KR101596120B1 - Porous organic-inorganic composite and fabricating method thereof - Google Patents

Abstract

A skeleton having a cross-linking structure between an alkoxysilane compound having an amine terminal group and a silica precursor; And a microporous structure into which an amine group is introduced by the alkoxysilane compound, wherein the cross-linking structure is a structure in which the alkoxysilane and the silica precursor are connected to each other by -Si-O- Is provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a porous organic-inorganic hybrid material,

The present invention relates to a porous composite comprising an organic material and an inorganic material and a method of manufacturing the porous composite material. More particularly, the present invention can be used as an adsorbent for adsorbing and absorbing the carbon dioxide separation method, which is the greenhouse gas having the greatest effect on global warming , Porous organic-inorganic hybrid materials capable of adsorbing and controlling various gas-phase materials such as nitrogen compounds and sulfur compounds, various volatile organic compounds, PFC as a fluorine gas, and the like, capable of controlling adsorption to heavy metals contained in a liquid phase, ≪ / RTI >

Recent methods for the reduction and treatment of carbon dioxide include absorption, adsorption, and membrane separation as post-combustion separation processes, and decarbonization is a pre-combustion separation process.

The absorption method, which is currently being commercialized in the process of separation after combustion, is a method of absorbing and separating carbon dioxide using a liquid amine-based absorbent, desorbing it by heat-applying the carbon dioxide chemically bonded to the amine, and isolating the carbon dioxide at a high concentration. At this time, the amine-based absorbent is used together with water, and the mass transfer in the solution of carbon dioxide acts as a rate-determining step. In addition, a large amount of energy is required in the separation process of the carbon dioxide-absorbed solution, and an additional purification process according to the oxidation of the used amine is indispensably required. Therefore, the process is very complicated, so facility and equipment costs are the highest among the existing CO2 separation methods. Therefore, it is advantageous in separation from a large-sized source but it is difficult to apply to a small-scale source. In the case of using a high-temperature dry absorbent (Korean Patent No. 10-060209), there is an advantage in that a high concentration of carbon dioxide can be directly obtained in the separation process of carbon dioxide and dry absorbent, but the operation temperature is very high, And the loss due to the collapse of the structure due to the regeneration is large. In addition, the membrane separation method is very expensive, and the equipment cost of the pretreatment apparatus for purifying the combustion gas is very high, and the cost for replacement and purification due to contamination of the separation membrane is very large. In the case of adsorption methods for various gas-phase materials, the presently used method mainly uses a pressure change and a temperature change, and a separation process is also performed by simultaneously changing pressure and temperature. At this time, zeolite molecular sieve or activated carbon, carbon molecular sieve and potassium system are mainly used as an adsorbent. In the case of zeolite molecular sieve, the adsorption efficiency is high, but the problem is caused by contamination by other components contained in the combustion gas and the desorption temperature is relatively high. In the case of activated carbon, the adsorption amount is lower than that of zeolite, High temperature is required for thermal desorption and additional energy cost is required by performing adsorption at high pressure for efficient use. Therefore, in order to increase the efficiency of adsorbing and separating carbon dioxide, it is operated at a high pressure in most cases, and since a high concentration of carbon dioxide can not be separated during the separation process, a high concentration of carbon dioxide is separated through a number of steps. In addition, since the adsorption amount of the adsorbent is greatly influenced by the temperature, the adsorption amount of the adsorbent is cooled to be supplied at a low temperature before the separation step, and the amount of adsorption due to moisture is greatly decreased. There is a disadvantage that a lot of power ratio is required due to such a driving method and restrictions, and it is difficult to increase the size. In addition, since the inorganic solid adsorbent is manufactured using a binder to prepare particles, the adsorbent per unit weight is decreased and the durability is low in the fluidized bed or moving bed due to high abrasion, so that the lifetime of the adsorbent is small. In the case of an adsorbent prepared using transition metals such as potassium, magnesium and calcium, the reaction and separation occur repeatedly in the solid phase during the chemical absorption process, so that fatigue accumulates in the structure, resulting in collapse of the structure, The poisoning is generated which reacts with the gas to generate a new compound, which deteriorates the separation ability. In addition, chlorine and chlorine compounds generated in the combustion process are introduced, causing an additional problem of generating a chlorination reaction. Most of the solid adsorbents have a disadvantage in that the energy required for separation is high due to the separation of adsorbed or absorbed carbon dioxide at a high temperature and the separation efficiency is low due to high selectivity to water. Recently, the organic covalent polymer (COP) and the metal organic skeleton (MOF), which are proposed as new concept adsorbents, have excellent adsorption ability for various gas phase components such as carbon dioxide, hydrogen and methane at low temperatures. However, Securing the physical properties that can be commercialized in terms of stability and the process composition are difficult to use at present.

The present invention has been made in order to overcome the problems of the above-described separation adsorbent, and it is an object of the present invention to provide an adsorbent for adsorbing and absorbing other physical adsorbents and solid adsorbents, And a porous organic-inorganic hybrid material having a very fast adsorption and absorption rate in the range of 50 to 100 占 폚. In other words, it shows a high adsorption and absorption rate and adsorption (absorption) rate at a temperature of 50 to 90 ° C. after passing through a device for cleaning polluted gas such as sulfur compounds due to exhaust gas regulation at a fossil fuel use emission source, The present invention provides a composite capable of separating and separating carbon dioxide at 200 ° C or lower without any effect of nitrogen, sulfur compounds, nitrogen compounds, and chlorine compounds contained in water and a partial pressure of combustion gas.

