KR102218847B1 - Fabrication method of organic-inorganic nanoporous material adsorbent and organic-inorganic nanoporous material adsorbent using it - Google Patents

Abstract

The method for manufacturing an organic-inorganic nanoporous body according to the present invention includes an aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a first step of preparing an organic-inorganic nanoporous material precursor by mixing water. And a second step of crystallizing the organic-inorganic nanoporous material precursor.

Description

Fabrication method of organic-inorganic nanoporous material adsorbent and organic-inorganic nanoporous material adsorbent using it}

The present invention relates to a method of manufacturing an organic-inorganic nanoporous body with a significantly high adsorption amount, and an organic-inorganic nanoporous body produced therefrom.

Due to global warming and the depletion of energy resources, attempts to recycle energy discarded by industries are continuing. Typical of the energy discarded by industries, etc. are generated in the form of waste heat furnaces, low and medium temperature water, and steam, and in most cases these are not utilized and are discarded.

As one of the ways to utilize such waste heat, adsorption refrigeration systems are in the spotlight. The adsorption refrigeration system uses refrigerants such as water, alcohol, ammonia, etc., and uses commonly known adsorbents such as silica gel, zeolite, and activated carbon.

Among them, the commercialized adsorption refrigeration system uses water as a refrigerant and silica gel as an adsorbent. However, silica gel tends to start adsorption at a low partial pressure of water vapor due to its strong hydrophilicity, and the adsorption rate is slow and desorption is not easy in _{the driving pressure range (P/P 0 = 0.1 to 0.3) on the adsorption refrigeration system.} There is a problem that the amount of water adsorbed per sugar is considerably low as 0.1 g/g (g-water/g-sorbent).

On the other hand, moisture adsorbents used in commercially available desiccant dehumidifiers, adsorption heat pumps, dehumidifying rotors, and cooling/cooling machines mainly include porous silica and zeolite, but in the case of porous silica or zeolite, the moisture adsorption rate is low or adsorption and desorption There is a problem that the moisture pressure is out of the driving pressure range or the adsorption amount is low.

Accordingly, there is a need to develop an adsorbent having a high adsorption rate and excellent adsorption amount as an adsorbent that can be used in the above-described adsorption refrigeration system, death control dehumidifier, adsorption heat pump, dehumidification rotor, air conditioner and heater.

Organic-inorganic nanoporous bodies are attracting attention as a substitute material for overcoming the above-described problems. In general, metals easily generate coordination compounds at room temperature with organic ligands having a non-shared electron pair. These coordination compounds are polymerized under water or an organic solvent to form a three-dimensional skeleton structure. The above compounds are generally referred to as "metal-organic frameworks (MOF)", and some compounds are also referred to as "organic-inorganic nanoporous bodies" because they have nano-sized pores while forming a three-dimensional skeleton structure. In addition, the organic-inorganic nanoporous material can be applied to various fields by variously modifying the structure according to the coordination number of metal ions and the type of organic ligand compound, and it is reported that the surface area is up to 3 to 15 times larger than that of zeolite. In addition, there is an advantage in that it is easy to impart reactivity and adsorption selectivity due to the presence of unsaturated metal ion sites that do not exist in the zeolite made of inorganic metal. Korean Patent Application Laid-Open No. 10-2011-0019804 also includes aluminum salts and Provides a method of preparing an organic-inorganic hybrid nanoporous body by reacting an organic ligand, but the specification required for use as an adsorbent for gas or moisture or a method for manufacturing in a form that is practically usable in the industry is not disclosed. There is a problem.

Korean Patent Application Publication No. 10-2011-0019804

It is an object of the present invention to provide a method of manufacturing an organic-inorganic nanoporous material having a remarkably high moisture adsorption amount.

Another object of the present invention is to provide a method of manufacturing an organic-inorganic nanoporous body having an adsorption amount superior to that of a conventional moisture adsorbent by overcoming the limitations of the conventional moisture adsorbent by a simple method, and an organic-inorganic nanoporous body manufactured therefrom.

An organic-inorganic nanoporous body manufacturing method according to an embodiment of the present invention includes an aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a first step of preparing an organic-inorganic nanoporous material precursor by mixing water. And a second step of crystallizing the organic-inorganic nanoporous material precursor.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the aluminum precursor is aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and One or two or more organic-inorganic nanoporous bodies selected from these hydrates.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the acid mixture may contain 3 to 25% by weight of succinic acid.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the molar ratio of the aluminum precursor: the acid mixture may be 1: 1 to 6.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the organic-inorganic nanoporous body precursor may further include an element.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the molar ratio of the aluminum precursor: urea may be 1:1 to 5.

In the method for manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention, the second step may be performed at 100 to 200° C. for 12 to 60 hours.

The present invention also provides an adsorbent, and the adsorbent according to the present invention includes the organic-inorganic nanoporous material according to an embodiment of the present invention.

The adsorbent including the organic-inorganic nanoporous material according to an embodiment of the present invention may be a moisture adsorbent.

