatus for performing separation and storage of a gaseous compound. For example, it may be a device capable of separating olefin/paraffin mixture, natural gas separation, carbon dioxide capture, ammonia capture, sulfur oxide capture, nitrogen oxide capture, VOC capture, and CWA capture.

According to an embodiment of the present invention, a central metal ion provided in a crystal lattice having a tetragonal structure; and a ligand linker connecting the crystal lattice containing the central metal ion to the adjacent crystal lattice in a plane, wherein the crystal lattice and the ligand linker are connected in a form including pores on the plane, and within the pores An organic-inorganic hybrid that adsorbs molecules, a plurality of the crystal lattices are connected in a direction penetrating the plane, and the plurality of crystal lattices connected in a direction penetrating the plane are connected in a cis-helix structure A nanoporous body is provided.

According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous body includes one or more kinds of the ligand linkers, and the different kinds of the ligand linkers are adjacent to the crystal lattice including the central metal ion. and an organic-inorganic hybrid nanoporous body provided in the form of forming pores on the plane by connecting on the plane.

According to an embodiment of the present invention, the ligand linker is 2,5-furanedicarboxylic acid (2,5-Furanedicarboxylic acid), 2,5-thiophenedicarboxylic acid (2,5-thiophenedicarboxylic acid), 2, 5-pyrrole dicarboxylic acid (2,5-pyrrole dicarboxylic acid), isophthalic acid (isophthalic acid), a material derived from 3,5-pyridine dicarboxylic acid (3,5-Pyridinedicarboxylic acid), organic-inorganic hybrid A nanoporous body is provided.

According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous body has a structure of the following formula (1),

[Formula 1-1]

Al(OH) _2-xy (PyDC) _x (L2) _y nH2O

In Formula 1-1, x is a number from 0.1 to 1, PyDC means pyrrole dicarboxylate, L2 means a linker ligand different from PyDC, and satisfies 0<x+y<1, n is a number of 0 to 5, the organic-inorganic hybrid nanoporous body is provided.

According to an embodiment of the present invention, there is provided an organic-inorganic hybrid nanoporous body, wherein the molecules adsorbed into the pores include at least one selected from water and a paraffin compound.

According to an embodiment of the present invention, a central metal ion provided in a crystal lattice having a tetragonal structure; and a ligand linker connecting the crystal lattice containing the central metal ion to the adjacent crystal lattice in a plane, wherein the crystal lattice and the ligand linker are connected in a form including pores on the plane, and within the pores Adsorbing molecules, a plurality of the crystal lattices are connected in a direction penetrating the plane, and the plurality of crystal lattices connected in a direction penetrating the plane are connected in a cis-helix structure, the adsorbent is provided do.

According to an embodiment of the present invention, there is provided a water treatment device comprising a moisture adsorption/desorption unit having an adsorbent.

According to an embodiment of the present invention, there is provided a gas processing apparatus comprising a gas adsorption/desorption unit having an adsorbent, wherein the gas adsorption/desorption unit performs separation and storage of gas compounds.

According to an embodiment of the present invention, the gas compound is at least one gas compound selected from the group consisting of olefin compounds, paraffin compounds, natural gas, carbon dioxide, ammonia, sulfur oxides, nitrogen oxides, VOC, and CWA (Chemical Warfare Agent). Including, separation and storage of the gas compound through the gas adsorption/desorption unit is at least one of separation of olefin/paraffin mixture, natural gas separation, carbon dioxide capture, ammonia capture, sulfur oxide capture, nitrogen oxide capture, VOC capture, and CWA capture A gas processing apparatus comprising one is provided.

According to the present invention, an olefin hybrid nanoporous body having high utility and excellent ability to adsorb moisture or gas compounds can be provided.

1 shows the structure of an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
Figure 2a is an X-ray diffraction analysis pattern showing the structure when the organic-inorganic hybrid nanoporous body is hydrated according to an embodiment of the present invention, Figure 2b is an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention dehydration It is an X-ray diffraction analysis pattern showing the structure when it is formed. Figure 2c is a scanning microscope image of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
3 is a graph showing the nitrogen adsorption isotherm of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
4 is a graph showing the results of thermogravimetric analysis of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
5 is a graph showing the results of X-ray diffraction analysis at elevated temperature of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
6 is a graph showing the hydrothermal stability test result of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
7 is a graph showing the stability test results of the organic-inorganic hybrid nanoporous body in an acid-based aqueous solution according to an embodiment of the present invention.
8 is a graph showing the measurement result of the moisture adsorption isotherm of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
9 is a graph showing the long-term stability evaluation results of moisture adsorption and desorption of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
10 is a graph evaluating the ethane/ethylene adsorption separation performance of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
11 is a cross-sectional view illustrating a heating and cooling device including an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.
12 is a cross-sectional view illustrating an olefin/paraffin separation device including an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

1 shows the structure of an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

The organic-inorganic hybrid nanoporous body according to an embodiment of the present invention includes a central metal ion provided in a crystal lattice; and a ligand linker connecting the crystal lattice including the central metal ion to the adjacent crystal lattice on a plane. In addition, the crystal lattice and the ligand linker are connected in a form including pores on a plane, and molecules may be adsorbed into the pores.