The organic-inorganic composite having micropores of the present invention is intended not only for separation of carbon dioxide but also for various uses. For example, various adsorbents and catalysts can be prepared by adsorbing and absorbing various organic compounds such as gaseous or liquid phase, acidic gas, alkali gas, heavy metals, etc. and polymerization of the present adsorbent and amine groups or covalent bonding of various catalyst precursors A porous organic-inorganic hybrid material which can be used as a drug delivery material, and a method for producing the same.

Solution to the Problem

According to an aspect of the present invention, there is provided a resin composition comprising: a skeleton having a cross-linking structure between an alkoxysilane compound having an amine terminal group and a silica precursor; And a microporous structure into which an amine group is introduced by the alkoxysilane compound, wherein the cross-linking structure is a structure in which the alkoxysilane and the silica precursor are connected to each other by -Si-O- Is provided.

According to another aspect of the present invention, there is provided a carbon dioxide adsorbent comprising the aforementioned porous organic-inorganic hybrid material.

According to another aspect of the present invention, there is provided a method for preparing a mixed solution comprising: (a) mixing an alkoxysilane compound having an amine terminal group, a silica precursor, water and an alcohol solvent to form a mixed solution; (b) reacting the mixed solution to form a porous structure having a crosslinked structure; And (c) purifying and drying the porous structure to obtain a final product.

According to another aspect of the present invention, there is provided a method for preparing a mixed solution comprising: (a) mixing an alkoxysilane compound having an amine terminal group, a silica precursor, water and an alcohol solvent to form a mixed solution; (b) forming a porous structure having a crosslinked structure by injecting a reaction mixture in which gelation proceeds by the reaction of the mixed solution; And (c) drying the porous structure to obtain a final product.

According to another aspect of the present invention, there is provided a porous organic-inorganic hybrid material comprising a skeleton formed by a cross-linking structure between an alkoxysilane compound having an amine terminal group and a silica precursor, and a microporous membrane into which an amine group is introduced by the alkoxysilane compound ; The microporous membrane of the porous polymer and the amine group are used to separate at least one substance to be separated selected from the group consisting of carbon dioxide, carbon monoxide, a volatile organic compound, an acidic gas, an alkali gas, a perfluorinated compound and a heavy metal into the porous organic- Adsorption; And separating the separation target material from the porous organic-inorganic hybrid material at a temperature elevation or a reduced pressure condition of the porous organic-inorganic hybrid material.

Effects of the Invention

The amine-group-present porous composite according to an embodiment of the present invention forms micropores and the diameter of various pores is kept constant. In addition, it has a wide surface area and high CO ₂ selectivity to N ₂ by amino group, low effect of moisture and excellent adsorption (absorption) amount and adsorption (absorption) rate at higher temperature than the operation temperature of other adsorbent. The desorption temperature is lower than that of the liquid absorbent and is lower than the desorption temperature of the solid adsorbent.

When the present adsorbent is applied to the separation process of carbon dioxide, it can exhibit a high operation effect, and it is possible to operate the separation process smoothly and economically by supplementing the disadvantages of the chemical absorption method using amine and the adsorption method using solid adsorbent. Therefore, the separation of carbon dioxide, which is a main cause of global warming, can be provided and a cleaner indoor environment can be provided in the case of a small indoor environment. Also, it is possible to separate the volatile organic compound, acid gas, alkali gas, PFCs, Removal is possible.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow chart showing a method for producing a porous polymer having micropores in which amine groups are distributed.
FIG. 2 is a porous organic-inorganic hybrid composite prepared by using 3-aminopropyltriethoxysilane (APTS) and tetraethyl orthosilicate (SiO ₂ ) according to the present invention. The FT-IR The results of the analysis are shown.
3 is a scanning electron microscope (SEM) image of a porous organic-inorganic hybrid material according to an embodiment of the present invention.
FIG. 4 shows the absorption characteristics of carbon dioxide in the presence of 15 vol.% Carbon dioxide and 3.8 vol.% Water.
5 shows the 8 wt% carbon dioxide absorption time versus the weight of the porous cross-linking structure according to the absorption temperature.
FIG. 6 shows the absorption and regeneration of carbon dioxide by repeated operation. It can be seen that the porous organic-inorganic hybrid material according to one embodiment of the present invention can be reversibly operated when using the porous organic-inorganic hybrid material.
7 shows the results of adsorption experiments on sulfur dioxide gas using porous organic-inorganic hybrid materials according to one embodiment of the present invention.
FIG. 8 shows the results of adsorption experiments on nitrogen monoxide using a porous organic-inorganic hybrid material according to an embodiment of the present invention.
9 shows the results of adsorption experiments on carbon monoxide using porous organic-inorganic hybrid materials according to one embodiment of the present invention.
FIG. 10 shows the results of adsorption experiments on methyl ethyl ketone (MEK), a volatile organic compound, using porous organic-inorganic hybrid materials according to an embodiment of the present invention.
11 shows the results of adsorption experiments on representative hydrogen sulfide using porous organic-inorganic hybrid materials according to one embodiment of the present invention.

Hereinafter, various embodiments of the present invention will be described in detail.

The porous organic-inorganic hybrid material according to one embodiment of the present invention includes a skeleton having a cross-linking structure between an alkoxysilane compound having an amine terminal group and a silica precursor, and micropores having an amine group introduced by the alkoxysilane compound . Wherein the cross-linking structure is a three-dimensional structure in which the alkoxysilane and the silica precursor are formed by -Si-O- linkage to each other. Since the alkoxysilane compound has an amine group at the terminal thereof, the micropores into which the amine group is introduced can serve to provide a wide effective surface area and an adsorption point when adsorbing external substances. And the micropores may be defined by a ring structure composed of the -Si-O- bond. A chain having an amine terminal group in the ring structure is grafted.