In the organic-inorganic nanoporous body according to an embodiment of the present invention, the adsorbent may be capable of adsorbing water at least 400 mg per 1 g of the adsorbent in a range of 0.1 to 0.3 _{in a driving pressure (P/P 0 ).}

The present invention has the advantage of having a remarkably superior adsorption amount compared to the case of manufacturing without succinic acid by preparing an organic-inorganic nanoporous body including the step of reacting and crystallizing an acid mixture containing fumaric acid and succinic acid with an aluminum precursor. .

1 is a measurement of the moisture adsorption amount of the organic-inorganic nanoporous material according to the preparation example of the present invention and shows the result.
Figure 2 shows the nitrogen adsorption isotherm of the organic-inorganic nanoporous body according to the preparation example of the present invention.
3 shows the results of X-ray diffraction analysis of the organic-inorganic nanoporous body according to Preparation Example of the present invention.

Advantages and features of the embodiments of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout this specification.

The present invention is an aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a first step of preparing an organic-inorganic nanoporous material precursor by mixing water. And

It relates to a method for manufacturing an organic-inorganic nanoporous material comprising; a second step of crystallizing the organic-inorganic nanoporous material precursor.

The method for manufacturing an organic-inorganic nanoporous body according to the present invention has the advantage of being able to manufacture an adsorbent having an excellent adsorption amount compared to the conventional organic-inorganic nanoporous body by reacting an acid mixture containing fumaric acid and succinic acid with an aluminum precursor.

Specifically, in the case of manufacturing an organic-inorganic nanoporous body using only fumaric acid, which is known in the prior art, 400 mg per 1 g of the organic-inorganic nanoporous body is adsorbed based on moisture adsorption in the range of 0.1 to 0.3 _{driving pressure (P/P 0 ).} It was difficult to exceed the amount, and there was a limit to the amount of moisture adsorption due to the level of 350 to 370 mg.

However, in the case of preparing an organic-inorganic nanoporous body by partially mixing fumaric acid with succinic acid as in the present invention, there is an advantage in that water adsorption of 400 mg or more, more preferably 415 to 440 mg per 1 g of the organic-inorganic nanoporous body is possible. . This advantage is believed to be caused by affecting the pore size of the organic-inorganic nanoporous body produced by the molecular size of some mixed succinic acid.

In this respect, the acid mixture of the first step may contain 3 to 25% by weight, preferably 5 to 20% by weight, more preferably 7 to 14% by weight of succinic acid, and may contain the remainder of fumaric acid. . In this range, as described above, there is an advantage of achieving a high moisture absorption amount of 400 mg or more, preferably 420 mg or more per 1 g of the organic-inorganic nanoporous material. When succinic acid is added in a smaller amount than the above-described range, it is difficult to achieve the effect of improving the adsorption amount by adding succinic acid, and when succinic acid is added in a larger amount than the above-described range, there is a problem that the manufacturing yield of the organic-inorganic nanoporous material may decrease. have.

An organic-inorganic nanoporous body manufacturing method according to an embodiment of the present invention includes an aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a first step of preparing an organic-inorganic nanoporous material precursor by mixing water. At this time, the molar ratio of the aluminum precursor: the acid mixture may be 1: 1 to 6, preferably 1: 1.5 to 4, and within this range, the problem of remaining aluminum or acid mixture in the reaction solution after reaction can be minimized. However, it has the advantage of securing a yield above a certain level.

The aluminum precursor used at this time may be used without limitation if it is an aluminum salt soluble in water. As a specific and non-limiting example, the aluminum precursor is one or two selected from _{aluminum nitrate (Al (NO 3} ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) _{3) and hydrates thereof} It may be more than that, more preferably aluminum sulfate, but the present invention is not limited thereto.

In addition, the amount of water mixed in the first step is not limited if it is added in a range capable of reacting by dissolving the aluminum precursor and the acid mixture. However, 10 to 50 parts by weight of water may be mixed with respect to 1 part by weight of the total of the aluminum precursor and the acid mixture in order to achieve a yield of at least a certain level and prevent the problem of partially undissolved aluminum precursors, etc. This is not limited to this.

In the method of manufacturing an organic-inorganic nanoporous material according to an embodiment of the present invention, the organic-inorganic nanoporous material precursor of the first step may further include _{urea (CO(NH 2} ) _{2 ).} Through the addition of these elements, it is possible to adjust the pH in the second step. Specifically, the urea maintains its state when there is no separate heating, but when heated, hydrolysis occurs into ammonia and carbon dioxide. Considering the properties of these elements and the specific conditions of the second step described later, it means that when urea is added as a base, it does not have basicity in the first step, but it can be adjusted to have basicity in the second step to be described later. . Accordingly, after the aluminum and the ligand are formed in the first step, the aluminum ligand can act as a base only in the second step in which the aluminum ligand is crystallized. There is an advantage that sieve can be manufactured. For example, urea is hydrolyzed to produce ammonia slowly, and by controlling the nucleation of the organic-inorganic nanoporous material, it is possible to manufacture the organic-inorganic nanoporous material having high efficiency and crystallinity.