The central metal ion is selected from the group consisting of trivalent such as vanadium (V), chromium (Cr), iron (Fe), aluminum (Al), gallium (Ga), indium (In), and lanthanum-based metals. It may be an ion of one or more metals.

The central metal ion may be provided in the crystal lattice. The crystal lattice may be composed of a central metal ion and oxygen or nitrogen, and may have various shapes. For example, the crystal lattice may have a tetragonal structure. In this case, the crystal lattice may have a form in which the central metal ion aluminum is located at the center of the crystal lattice of the tetragonal structure, and oxygen is located at each vertex of the crystal lattice of the tetragonal structure.

The central metal ion is provided in the form described above to form a bond between the crystal lattice-ligand linker-crystal lattice on a plane or crystal lattice-to-crystal lattice bond in a direction penetrating the plane. Accordingly, the organic-inorganic hybrid nanoporous body is provided in a form including pores, and molecules provided in the pores may be adsorbed by receiving electrostatic attraction by the crystal lattice and the ligand linker. In this case, the adsorbed molecule may include at least one selected from the group consisting of water and paraffin.

The linker ligand binds to a crystal lattice containing a central metal ion, and connects the crystal lattice to an adjacent crystal lattice. The linker ligand may be an organic ligand. For example, the linker ligand may be Pyrroledicarboxylate. The linker ligand including the above-described heteroaryl has polarity inside the ligand, and thus the hydrophilicity and low-temperature regeneration characteristics of the organic-inorganic hybrid nanoporous body including the linker ligand may be improved.

A plurality of linker ligands may be provided between adjacent crystal lattices. For example, two linker ligands may be provided between two adjacent crystal lattices to connect the adjacent crystal lattices. The number of linker ligands may vary depending on the shape of the crystal lattice.

The linker ligand and the crystal lattice form a bonding structure of the crystal lattice-linker ligand-crystal lattice on a plane. Accordingly, when viewed in a plan view, the plurality of crystal lattices and the plurality of linker ligands may be arranged in a form to form pores. For example, a plurality of crystal lattices may form checkered vertices, and a plurality of pores may be provided by providing a linker ligand as a line segment connecting each vertex. However, the above and those shown in the drawings are exemplary arrangements of the linker ligand and the crystal lattice, and the pores may be arranged to have other forms, for example, rhombic, hexagonal, octagonal, and the like. In the above description, a plane may be interpreted in a broad sense including a plane in a mathematical sense and the same layer.

Crystal lattices adjacent to each other in a direction passing through the plane formed by the linker ligand and the crystal lattice may be bonded. In this case, the crystal lattices may be directly coupled to each other. A plurality of crystal lattices connected in a direction penetrating the plane may be connected in a cis-helix structure. Accordingly, the structural stability of the organic-inorganic hybrid nanoporous body may be improved. Accordingly, the structure of the organic-inorganic hybrid nanoporous body may be maintained even under acidic conditions, basic conditions, or high temperature conditions, and the surface area and pore volume may be maintained. Accordingly, even if the process is performed under severe conditions, the function of the organic-inorganic hybrid nanoporous body may not be deteriorated.

The organic-inorganic hybrid nanoporous body described above has a structure of the following formula (1),

[Formula 1]

Al(OH) _2-x (PyDC) _x nH2O

In Formula 1, x may be a number from 0.8 to 1, and n may be a number from 0 to 4.5. The organic-inorganic hybrid nanoporous body having the structure of Formula 1 as described above has very high moisture adsorption rate and selective adsorption rate of paraffin compounds in the olefin/paraffin mixture. In addition, since it is possible to regenerate at a low temperature after adsorption of moisture, it can be used to implement an energy-saving heating and cooling device. In addition, it has excellent hydrothermal stability, acid-base chemical stability, and long-term stability.

One or more linker ligands may be included. For example, in configuring the organic-inorganic hybrid nanoporous body, two or more different types of ligand linkers may be provided. Different types of ligand linkers may be provided in the form of forming pores by linking a crystal lattice including a central metal ion with an adjacent crystal lattice on a plane. Accordingly, the organic-inorganic hybrid nanoporous body may have a M _a (L1) _x (L2) _y shape. In this case, M denotes a central metal ion, and L1 and L2 denote different ligand linkers. In the above formula, a may mean a rational number greater than 0, and x and y may each mean a rational number greater than or equal to 0. However, x and y do not become 0 at the same time.

When one or more linker ligands are included as described above, the organic-inorganic hybrid nanoporous body may have a form as shown in Formula 1-1 below.

[Formula 1-1]

Al(OH) _2-xy (PyDC) _x (L2) _y nH2O

In Formula 1-1, x is a number from 0.1 to 1, PyDC means pyrrole dicarboxylate, L2 means a linker ligand different from PyDC, and satisfies 0<x+y<1, n is a number from 0 to 5.

The linker ligand is 2,5-furanedicarboxylic acid (2,5-Furanedicarboxylic acid), 2,5-thiophenedicarboxylic acid (2,5-thiophenedicarboxylic acid), 2, 5-pyrrole dicarboxylic acid (2,5-pyrrole dicarboxylic acid), isophthalic acid (isophthalic acid), may be selected from 3,5-pyridine dicarboxylic acid (3,5-Pyridinedicarboxylic acid).