The alkoxysilane compound may preferably have a structure of H ₂ NL-Si (OR) ₃ . Wherein L is C ₁ to C ₁₂ alkylene or C ₆ to C ₂₀ arylene, or the alkylene and arylene are optionally bonded. Also part of the backbone of L may be substituted with 0 to 4 -NH-, wherein R is hydrogen or C ₁ to C ₈ alkyl.

Specific examples of the alkoxysilane compound include 3-aminopropyltriethoxy silane, aminosilane hydrolyzate, 3-aminopropyltrimethoxysilane, 2-amino Aminoethyl-3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropyltriethoxysilane, 2-aminoethyl- Aminopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, 2-aminopropylmethyldimethoxysilane, (Triethoxysilylpropyl) amine] can be used. Preferably, 3-aminopropyltriethoxysilane or 2-aminoethyl-3-aminopropyltrimethoxysilane is taken into consideration, considering economical efficiency.

In one embodiment, the hydrogen of the amine end group may be substituted with alkyl.

Also, in one embodiment, the alkoxysilane compound may be an ionic liquid. The ionic liquid has a combination of a cation and an anion, and a lower aliphatic quaternary ammonium is used as a cation. As the anion, an imide compound such as metal chloride ion, metal fluoride ion and bis (fluorosulfonyl) imide may be used have.

The silica precursor is preferably a silicate as the silica precursor, as a base material constituting the -Si-O- bond constituting the skeleton of the organic-inorganic hybrid material. The silica precursor may comprise a silicate of 3 to 200 carbon atoms, preferably 3 to 50 carbon atoms, more preferably 3 to 12 carbon atoms. More specifically, the silica precursor may be selected from the group consisting of tetramethoxysilane, tetramethyl orthosilicate, tetraethoxysilane, tetraethyl orthosilicate, tetra-n-propyl silicate -n-propyl silicate) and tetrabutylglycol silicate.

The terminal group of the cross-linking structure of the porous organic-inorganic hybrid material may be selected from an amine group or a hydroxyl group. The amine group may be introduced by an alkoxysilane group having an amine terminal group, and the hydroxyl group may be introduced by the water used during the reaction. The amine group does not participate in the cross-linking reaction of the synthesis of the complex, separates carbon molecules connected to the oxygen of the alkoxysilane, and initiates the reaction of oxygen and the silica molecules of the silica precursor and oxygen of the alkoxysilane.

The amount of water (preferably purified water) used in the synthesis and the type and amount of alcohol used as a structural culture agent will be described in the production of a porous organic-inorganic hybrid material to be described later. The surface characteristics such as particle surface area, pore size, pore size Distribution, and distribution of amine groups can be controlled.

The skeleton of the porous organic-inorganic hybrid material may have a crosslinking structure by the reaction of the silica precursor, the alkoxysilane compound, water and a solvent. At this time, the pore structures into which various amine groups are introduced can provide a wide effective surface area and adsorption point in CO ₂ adsorption. Also, the surface and void structure of the crosslinked structure complex in which the amine group is present can be irreversibly fixed. Thus, CO ₂ For gases such as Chemical and physical Sorption performance can be maintained.

The following Reaction Scheme 1 shows the reaction process of the porous organic-inorganic hybrid material according to one embodiment of the present invention, and the following Formula 1 shows the structure of the porous organic-inorganic hybrid material according to one embodiment of the present invention.

[Reaction Scheme 1]

[Chemical Formula 1]

In the above formula (1), the entire skeleton is connected to each Si and Si by -Si-O- bond to form a crosslinked structure. For example, such a cross-linking structure can be obtained by reacting a mixed solution of (C ₂ H ₅ O) ₄ Si and (C ₂ H ₅ O) ₄ SiCH ₂ CH ₂ CH ₂ NH ₂ and water (H ₂ O) Can be obtained.

While the -OH end groups are derived from the water used during the reaction. The molar ratio of the silica precursor to the alkoxysilane in the porous organic-inorganic hybrid material may be preferably 1: 0.01 to 0.5. If the molar ratio of the silica precursor is less than 0.01, the porous structure is hardly formed. If the molar ratio of the silica precursor is more than 0.5, the amine group is insufficient and sufficient absorption is difficult, and the porous structure may not be formed.

The micropores may be formed by a cyclic structure composed of -Si-O- bonds. An amine group is introduced into each micropore because an alkoxysilane compound having an amine end group (aka aminosilane) is crosslinked together with a silica precursor.

The surface area of the micropores may vary from 1 to 1,000 m ² / g, preferably from 5 to 500 m ² / g, depending on the type of silicate and aminosilane used. If the surface area is less than the above range, the specific surface area may be insufficient and the adsorption amount of carbon dioxide may be low. If the surface area is above the above range, the pore size may be small, so that diffusion of carbon dioxide into the pores is delayed.

The average pore diameter of the micropores may be 0.01 to 200 nm, preferably 1 to 100 nm, depending on the type of silicate and aminosilane used, the amount of purified water, and the amount and type of alcohols. If the average pore diameter is less than the above range, it is difficult to freely enter and exit the adsorbent material depending on the pore resistance. If the average pore diameter is less than the above range, the surface area may be decreased and the adsorption amount may be decreased.

The porous organic-inorganic hybrid material may have excellent CO ₂ absorption capacity. Thus, according to one embodiment of the present invention, there is provided a carbon dioxide adsorbent comprising the porous organic-inorganic hybrid material. For example, the carbon dioxide adsorbent may have a pressure of 1 bar and an adsorption amount of CO ₂ measured at 25 at a thermogravimetric analyzer of 18 wt% or more. The desorption temperature of CO ₂ adsorbed on the carbon dioxide adsorbent may be 170 ° C or less.

According to one embodiment of the present invention, there is provided a carbon dioxide adsorbent comprising a porous organic-inorganic hybrid material having micropores having a cross-linking structure represented by Chemical Formula 1 and having amine groups distributed therein.

According to one embodiment, the porous cross-linking structure having the above-mentioned chemical structure cross-linking structure can be produced by the following method. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow chart showing a method for producing a porous polymer having micropores in which amine groups are distributed. Referring to FIG. 1, in step S1, a mixed solution is formed by mixing an alkoxysilane compound having an amine terminal group, a silica precursor, water, and an alcohol solvent.

By adjusting the molar ratio of the alkoxysilane compound, the silica precursor, water, and the amount and type of alcohol as a solvent, the surface area and the void volume of the porous composite can be controlled and the formation speed can be controlled.

The silica precursor is preferably a silicate as the silica precursor, as a base material constituting the -Si-O- bond constituting the skeleton of the organic-inorganic hybrid material. The silica precursor may comprise a silicate of 3 to 200 carbon atoms, preferably 3 to 50 carbon atoms, more preferably 3 to 12 carbon atoms. More specifically, the silica precursor may be selected from the group consisting of tetramethoxysilane, tetramethyl orthosilicate, tetraethoxysilane, tetraethyl orthosilicate, tetra-n-propyl silicate -n-propyl silicate) and tetrabutylglycol silicate.

The alkoxysilane compound serves to provide an amine group to give an adsorption point of carbon dioxide, and it is preferable to use 50 to 600 parts by weight of the alkoxysilane compound based on 100 parts by weight of the silica precursor. When the amount of the alkoxysilane compound is less than 50 parts by weight, the amine group may not be sufficient, so that the surface properties of the amine may be reduced. When the amount of the alkoxysilane compound is more than 600 parts by weight, the crosslinking structure may be difficult to form.

Specific examples of the alkoxysilane compound include 3-aminopropyltriethoxy silane, aminosilane hydrolyzate, 3-aminopropyltrimethoxysilane, 2-amino Aminoethyl-3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropyltriethoxysilane, 2-aminoethyl- Aminopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, 2-aminopropylmethyldimethoxysilane, (Triethoxysilylpropyl) amine] can be used. Preferably, 3-aminopropyltriethoxysilane or 2-aminoethyl-3-aminopropyltrimethoxysilane is taken into consideration, considering economical efficiency.

On the other hand, water (preferably purified water) constituting the mixed solution causes the silica precursor and the alkoxysilane to react with each other through hydrolysis of the alkoxysilane compound. For example, 3-aminopropyltriethoxysilane in alkoxysilane reacts with silicate silicon by reacting ethoxy group with water, decomposing into ethanol form and generating three hydroxyl groups in silicon molecule. That is, it functions to initiate the hydrolysis of ethoxysilane. The amount of water may be 10 to 500 parts by weight, preferably 30 to 300 parts by weight based on 100 parts by weight of the silica precursor. When the amount of water is out of the above range, the reaction rate is slow or rapidly proceeded, the crosslinking is not complete, and the specific surface area and pore structure are not developed, so it is preferable to use a predetermined amount.

The alcohol solvent serves as a structural culture agent for controlling the reaction rate to form pores and surface structure of the crosslinked structure complex. The alcohol solvent may be used in an amount of 0.0001 to 500 parts by weight, preferably 0.001 to 200 parts by weight, based on 100 parts by weight of the silica precursor. If the amount of the alcohol solvent is less than the above range, a porous structure is not formed. If the amount is less than the above range, the reaction time and drying time become long and the structure may not be formed. The alcohol solvent can be used to control the gelation and solidification rate of the liquid reactant as the synthesis unit increases, and to maintain the gel state at the time of injection. Specific examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutanol, pentanol, isopentanol, isopentanol, Hexadecan-1-ol, Ethane-1,2-diol, Propane-1,2-diol, Propane-1,2,3-triol, butane-1,2,3,4-tetraol, pentane- 1,2,3,4,5-pentol, hexane-1,2,3,4,5,6-hexol (Hexane-1,2,3 , 4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (Heptane-1,2,3,4,5,6,7-heptol) Prop-2-ene-1-ol, 3,7-dimethoxyocta-2,6-dien- 1-ol, Prop-2-in-1-ol, Cyclohexane-1,2 2- (2-propyl) -5-methyl-cyclohexane-1-ol] or the like One or more selected, and half When it not so limited. Preferably, butanol can be used as the alcohol in terms of mixing degree, molecular size and vapor pressure.

Micropores may be formed upon crosslinking by the alcohol solvent. The crosslinked structure thus formed has a structure in which oxygen molecules of the alkoxysilane are crosslinked around the silicon of the silicate.

When mixing the raw materials to form a mixed solution, the mixing time can be adjusted to 5 seconds or more and 10 hours or less. When the mixing time is less than 5 seconds, the mixing is not performed well. On the other hand, when the mixing time is longer than 10 hours, the gelation proceeds and the reaction proceeds in a state where the drying is not carried out to reduce the surface area of the formed structure, can do.

In some embodiments, a cross-linking agent may be added to the mixed solution of step S1. The crosslinking agent serves to increase the particle size of the composite. Wherein the crosslinking agent is selected from the group consisting of dimethoxymethane, 1,3,5-trioxane, paraformaldehyde?,? '-Dichloro-o-xylene and?,? Or more. Preferably, 1,3,5-trioxane or paraformaldehyde can be used in view of economical efficiency.