When the linker ligand includes two or more different kinds of compounds as described above, the different kinds of linker ligands may be used together in a single process. For example, after preparing the metal precursor, each precursor solution of different types of linker ligands of the metal precursor may be added at once to prepare an organic-inorganic hybrid nanoporous body. As described above, by using two or more types of linker ligands together, advantageous effects exhibited by different linker ligands, for example, adsorption capacity improvement can be obtained.

The organic-inorganic hybrid nanoporous body according to an embodiment of the present invention has a large surface area and a large pore volume, and thus, when used as an adsorbent, the adsorption amount is very excellent. For example, the organic-inorganic hybrid nanoporous body may have a surface area of 1000 m ² /g or more and a pore volume of 0.4 cm ³ /g or more. Since the organic-inorganic hybrid nanoporous body has a large surface area and large pore volume as described above, a large amount of molecules can be adsorbed to the organic-inorganic hybrid nanoporous body. The adsorbed molecule may be, for example, a water molecule (moisture) or a paraffinic compound.

The organic-inorganic hybrid nanoporous body according to an embodiment of the present invention has very excellent adsorption power to water molecules (moisture). Specifically, the organic-inorganic hybrid nanoporous body may be almost saturated with moisture adsorption at P/P ⁰ < 0.20, and in this range, the organic/inorganic hybrid nanoporous body may have a moisture adsorption amount of 0.3 g or more per 1 g of the organic/inorganic hybrid nanoporous body. In addition, the organic-inorganic hybrid nanoporous body to which moisture is adsorbed can desorb the adsorbed moisture at a temperature of about 100° C. or less. This is very good compared to the prior art adsorbents that require a desorption temperature of about 150° C. or higher under the condition of P/P ⁰ < 0.05.

In the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention, the difference between the adsorption amount of the olefin compound having 3 or less carbon atoms and the paraffin compound adsorption amount having 3 or less carbon atoms may be 3.5 mmol/g or more under the liquefaction pressure of the olefin compound. As described above, since the difference in the adsorption amount for the olefin compound and/or paraffin compound having 3 or less carbon atoms is large, the organic/inorganic hybrid nanoporous body may be used for olefin/paraffin separation. In particular, in the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention, the adsorption power to paraffin in the olefin/paraffin mixture is relatively greater than the adsorption power to the olefin.

Adsorbents according to the prior art mostly adsorb more olefins in the olefin/paraffin mixture. However, it is common that the olefin compound is contained more than the paraffin compound in the olefin/paraffin mixture supplied from the feed. Accordingly, when using the adsorbent according to the prior art, a very complex process is required to produce high-purity olefins in a PSA (Pressure Swing Adsorption) process for separating olefins/paraffins. In addition, a large amount of adsorbent is required to prevent loss of olefins during the separation process. In addition, high vacuum pressure reduction is required to desorb the olefin adsorbed to the adsorbent during the olefin recovery process, and thus energy consumption is large. However, when a paraffin-selective adsorbent is used as in the present invention, a low-concentration paraffin compound can be selectively removed from the olefin/paraffin mixture, thereby simplifying the separation process and remarkably reducing the consumption of the adsorbent.

Hereinafter, the structure of the organic-inorganic hybrid nanoporous body will be looked at in more detail through the structure analysis of the organic-inorganic hybrid nanoporous body according to the embodiment.

Figure 2a is an X-ray diffraction analysis pattern showing the structure when the organic-inorganic hybrid nanoporous body is hydrated according to an embodiment of the present invention, Figure 2b is an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention dehydration It is an X-ray diffraction analysis pattern showing the structure when it is formed. Figure 2c is a scanning microscope image of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

Example 1. Preparation of organic-inorganic hybrid nanoporous body

For the synthesis of an Al-based organic-inorganic hybrid nanoporous body having an Al-Pyrroledicarboxylate crystal structure, 16.663 g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O was dissolved in 135 g of distilled water to prepare a metal precursor solution. Thereafter, 5.0 g of caustic soda (NaOH) was dissolved in 135 g of distilled water, and then 7.755 g of 2,5-Pyrroledicarboxylic acid was additionally added to prepare a ligand precursor solution. After putting the metal precursor solution in a round flask, the ligand precursor solution was slowly added to prepare a synthesis solution. Thereafter, a round flask was mounted on an oil bath equipped with a reflux cooling device, the temperature was raised to 120°C, and the reaction was completed after maintaining for 15 hours. After cooling the reaction solution, the Al-Pyrroledicarboxylate organic-inorganic hybrid nanoporous crystals produced in the round flask were washed once with distilled water and ethanol, respectively, and dried at 100°C for 12 hours to obtain a crystal powder.

The yield compared to the input raw material was 93%, and the space-time-yield productivity (STY) was 68kg/m ³ ·day.