In step S2, the mixed solution is reacted to form a porous structure having a crosslinked structure. The reaction time is preferably 5 seconds or more and 50 hours or less. When the reaction time is less than 5 seconds, the reaction is not performed well, and when the reaction time exceeds 50 hours, the complete reaction proceeds and the reaction is meaningless. It is usually preferable to carry out the reaction for 10 seconds to 1 hour. The reaction temperature may be from 0 to 70, and usually from room temperature to about 50 or less in terms of formation of the surface structure depending on the reaction rate of the structure and by-products generated and the diffusion rate of the unreacted raw material.

 In the next step S3, the crosslinking structure is purified and dried to obtain the final product. After completion of the reaction, the cross-linked structure may be filtered to separate the solid end product and the liquid non-reactant and side reactants. After filtration, it can be washed with an appropriate organic solvent. The final product can be dried at room temperature for several hours after the next washing, but most of the by-products are removed by drying. Therefore, drying using high purity raw materials is sufficient. In general, it is preferable to dry at a temperature near the room temperature, and in some cases, the structure may be destroyed during drying by raising the temperature to room temperature or higher.

In another embodiment, in the preparation of the porous organic-inorganic hybrid material, the reaction mixture in which gelation proceeds by the above-mentioned reaction in step S2 described above can be injected. The reaction mixture can preferably be injected through a nozzle having a diameter of 0.05 to 10 mm in order to make the structure of the desired shape. If the diameter of the nozzle is less than 0.05 mm in the injection process, the injection does not occur smoothly, and the completion of the reaction may be lowered due to the quick drying. In addition, if it exceeds 10 mm, the internal drying process of the injection-molded structure may be slow, and it is difficult to obtain desired surface characteristics. If the drying time is less than 1 hour, the desired properties can not be obtained because the drying process and the completion degree of the reaction are lowered. It is advantageous in that it can be manufactured only by drying without washing and filtration step by the injection method.

As a specific example of the above-mentioned production method, there is a method in which an aminosilane such as 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane is reacted with purified water and tetraethylorthosilicate in an ethanol solvent to perform a crosslinking reaction. In this case, the final crosslinked porous body may have an excellent CO ₂ adsorption / absorption capacity of 18% by weight or more with an amine group-containing porosity. The resulting porous organic-inorganic hybrid material may have a rigid bonding structure of three-dimensional shape around the silicon as shown in the above formula (1). As a result, the initially colorless raw material mixture becomes white after the final organic / inorganic composite is formed.

FIG. 2 is a porous organic-inorganic hybrid composite prepared by using 3-aminopropyltriethoxysilane (APTS) and tetraethyl orthosilicate (SiO ₂ ) according to the present invention. The FT-IR The results of the analysis are shown. Each of the mixing ratio (a) APTS, (b) 5% SiO 2 / APTS (c) 10% SiO 2 / APTS (d) 20% SiO 2 / APTS (e) 30% SiO 2 / APTS (f) 40% SiO ₂ / APTS (g) 50% SiO ₂ / APTS. Percentage notation in the above SiO ₂ indicates the weight of SiO ₂ present in the structure after the reaction, which is a value changed according to the amount of tetraethyl orthosilicate as the reaction raw material. That is, since the ethane groups of tetraethylorthosilicate and 3-aminopropyltriethoxysilane are separated during the reaction, the ethane groups of the two raw materials are removed and the weight ratio is shown. Therefore, it shows the infrared absorption characteristic according to the mixing ratio of the two components. In FIG. 2, the wavelength of 1620 cm ^-1 indicates -OH bonding, and the peak intensity is increased as the amount of silicon oxide is increased. The wavelength of 1300 cm ^-1 indicates -CN and the peak intensity decreases as the content of APTS decreases. A wavelength of 1000 to 1200 cm ^-1 represents Si-O-Si, and the absorbance increases as the width of the peak increases. The wavelength of 960 cm ^-1 represents Si-OH. Therefore, it can be understood that the amine-group-containing porous organic-inorganic hybrid material of the present invention is formed by reacting a raw material with purified water.

3 is a scanning electron microscope (SEM) image of a porous organic-inorganic hybrid material according to an embodiment of the present invention. Referring to FIG. 3, it can be seen that the porous organic-inorganic hybrid material is a silica-like structure having a structure in which an amine group is bonded around silicon as shown in Formula 1.

As described above, the porous organic-inorganic hybrid material according to one embodiment of the present invention can be used as an adsorbent capable of improving the disadvantages of the conventional adsorbent and increasing the efficiency of adsorbing and separating. In addition, the porous organic-inorganic hybrid material described above can be used for various purposes other than separation of carbon dioxide. It is possible to adsorb and separate volatile organic compounds, acidic and alkali gases, fluorine compound gases, heavy metals, etc. using micropores, which can be operated in the gas and liquid environments. In addition, it has a composite structure of organic and inorganic materials. Therefore, it can be used for various powder processes because it is resistant to abrasion, and exhibits high adsorption efficiency in a temperature range of 0 to 150 than that of the existing adsorbent.

Also, in the adsorption process occurring in the amine groups and micropores existing in the structure of the complex, the binding energy between the amine group and carbon dioxide on the surface of the porous organic-inorganic hybrid material according to one embodiment of the present invention is smaller than the binding energy between the liquid amine and carbon dioxide So the desorption energy transfer can be lower compared to the liquid amine. Therefore, the carbon dioxide separation process shows better performance than other solid adsorbents and solid absorbents due to low energy consumption, high resolution, and excellent selectivity. In addition, it exhibits a high adsorption amount for SOx and NOx which are acid gases, reversible adsorption and desorption occur, and volatile organic compounds and CF ₄ And also has a high adsorption amount and regeneration ability.