Experimental Example 1. Structural Analysis

과 λ=0.9000

이었다. 유무기 하이브리드 나노세공체가 수분으로 포화된 상태와 탈수된 상태 각각의 구조로부터 얻은 X-선 회절패턴을 DICVOL06 및 Fullprof 프로그램을 이용하여 인덱싱하였다. 또한 해당 회절 패턴을 JANA2006 package 및 GSAS 프로그램을 이용하여 Rietveld refinement를 수행하였으며, pseudo-Voigt function, microscopic broadening 및 manual interpolation 방법을 통한 background 보정법을 부수적으로 이용하였다.The crystal structure analysis of various types of Al-based organic-inorganic hybrid nanoporous bodies obtained from the above synthesis method can be easily performed using X-ray diffraction analysis. The organic-inorganic hybrid nanoporous body synthesized in the present invention was analyzed using Synchrotron radiation of the Pohang Accelerator Laboratory. The beamline equipment used for analysis used 9B and 2D beamlines, and the wavelength of the beamline was λ=1.5225, respectively.

and λ=0.9000

it was The X-ray diffraction patterns obtained from the structures of the organic-inorganic hybrid nanoporous body in a saturated and dehydrated state were indexed using DICVOL06 and Fullprof programs. In addition, Rietveld refinement was performed on the diffraction pattern using the JANA2006 package and GSAS program, and the background correction method through the pseudo-Voigt function, microscopic broadening and manual interpolation method was used incidentally.

The structure of the organic-inorganic hybrid nanoporous body obtained in Example 1 was analyzed through X-ray diffraction analysis using Synchrotron beamline, and the crystal structure was identified. As shown in Figs. 2a, 2b, and Table 1, in the case of an X-ray diffraction analysis sample measured at room temperature of the organic-inorganic hybrid nanoporous body, moisture is adsorbed inside the pores of the organic-inorganic hybrid nanoporous body according to the present invention In the case of the organic-inorganic hybrid nanoporous body measured in a vacuum condition of 150 degrees, it was expressed as a hydrated structure, and it was expressed as a dehydrated structure as a sample in a state in which all of the moisture and gas adsorbed inside the pores were removed. The hydrated and dehydrated structures were confirmed to have a tetragonal structure, and there was a difference in the space group according to the presence or absence of moisture. The hydrated structure had an I4 ₁ md space group, and the dehydrated structure had an I4 ₁ /amd space group (Table 1). The crystal lattice constants were slightly different, but similarly observed. This is because, depending on the presence or absence of moisture present inside the pores, rotation of the heterocyle of the PyDC linker occurs, and the structural change occurs minutely accordingly.

sample Hydrated organic-inorganic hybrid nanoporous body (KMF-1 hydrated) Dehydrated organic-inorganic hybrid nanoporous body (KMF-1 dehydrated) Unit Cell Composition C ₉₆ Al ₁₆ N ₁₆ O ₁₅₂ C ₉₆ Al ₁₆ N ₁₆ O ₈₀ symmetry Tetragnoal Tetragnoal space group I4 _One md I4 _One /amd

a,

21.1772(2) 21.225(2) c,

10.70115(17) 10.6424(16) cell volume (cell volume,

³ ) 4799.18(10) 4794.5(10) Wavelength

) 1.5225 0.9000 Radiation type Synchrotron Radiation Synchrotron Radiation No. Observation 1134 1071 No. Parameters 74 44 No. Restraints 0 0 No. Constraints 2 One Max Change/s.u. 0.0389 0.0342 Largest Peak 0.59 0.49 Deepest Hole -0.57 -0.62 R _p, % 8.21 4.09 R _wp, % 10.71 5.97 R _F, % 7.90 7.62 GOF 0.52 1.02

Experimental Example 2. Particle size and crystal shape analysis

Scanning electron microscope images were measured using Carl Zeiss, Sigma HD after Pt coating in a high vacuum chamber. For quantitative analysis, the contents of C, H, and N components of the sample were measured using the Thermo Scientific FLASH 2000 series.

The scanning electron microscope image shown in FIG. 2c means that the organic-inorganic hybrid nanoporous body prepared according to the present invention exhibits very high crystallinity, and it can be confirmed that the particles are generated with a size of a micrometer level. The chemical formula of the sample was calculated through the component analysis in Table 2, and it was calculated from the calculated values in Table 2 and the measured values obtained from the component analysis. As a result, the chemical formula is Al(OH)(PyDC) _0.93 (H2O2) _0.23 The chemical formula was calculated, and it is a value close to the theoretical value. Depending on the synthesis method, it can have a formula of Al(OH)(PyDC) _x nH2O, where x is in the range of 0.8 to 1.0 depending on the concentration of the linker defect. In the case of n, it may be 0 to 4.5 depending on the degree of moisture.

Carbon weight ratio (wt %) Nitrogen weight ratio (wt %) Hydrogen weight ratio (wt %) defined chemical formulas calculation figure 35.78 6.96 2.22 Al(OH)(PyDC)(H ₂ O) _0.23 observed figures 33.27 6.64 2.22 Al(OH)(PyDC) _0.93 (H ₂ O) _0.23

Experimental Example 3. Analysis of porosity of organic-inorganic hybrid nanoporous body

3 is a graph showing the nitrogen adsorption isotherm of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

Nitrogen adsorption isotherm is measured at a liquid nitrogen temperature of -196 degrees using Tristar 3020 (Micromeritics) equipment after pre-treating about 0.15 g of a sample in a high vacuum (~10 ^-6 torr) condition at a temperature of 150 to 200 degrees at 150 degrees for 12 hours. and the surface area of the sample was calculated using the BET (Brunauer-Emmett-Teller) equation.

From the nitrogen adsorption isotherm result of FIG. 3, it was confirmed that the organic-inorganic hybrid nanoporous body prepared according to the present invention had high porosity. The surface area and pore volume calculated from the nitrogen adsorption isotherm showed high values of about 1130 m ² /g and about 0.473 cm ³ /g, respectively.

Experimental Example 4. Thermal stability test of organic-inorganic hybrid nanoporous body

4 is a graph showing the results of thermogravimetric analysis of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention. 5 is a graph showing the results of X-ray diffraction analysis at elevated temperature of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

For thermal stability analysis of the sample, the weight change was measured while raising the temperature at a rate of 5 ^o C/min under a nitrogen flow of 30 ml/min using a thermogravimetric analyzer (N-1000, Shinko Co., Ltd.). In addition, the structure collapse temperature was measured through the change of the X-ray diffraction pattern according to the temperature through the elevated temperature X-ray diffraction analysis.

In addition, as shown in FIG. 4 for thermal stability analysis of the organic-inorganic hybrid nanoporous body, thermogravimetric analysis was performed. The weight reduction at a temperature of 100 degrees or less is a weight reduction observed from the desorption of adsorbed water, and a weight reduction between 300-400 degrees is a weight reduction due to the decomposition of the PyDC linker coordinated with the Al metal. It means the point at which the three-dimensional framework structure of the group hybrid nanoporous body collapses.

In addition, as can be seen from the result of the elevated temperature X-ray diffraction analysis measured in FIG. 5 , an intrinsic diffraction pattern was observed up to a temperature of 300°C, whereas in the case of the X-ray diffraction pattern measured at 350°C, the intensity of the intrinsic diffraction peak was very low. It can be seen that lost Therefore, it was confirmed that the organic-inorganic hybrid nanoporous body had thermal durability up to 300 degrees.

Experimental Example 5. Hydrothermal stability and chemical stability test

6 is a graph showing the hydrothermal stability test result of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention. 7 is a graph showing the stability test results of the organic-inorganic hybrid nanoporous body in an acid-based aqueous solution according to an embodiment of the present invention.

For the hydrothermal stability test of the sample, 0.3 g of organic-inorganic hybrid nanoporous body and 20 ml of DI water were mixed in a Teflon reactor, installed in an autoclave reactor, and maintained in an oven at 100° C. for 24 hours. Physical properties of the sample before and after hydrothermal treatment The change was measured.

In addition, hydrothermal stability evaluation of the organic-inorganic hybrid nanoporous body was performed, and the results are shown in FIG. 6 . After hydrothermal treatment, almost no change in X-ray diffraction pattern was observed, and changes in surface area and pore volume calculated from nitrogen adsorption isotherms were also reduced to insignificant levels. These characteristics mean that the organic-inorganic hybrid nanoporous body has high hydrothermal stability.

In addition, for chemical stability test in acid-basic aqueous solution, 0.3 g organic-inorganic hybrid nanoporous body was dispersed in 20 ml of an aqueous solution whose pH was adjusted with HCl and NaOH, stirred at room temperature, and maintained for 24 hours, then the change in physical properties of the sample was measured. did The equipment used to observe the crystallinity change was measured using an X-ray diffractometer (Rigaku Diffractometer D/MAX IIIB, Ni-filtered Cu Kα-radiation), and the porosity change of the sample was measured by measuring the nitrogen adsorption isotherm. did

In addition, the results presented in FIGS. 7 and 3 are porosity data calculated from X-ray diffraction analysis and nitrogen adsorption isotherms of samples obtained through structural stability experiments in acidic or basic aqueous solutions. The surface area value of the sample treated in an acidic solution of pH 1 was maintained at a high level of 1060 m ² /g, and showed a high value of 1100 m ² /g even under a basic condition of pH 12. In the case of the sample treated with the pH 13 basic solution, a large decrease in the surface area was observed at 980 m ² /g, but a somewhat high level of porosity was maintained. Therefore, it was confirmed that the organic-inorganic hybrid nanoporous body according to the present invention had very high hydrothermal stability and acid-base chemical stability.

Sample of organic-inorganic hybrid nanoporous body BET area SBET
(m ² g ^-1 ) Total pore volume, Vp
(cm ³ g ^-1 ) untreated sample 1130 0.472 After hydrothermal treatment 1090 0.438 After pH 1 treatment 1060 0.452 After pH 3 treatment 1100 0.451 After pH 10 treatment 1100 0.451 After pH 12 treatment 1100 0.477 After pH 13 treatment 980 0.505

Experimental Example 6. Moisture adsorption isotherm measurement

8 is a graph showing the measurement result of the moisture adsorption isotherm of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

The moisture adsorption isotherm was analyzed using HIDEN's Intelligent gravimetric analyzer, and it is an equipment that can precisely analyze the adsorption temperature and saturated water vapor pressure. Before measuring the moisture adsorption isotherm, the sample is mounted on the electronic balance in the analysis chamber, and then the gas and moisture adsorbed to the sample are removed using a heating furnace outside the chamber at 150°C and high vacuum (<10 ^-6 torr) conditions. The dry weight was measured, and the adsorption amount was measured from the weight increase according to the relative pressure of water vapor under the adsorption temperature condition.