According to the prior art, the process is complicated and costly because the meso structure is synthesized and the amine group compound is grafted to produce the silica-based amine-imparting compound. On the other hand, according to the process for producing a porous organic-inorganic hybrid material according to an embodiment of the present invention, an amine group-containing silica compound can be produced by a simple process, and a high adsorption And the speed can be obtained.

Hereinafter, the present invention will be described with reference to specific embodiments, but the technical idea of the present invention is not limited by the following embodiments.

≪ Example 1 >

Preparation of amine group-containing organic / inorganic composite (5% SiO ₂ / APTES) using 3-aminopropyltriethoxysilane and tetraethylorthosilicate.

0.17 g of tetraethyl orthosilicate (Aldrich Chemical, USA) and 0.3 g of purified water were added to 1.0 g of 3-aminopropyltriethoxysilane (Aldrich Chemical Co., USA). After the addition, they were mixed so as to be completely mixed at room temperature. The mixing time was 5 minutes.

The reaction mixture, which was mixed and gelled, was injected through a nozzle having a diameter of 0.1 mm or more and 10 mm or less. The injected mixture changes from transparent color to white by the reaction, and the reaction is completed within 10 to 15 minutes at room temperature, so it is dried at the same time as the reaction. Drying time was maintained at least 1 hour. After drying at room temperature, a white rod-like cross-linked structure was completed and pulverized to prepare a structure having an average size of 200 μm and a density of 1440 kg / m ³ .

In this case, the drying temperature is from 0 to 100, and if it is less than 0, the reaction and drying are slow, the crosslinking is not sufficiently performed, the diffusion of reaction by-products is slow and the crosslinking structure can not be obtained. The crosslinking structure can not be obtained.

≪ Example 2 >

Preparation of amine group-containing organic / inorganic composite (10% SiO ₂ / APTES) using 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid

Except that 0.2 g of tetraethyl orthosilicate (Aldrich Chemical Co., USA) and 3.2 g of purified water were added to 1.0 g of 3-aminopropyltriethoxysilane (Aldrich Chemical Co., USA) . The composition of various samples is shown in Table 1 below.

 Example of raw material composition (unit g) Example Name of sample Tetraethyl orthosilicate < RTI ID = 0.0 > Aminopropyl triethoxysilane (3-aminopropyl) Purified water One 5% SiO _{2 -} APTS 0.17 1.0 0.30 2-1 10% SiO _{2 -} APTS 0.24 1.0 0.32 2-2 20% SiO ₂ -APTS 0.54 1.0 0.42 2-3 30% SiO _{2 -} APTS 0.93 1.0 0.54 2-4 40% SiO _{2 -} APTS 1.31 1.0 0.67 2-5 50% SiO _{2 -} APTS 2.16 1.0 0.95

≪ Example 3 >

(5% SiO ₂ / APTES-1) using butanol, 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid.

1.0 g of 3-aminopropyltriethoxysilane (Aldrich Chemical Co., USA), 0.163 g of tetraethyl orthosilicate (Aldrich Chemical, USA) and 1.0 g of butanol [Aldrich Chemical Co., USA] were added and thoroughly mixed. . After the addition, the mixture was stirred at room temperature for 7 minutes to carry out the reaction. As the reaction proceeded, the color changed to white. After completion of the reaction, filtration was carried out. For filtration, the reaction product was separated from the solid product and a small amount of the liquid non-reactant and by-product using a filter cloth. After filtration, the mixture was washed with 25 ml of diethyl ether (Aldrich Chemical, USA). After washing, it was dried at room temperature for 2 hours or more. The raw material compositions of the various samples are shown in Table 2 below.

Example of raw material composition (unit g) Example Name of sample Tetraethyl orthosilicate < RTI ID = 0.0 > Aminopropyl triethoxysilane (3-aminopropyl) Purified water Butanol 3-1 5% SiO _{2 -} APTS 0.163 1.5 0.42 1.0 3-2 6% SiO _{2 -} APTS 0.197 1.5 0.44 1.0 3-3 8% SiO _{2 -} APTS 0.27 1.5 0.46 1.0 3-4 10% SiO _{2 -} APTS 0.36 1.5 0.49 1.0

<Example 4>

(5% SiO ₂ / APTES-1) using ethanol, 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid.

An organic-inorganic hybrid material was prepared in the same manner as in Example 3, except that ethanol was used instead of butanol to prepare a crosslinked product. Ethanol (Aldrich Chemical, USA) was used in an amount of 1.0 g.

&Lt; Examples 5 to 7 >

(5% SiO ₂ / APTES-2) with 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid.

(Example 5), 1.0 g of pentanol (Example 6) and 1.0 g of methanol (Example 7) were used in the same manner as in Example 3, except that propanol 1.0 g (Example 5), 1.0 g 0.06 mol of paraformaldehyde was used to prepare a crosslinked structure.

&Lt; Examples 8 to 10 >

(5% SiO ₂ / APTES-2) with various silanes and tetraethylorthosilicic acid.

Except that 1.0 g of 3-aminopropyltrimethoxysilane (Example 8) and 2 g of 3-aminopropyltrimethoxysilane were used in place of 3-aminopropyltriethoxysilane for Examples 8 to 7, respectively, 1.0 g of 3-aminopropylmethyldiethoxysilane (Example 10), 1.0 g of 2-aminoethyl-3-aminopropyltrimethoxysilane (Example 9) and 1.0 g of 3-aminopropylmethyldiethoxysilane ) Was used to prepare a crosslinked structure.