이상의 탈착 온도를 필요로 하는 반면에 수분에 의해 포화된 상기 유무기 하이브리드 나노세공체의 경우 100

이하의 저온에서 탈수된다는 것을 의미한다. 이러한 특성은 유무기 하이브리드 나노세공체 내 Al-OH 그룹의 존재와 극성의 헤테로고리화 유기 리간드가 유무기 하이브리드 나노세공체의 친수성을 높일 뿐 아니라 물분자와 적절한 세기의 상호작용을 갖기 때문에 제올라이트보다 훨씬 낮은 온도에서 재생이 가능한 특징을 나타내었다. As the moisture adsorption result of the organic-inorganic hybrid nanoporous body is shown in FIG. 8, the characteristic of the moisture adsorption and desorption isotherm is that it has an S-shaped reversible isotherm of a substantially saturated form at P/P ⁰ < 0.20. In this range, it showed a high adsorption amount value close to 0.393 g per 1 g. Aluminosilicate zeolite with excessively strong hydrophilicity, typically NaX zeolite, shows Type-I water adsorption isotherm under the condition of P/P ⁰ < 0.05, so desorption is difficult, so it is generally 150

In the case of the organic-inorganic hybrid nanoporous body saturated with moisture, while requiring a desorption temperature of 100 or more

It means that it is dehydrated at a low temperature below. These characteristics are superior to zeolite because the presence of Al-OH groups in the organic-inorganic hybrid nanoporous body and the polar heterocyclic organic ligand not only increase the hydrophilicity of the organic-inorganic hybrid nanoporous body, but also have an appropriate strength interaction with water molecules. It exhibited the characteristics of being able to regenerate at a much lower temperature.

The characteristics of the organic-inorganic hybrid nanoporous body according to the present invention as an energy-saving moisture adsorbent showed high moisture adsorption properties compared to silica gel, silicoaluminophosphate SAPO-34, and the like, which are other conventional commercial moisture adsorbents. The moisture adsorption amount suggested in the previous literature is SAPO-34 (0.282 gH2O/g at P/P°=0.2), MOF-303 (0.373 gH2O/gMOF at P/P°=0.2), CAU-23 (0.334 gH2O/ gMOF at P/P°=0.3), CAU-10 (0.293 gH2O/gMOF at P/P°=0.2), MIP-200 (0.360 gH2O/gMOF at P/P°=0.2) and Co-CUK-1 ( It was confirmed that the adsorption amount of the organic-inorganic hybrid nanoporous body according to the present invention was the highest as 0.263 gH2O/gMOF at P/P°=0.2). In addition, it is calculated by the method presented in the prior literature (de Lange MF, Verouden KJ, Vlugt TJ, Gascon J, Kapteijn F. Adsorption-Driven Heat Pumps: The Potential of Metal-Organic Frameworks. Chem Rev 115, 12205-12250 (2015)) The COP _C (Coefficient of Performance for Cooling Purposes) and COP _H (Coefficient of Performance for Heating Purposes) for cooling purpose showed very high values, respectively, above 0.75 and 1.75. SCP (Specific cooling power, kW/kg) and SHP (Specific heating power, kW/kg) values, which mean output when applied, were measured as 3.74 kW/kg and 5.34 kW/kg. In application, it means that the performance of the organic-inorganic hybrid nanoporous body according to the present invention is very excellent, and it means that the application possibility is large.

Experimental Example 7. Measurement of moisture adsorption and desorption stability

9 is a graph showing the long-term stability evaluation results of moisture adsorption and desorption of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

A long-term stability test of the organic-inorganic hybrid nanoporous body prepared according to the present invention as a moisture adsorbent was performed through repeated moisture adsorption and desorption experiments. Moisture adsorption and desorption repeated experiments were performed using Q600 SDT equipment from TA Instruments, and during moisture adsorption, the internal temperature was fixed at 30 degrees and nitrogen gas containing 35% relative humidity was applied inside the chamber loaded with the organic/inorganic hybrid nanoporous body. The weight increase due to moisture adsorption was collected as data, and the weight loss was measured by heating the chamber to a temperature of 70°C or 100°C during desorption. During desorption, nitrogen with a relative humidity of 4.8% was flowed at 70°C, and nitrogen with a relative humidity of 1.4% was flowed at 100°C. The change in the amount of moisture adsorption was measured by repeating the experiment 20 or 30 times under the adsorption and desorption conditions presented above.

9 is a result of evaluating the stability of the organic-inorganic hybrid nanoporous body according to the present invention through repeated cycles of moisture adsorption and desorption. The level of 0.37 g/g, the initial adsorption capacity of the organic-inorganic hybrid nanoporous body, was maintained at the same low temperature desorption condition at 70° C. until 20 cycles, and at the desorption temperature of 100° C., the adsorption capacity of 0.39 g/g was maintained up to 30 cycles. did The moisture adsorption capacity of the organic-inorganic hybrid nanoporous body was very high under the measurement conditions, and no performance change was observed, which means that the organic-inorganic hybrid nanoporous body had very good durability. In order for the organic-inorganic hybrid nanoporous body to be commercially applied, the adsorption capacity of the adsorbent must be maintained for a long time in repeated cycles of water adsorption/desorption. The organic-inorganic hybrid nanoporous body according to the present invention is suitable for commercial application because it has very excellent durability.

Experimental Example 8. Gas adsorption isotherm measurement

10 is a graph evaluating the olefin/paraffin adsorption separation performance of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

In order to evaluate the olefin/paraffin adsorption separation performance of the organic-inorganic hybrid nanoporous body, adsorption isotherms for ethane and ethylene, respectively, were measured. The adsorption isotherms of ethane and ethylene were measured using Micromeritics' Tristar 3020 equipment after pre-treating about 0.15 g of a sample at 150 °C and high vacuum (~10 ^-6 torr) for 12 hours at 150 °C.

From the ethane/ethylene adsorption experiment result of FIG. 10, it was confirmed that the organic-inorganic hybrid nanoporous body could be applied as an adsorbent for olefin/paraffin separation. Since the compound produced from the general cracking process is an olefin/paraffin mixture, a separation process for olefin production is required. For separation of olefins/paraffins, for example, separation of ethane/ethylene, a deep cold distillation method is used and is one of the energy-consuming processes.

Most of the previously known adsorption separation materials are zeolite or adsorbents modified with Ag or Cu, and these adsorbents are mostly olefin-selective adsorbents that adsorb more olefins. However, since the composition of the olefin/paraffin mixture supplied from the cracking process contains much more olefins, a very complicated process is required to prepare a high-purity olefin compound in the PSA process. In addition, a fairly large amount of adsorbent is required to prevent olefin loss during the separation process. In addition, in order to desorb the olefin adsorbed to the adsorbent during the olefin recovery process, high vacuum pressure reduction is required, and thus energy consumption is high.

In contrast, since the organic-inorganic hybrid nanoporous body according to the present invention can function as a paraffin-selective adsorbent, there is no above-mentioned problem. When a paraffin-selective adsorbent such as an organic-inorganic hybrid nanoporous body according to the present invention is used, a low-concentration paraffin compound can be selectively removed from the olefin/paraffin mixture, thereby simplifying the separation process and dramatically reducing the consumption of the adsorbent. there are advantages to

Looking at the adsorption isotherms of ethane and ethylene shown in FIG. 10, it can be seen that ethane adsorbs more than ethylene at the adsorption temperature in the range of 10-30 degrees to the organic-inorganic hybrid nanoporous body according to the present invention. In addition, it can be seen that the shape of the adsorption curve according to the pressure increases rapidly in the low pressure region of 0.4 bar or less and then gradually increases at 0.4 bar or more. It also means easy. The organic-inorganic hybrid nanoporous body according to the present invention has an ethane-selective adsorbent ZIF-7 (1.7 mmol/g), ZIF-8 (2.5 mmol/g), MAF-49 (2.6 mmol/g), UTSA-35 (2.43 mmol/g), Cu(Qc) ₂ (1.9 mmol/g), MIL-53 (2.5 mmol/g), MOF-74 It can be seen that (Fe)-peroxo (3.3 mmol/g) is higher than the ethane adsorption amount of the adsorbent.

In the above, the structure and function of the organic-inorganic hybrid nanoporous body according to an embodiment of the present invention has been examined. Hereinafter, an application device including an organic-inorganic hybrid nanoporous body will be examined.

11 is a cross-sectional view illustrating a heating and cooling device including an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

The air conditioning unit includes a moisture adsorbent bed (AB) comprising an organic-inorganic hybrid nanoporous body (NP); moisture condenser (CP); and a moisture evaporator (EV), wherein the organic-inorganic hybrid nanoporous body (NP) includes a central metal ion provided in a crystal lattice; and a ligand linker connecting the crystal lattice containing the central metal ion to the adjacent crystal lattice on a plane, wherein the crystal lattice and the ligand linker are connected in a form including pores on the plane, and moisture can be adsorbed in the pores .

In the air conditioning system according to FIG. 11, the organic-inorganic hybrid nanoporous body (NP) is the same as described above, and the description will be omitted here to avoid duplication of content.

The air conditioning unit can adsorb the moisture evaporated from the moisture evaporator (EV) in the moisture adsorbent bed (AB), and send the moisture desorbed from the moisture absorbent bed (AB) to the moisture condenser (CP) to condense it. there is. In the process of condensation and evaporation of moisture, heat of vaporization enters and exits, and cooling and heating can be performed using this. For example, as moisture is evaporated in the moisture evaporator (EV), necessary heat may be absorbed from the surroundings. A cooling effect can thus be provided. In addition, the moisture adsorbent bed AB may remove moisture supplied from the moisture evaporator EV by adsorbing/desorbing moisture, or may supply moisture to the moisture condenser CP. In particular, since the organic-inorganic hybrid nanoporous body (NP) according to an embodiment of the present invention can adsorb and desorb moisture in a low temperature range, the air conditioner according to the present invention can be driven with little energy.

As described above, the organic-inorganic hybrid nanoporous body (NP) may be used to adsorb and desorb moisture. According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous body (NP) may be provided to a moisture adsorption/desorption unit that performs moisture adsorption/desorption. In addition, a water treatment device including a moisture adsorption/desorption unit having an organic-inorganic hybrid nanoporous body (NP) may be provided. The water treatment device includes, for example, an air-conditioning device using adsorption/desorption of moisture, a dehumidifying device, a thermal battery, a water harvesting device that produces water by condensing water vapor in the air, and a seawater desalination device. ) and so on. However, the above-described types of water treatment devices are merely exemplary, and more various types of water treatment devices may be provided. The water treatment apparatus may have a structure similar to the above-described air conditioning apparatus.

12 is a cross-sectional view illustrating an olefin/paraffin separation device including an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention.