&Lt; Example 11 >

(5% SiO ₂ / APTES-3) using butanol, 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid.

The crosslinking structure was prepared by the same method as in Example 3 except that the mixing reaction step was carried out but the method of Example 3 was used and the filtration washing step was not carried out, followed by injection and drying by the method of Example 1. [ Also, it was possible to produce the composition of Table 2 and showed similar carbon dioxide adsorbing ability.

&Lt; Examples 12 to 15 &

(5% SiO ₂ / APTES-3) using butanol, 3-aminopropyltriethoxysilane and tetraethylorthosilicic acid.

Except that 1.0 g of ethanol (Example 12), 1.0 g of propanol (Example 13), 1.0 g of pentanol (Example 14), and 1.0 g of ethanol were used in place of butanol for Examples 12 to 15, respectively, A cross-linked structure was prepared using 1.0 g of methanol (Example 15) and 0.06 mol of paraformaldehyde, respectively.

<Comparative Example>

2 g of silica (MCM-48, specific surface area 1012 / g, pore size 3.1 nm) is vacuum-dried. 30 cc of anhydrous toluene [Aldrich Chemical, USA] was added to the dried silica in an argon gas atmosphere, and toluene was evenly injected into the pores by using a vacuum. Aminopropyltriethoxysilane (Aldrich Chemical Co., USA) Add the pear. The mixture was stirred at room temperature in an argon atmosphere for 6 hours to be evenly dispersed. This was placed in a reflux apparatus equipped with a condenser, and the mixture was heated with stirring for 12 hours while maintaining the surface temperature of the heater at 150 占 폚. After the heating is completed, the silica adsorbent, in which the amine group is grafted, is separated by filtration, the unreacted reactant and the reaction product. Cleaning is carried out using methylchloride [Aldrich Chemical, USA] during the separation process. After the washing, the separated adsorbent is put in a Solex type washing machine and 100 cc of methyl chloride (Aldrich Chemical, USA) is added, and the reaction is continued for 3 hours while the surface temperature of the reactor is maintained at 80 ° C. After stirring is completed, the mixture is washed with ethyl alcohol (Aldrich Chemical, USA). The filtered adsorbent is dried in a 110 ° C drier for 24 hours to completely remove the organic solvent

<Evaluation>

The diffuse reflected ultraviolet-visible light (DRS UV-Vis) spectrum of the samples obtained in the examples was recorded with a SCINCO Neosys 2000 spectrometer. Between FT-IR spectrometer (Nicolet IR 200) 4000 and 400cm ^-1 at room temperature with a resolution of 4cm ^-1 it was recorded transform infrared (FT-IR) spectrum Fourier.

The nitrogen adsorption / desorption isotherms were measured at-196 using a Belsorp mini II sorption analyzer. Before each adsorption measure, the samples were degassed at 150 ° C in a vacuum of less than 10 ^-5 mbar. The surface area from the Brunauer-Emmett-Teller (BET), the linear portion of the expression was measured. Thermogravimetric analysis (Scinco TGA N1000) the CO ₂ absorbing and for each of the samples using a CO ₂ (99.999% purity) and N ₂ using Desorption measurements were performed. Approximately 10 mg of sample was loaded into a platinum sample pan and initial activation was performed at 150 캜 in an N ₂ atmosphere. And lowered to 25 ° C for CO ₂ adsorption. The desorption was carried out by gradually raising the temperature to 25 to 150 캜 while flowing N ₂ . In addition, adsorption / desorption experiments on carbon dioxide were carried out under the exhaust gas simulation conditions for carbon dioxide using a desorption analyzer (Autochem II 2920). The experimental conditions were as follows: the adsorption rate and the amount of adsorption were verified in the presence of water at a measurement temperature of 55 ° C and a flow rate of 80 mL / min (CO ₂ 15%, H ₂ O 3.8%, He 81.2%). In addition, the adsorption capacity of not only carbon dioxide but also volatile organic compounds, SO ₂ , NO, and CF _{4, which} is a typical fluorinated gas, was measured.

The BET surface area and CO ₂ sorption capacity of the above Examples and Comparative Examples are shown in Table 3. Referring to Table 3, the surface area and the amount of carbon dioxide adsorption differ depending on the raw materials according to each example, which can be controlled by the reaction time and the mixing ratio of the silicon precursor and the alkoxysilane compound. It can be seen that a porous organic-inorganic hybrid material exhibiting excellent adsorptivity can be obtained by various combinations of the raw materials.

The pore characteristics and the amount of adsorbed carbon dioxide Example Carbon dioxide adsorption amount (wt%, 40 캜) Specific surface area (m ² / g) Pore Diameter (nm) One 13.3 20.12 34.22 2-1 13.0 18.21 33.05 2-2 12.6 19.35 32.68 2-3 10.8 78.30 21.59 2-4 9.2 18.71 27.29 2-5 5.1 112.59 20.76 3-1 16.5 35.21 28.20 3-2 17.2 24.22 29.20 3-3 18.2 50.12 33.12 3-4 17.8 53.11 20.12 4 14.0 42.12 18.11 5 13.1 35.12 10.22 6 11.2 42.21 22.34 7 10.8 15.15 10.24 8 4.2 16.22 55.35 9 3.8 14.20 24.36 10 5.7 12.05 22.84 11 4.6 7.25 80.23 12 7.2 53.26 3.21 13 8.5 65.57 5.22 14 5.1 84.32 1.31 15 6.2 96.02 2.21 Comparative Example 12.0 870.54 1.85