The olefin/paraffin separation apparatus comprises a separation column (SC) comprising an adsorbent bed; and a feed pipe (FL) for supplying a mixture of olefin compound and paraffin compound to the separation column (SC), wherein the adsorbent bed includes an organic-inorganic hybrid nanoporous body (NP), and an organic-inorganic hybrid nanoporous body (NP) ) is the central metal ion provided in the crystal lattice; and a ligand linker connecting the crystal lattice containing the central metal ion to the adjacent crystal lattice on a plane, wherein the crystal lattice and the ligand linker are connected in a form including pores on the plane, and the paraffin compound is selectively adsorbed in the pores do.

The separation column SC may have a shape extending in one direction, and a plurality of organic-inorganic hybrid nanoporous bodies NP are provided in the separation column. The plurality of organic-inorganic hybrid nanoporous bodies (NP) may be provided in the form of an adsorbent bed, and the adsorbent bed may be provided in the form of, for example, a fluidized bed.

The pressure in the separation column SC can be controlled. Depending on the pressure in the separation column SC, the paraffin compound may be adsorbed or desorbed to the organic-inorganic hybrid nanoporous body NP. Accordingly, the paraffin compound can be separated from the olefin/paraffin mixture while changing the pressure in the separation column SC.

As described above, the organic-inorganic hybrid nanoporous body (NP) can be used to adsorb and desorb gas-phase compounds. According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous body (NP) may be provided in a gas adsorption/desorption unit for adsorption/desorption of a gas compound. In addition, a gas processing apparatus including a gas adsorption/desorption unit having an organic-inorganic hybrid nanoporous body (NP) may be provided. The gas processing apparatus may be an apparatus for performing separation and storage of gaseous compounds. For example, it may be a device capable of separating olefin/paraffin mixture, natural gas separation, carbon dioxide capture, ammonia capture, sulfur oxide capture, nitrogen oxide capture, VOC capture, and CWA capture. However, the above-described types of gas processing apparatuses and types of gas compounds are merely exemplary, and a gas processing apparatus for removing more various types of gas compounds may be provided. The gas treatment apparatus may have a structure similar to the above-described olefin/paraffin separation apparatus.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art or those having ordinary skill in the art will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (8)

a central metal ion provided in a crystal lattice having a tetragonal structure; and
and a ligand linker connecting the crystal lattice including the central metal ion to the adjacent crystal lattice on a plane,
The crystal lattice and the ligand linker are connected in a form including pores on the plane,
adsorbing molecules in the pores,
A plurality of the crystal lattices are connected in a direction penetrating the plane,
The plurality of crystal lattices connected in a direction penetrating the plane are connected in a cis-helix structure,
The ligand linker is an organic-inorganic hybrid nanoporous body comprising a material derived from 2,5-pyrrole dicarboxylic acid. The method of claim 1,
The organic-inorganic hybrid nanoporous body includes at least one ligand linker,
The different types of the ligand linkers are provided in the form of forming pores on the plane by connecting the crystal lattice including the central metal ion to the adjacent crystal lattice on a plane. 3. The method of claim 2,
The ligand linker is 2,5-furanedicarboxylic acid (2,5-Furanedicarboxylic acid), 2,5-thiophenedicarboxylic acid (2,5-thiophenedicarboxylic acid), isophthalic acid (isophthalic acid), 3, The organic-inorganic hybrid nanoporous body further comprising a material derived from 5-pyridinedicarboxylic acid (3,5-Pyridinedicarboxylic acid). The method of claim 1,
The organic-inorganic hybrid nanoporous body has a structure of the following formula (1),
[Formula 1-1]
Al(OH) _2-xy (PyDC) _x (L2) _y nH2O
In Formula 1-1, x is a number from 0.1 to 1, PyDC means pyrrole dicarboxylate, L2 means a linker ligand different from PyDC, and satisfies 0<x+y<1, n is a number of 0 to 5, organic-inorganic hybrid nanoporous body. a central metal ion provided in a crystal lattice having a tetragonal structure; and
and a ligand linker connecting the crystal lattice including the central metal ion to the adjacent crystal lattice on a plane,
The crystal lattice and the ligand linker are connected in a form including pores on the plane,
adsorbing molecules in the pores,
A plurality of the crystal lattices are connected in a direction penetrating the plane,
The plurality of crystal lattices connected in a direction penetrating the plane are connected in a cis-helix structure,
The ligand linker is an adsorbent comprising a material derived from 2,5-pyrrole dicarboxylic acid (2,5-pyrrole dicarboxylic acid). A water treatment device comprising a moisture adsorption/desorption unit having the adsorbent according to claim 5 . A gas adsorption/desorption unit having the adsorbent according to claim 5,
The gas adsorption/desorption unit performs separation and storage of the gas compound, a gas processing device. 8. The method of claim 7,
The gas compound includes at least one gas compound selected from the group consisting of olefin compounds, paraffin compounds, natural gas, carbon dioxide, ammonia, sulfur oxides, nitrogen oxides, VOC, and CWA (Chemical Warfare Agent),
Separation and storage of the gas compound through the gas adsorption/desorption unit includes at least one of separation of olefin/paraffin mixture, natural gas separation, carbon dioxide capture, ammonia capture, sulfur oxide capture, nitrogen oxide capture, VOC capture, and CWA capture , gas processing equipment.

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