In addition, the adsorption rate is an important characteristic in the separation process of carbon dioxide. The measured adsorption rate is shown in Fig. FIG. 4 shows the absorption characteristics of carbon dioxide in the presence of 15 vol.% Carbon dioxide and 3.8 vol.% Water. It shows a very fast absorption rate as compared with other adsorbents or absorbents. FIG. 5 is a graph showing absorption rates of porous organic-inorganic hybrid materials having amine groups according to the present invention. FIG. 5 shows the absorption time of 8 wt.% Of the weight of the porous organic-inorganic hybrid material, indicating a rapid absorption rate over a wide temperature range. FIG. 6 shows the absorption and regeneration of carbon dioxide by repeated operation. It can be seen that the porous organic-inorganic hybrid material according to one embodiment of the present invention can be reversibly operated when using the porous organic-inorganic hybrid material. 7 shows the results of adsorption experiments on sulfur dioxide gas using porous organic-inorganic hybrid materials according to one embodiment of the present invention. It shows higher adsorption amount and rate than carbon dioxide. FIG. 8 shows the results of adsorption experiments on nitrogen monoxide using a porous organic-inorganic hybrid material according to an embodiment of the present invention. 9 shows the results of adsorption experiments on carbon monoxide using porous organic-inorganic hybrid materials according to one embodiment of the present invention. FIG. 10 shows the results of adsorption experiments on methyl ethyl ketone (MEK), a volatile organic compound, using porous organic-inorganic hybrid materials according to an embodiment of the present invention. 11 shows the results of adsorption experiments on hydrogen sulfide using porous organic-inorganic hybrid materials according to one embodiment of the present invention.

From the above-described experimental results, it can be seen that the porous organic-inorganic hybrid material according to one embodiment of the present invention has adsorbability to various gases, and particularly has a high reversible adsorbability against acid gas.

Claims (14)

A skeleton having a cross-linked structure in which an alkoxysilane compound having an amine terminal group and a silica precursor are connected to each other by -Si-O- bond; And
And micropores into which an amine group provided by the alkoxysilane compound constituting the above skeleton is introduced,
The -Si-O- linkage includes at least one ring structure selected from a triple ring represented by the following formula (2) and a double ring structure represented by the following formula (3)
The number of the amine groups contained in the alkoxysilane compound constituting the skeleton constitutes the side chain of the skeleton and the remaining side chain constitutes the hydroxy group,
Wherein the alkoxysilane compound having an amine terminal group and the silica precursor are contained in a molar ratio of 1: 0.01 to 0.5:
(2)

(3)

The method according to claim 1,
Wherein said alkoxysilane compound has a structure of H ₂ NL-Si (OR) ₃ , L is C ₁ to C ₁₂ alkylene or C ₆ to C ₂₀ arylene, or said alkylene and said arylene are optionally And wherein part of the backbone of L is substituted with 0 to 4 -NH-, wherein R is hydrogen or C ₁ to C ₈ alkyl. The method according to claim 1,
Wherein the silica precursor is a silicate. delete delete The method according to claim 1,
And the surface area of the micropores is 5 to 500 m ² / g. The method according to claim 1,
Wherein the average pore diameter of the micropores is 1 to 100 nm. The method according to claim 1,
Wherein the micropores are formed by a ring structure composed of the -Si-O- bond. 9. The method of claim 8,
And a chain having an amine terminal in the ring structure is grafted. A porous organic-inorganic hybrid material according to any one of claims 1 to 3 or 6 to 9, which is a carbon dioxide adsorbent comprising a composite having the following formula:
[Chemical Formula 1]

(a) an alkoxysilane compound having an amine end group, a silica precursor, water and an alcohol solvent, wherein the alkoxysilane compound having an amine end group and the silica precursor are mixed in a molar ratio of 1: 0.01-0.5 in water and an alcohol Wherein the solvent comprises 10 to 500 parts by weight and in the range of 0.0001 to 500 parts by weight based on 100 parts by weight of the silica precursor;
(b) crosslinking in which the alcohol is decomposed and removed through the hydrolysis of alkoxysilane compound of water by reacting with the mixed solution, and the silicon is reacted with silicon of the silica precursor in the state where hydroxyl groups are generated in the silicon molecules and are connected to each other by Si- Structure, wherein the -Si-O- bond comprises at least one ring structure selected from a double ring and a triple ring structure,
Forming a porous structure in which a number of amine groups contained in the alkoxysilane compound constitutes the side chain of the backbone and the remaining side chain is composed of hydroxy groups and micropores are formed; And
(c) purifying and drying the porous structure to obtain a final product. (a) an alkoxysilane compound having an amine end group, a silica precursor, water and an alcohol solvent, wherein the alkoxysilane compound having an amine end group and the silica precursor are mixed in a molar ratio of 1: 0.01-0.5 in water and an alcohol Wherein the solvent comprises 10 to 500 parts by weight and in the range of 0.0001 to 500 parts by weight based on 100 parts by weight of the silica precursor;
(b) injecting the reaction mixture in which the gelation proceeds by the reaction of the mixed solution through a nozzle having a diameter of 0.05 to 10 mm to form a porous structure, wherein the alcohol is decomposed and removed through hydrolysis of the alkoxysilane compound of water, Wherein the -Si-O- linkages form a skeleton of a crosslinked structure in which hydroxyl groups are generated in the molecule and are reacted with silicon of the silica precursor and connected to each other by Si-O- &Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
Forming a side chain of the skeleton by the number of amine groups contained in the alkoxysilane compound and forming a microporosity of the remaining side chain by the hydroxyl group; And
(c) drying the porous structure to obtain a final product. 13. The method according to claim 11 or 12,
Wherein the mixed solution further contains a crosslinking agent. delete

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