In this case, the urea may have an aluminum precursor: urea molar ratio of 1:1 to 5, preferably 1:1.5 to 4, based on the aluminum precursor, and in such a range, an excessive increase in pH may prevent other yield degradation. There is an advantage.

The method for manufacturing an organic-inorganic nanoporous body according to the present invention includes an aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a second step of crystallizing the organic-inorganic nanoporous material precursor after the first step of preparing the organic-inorganic nanoporous material precursor by mixing water. By going through such a crystallization step, an acid mixture coordinating to aluminum can grow into an organic-inorganic nanoporous body. The second step may be performed at 100 to 200 °C for 12 to 60 hours, and when the temperature of the second step is lower than 100 °C, there is a problem that the reaction rate is too slow and the reaction efficiency is excessively decreased, and the second step When the temperature of the step is higher than 200 ℃, there is a problem that the reaction rate is too fast, impurities can be easily mixed.

The method of manufacturing an organic-inorganic nanoporous body according to an embodiment of the present invention may further include filtering, purifying, and drying the product generated after the second step. There is an advantage in that it is possible to manufacture high-purity organic-inorganic nanoporous bodies by excluding impurities mixed through this process. At this time, the drying may be performed at 100 to 200° C., and there is an advantage of further improving the moisture adsorption power of the organic-inorganic nanoporous body manufactured with excellent drying effect while preventing damage to the organic-inorganic nanoporous body within this range. .

As described above, the organic-inorganic nanoporous body manufactured through the above-described steps has the advantage of excellent moisture adsorption ability. Specifically, the average diameter of the pores formed in the organic-inorganic nanoporous body may be 0.3 to 15 nm, specifically 0.4 to 1.2 nm, and more specifically 0.45 to 1.0 nm. If the size of the pores is too small, it is difficult for moisture to penetrate and the moisture adsorption power is deteriorated. If the pore size is too large, the specific surface area may decrease, resulting in a problem that the adsorption power is rather reduced. In addition, pore size is a factor that can determine the driving pressure range during moisture adsorption. If the pores are too small or too large, the moisture adsorption driving moisture pressure may deviate from the driving pressure. However, the organic-inorganic nanoporous body according to an embodiment of the present invention has the advantage of exhibiting excellent moisture adsorption ability by satisfying the average pore diameter in the above-described range.

The present invention also provides an adsorbent, and the adsorbent according to the present invention includes the organic-inorganic nanoporous material according to an embodiment of the present invention. The organic-inorganic nanoporous body included in the adsorbent according to the present invention is characterized in that it includes nanopore of a certain size through regular arrangement of aluminum and organic ligands, and thus has a remarkably high moisture adsorption amount and moisture adsorption rate. .

_{Specifically, the adsorbent according to the present invention has a driving pressure (P/P 0} ) of 0.1 to 0.3 compared to an adsorbent including an organic/inorganic nanoporous material manufactured by a conventionally known method, and the amount of moisture adsorption based on 1 g of the adsorbent is It is characterized by being superior to 20 mg or more. More specifically, the adsorbent according to the present invention has the advantage of capable of adsorbing water of 400 mg or more, preferably 415 to 440 mg per 1 g of the adsorbent.

Further, the adsorbent according to the present invention can be used not only as moisture but also as a gas adsorbent such as carbon dioxide, and the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[Production Example 1]

Aluminum sulfate (Al ₂ (SO ₄ ) ₃ 18H ₂ O) 1.33 g (2.1 mmol), succinic acid 0.0236 g (0.2 mmol), fumaric acid 0.44 g (3.8 mmol), and urea 0.24 g (4 mmol) with 40 g of deionized water Mix and stir for 10 minutes. Thereafter, this was put into an autoclave reactor, reacted at 110° C. for 48 hours, and then cooled to room temperature. Then, the white precipitate was collected through filtration, washed repeatedly 5 times with 20 ml of deionized water, and dried in an oven at 100° C. for 24 hours to obtain an organic-inorganic nanoporous body.

[Production Examples 2 to 9]

It was prepared in the same manner as in Preparation Example 1, but by changing the content ratio of succinic acid and fumaric acid as shown in Table 1 below, each organic-inorganic nanoporous body was prepared.

[Comparative Production Example 1]

It was prepared in the same manner as in Preparation Example 1, but without adding succinic acid, but adding 0.46 g of fumaric acid to prepare an organic-inorganic nanoporous body.

Sample name Succinic acid Fumaric acid Manufacturing Example 1 AlFS5 0.0236g (0.20 mmol) 0.4400g (3.80 mmol) Manufacturing Example 2 AlFS7 0.0330g (0.28 mmol) 0.4315g (3.72 mmol) Manufacturing Example 3 AlFS9 0.0425 g (0.36 mmol) 0.4222 g (3.64 mmol) Manufacturing Example 4 AlFS10 0.0472g (0.40 mmol) 0.4176g (3.60 mmol) Manufacturing Example 5 AlFS11 0.0519g (0.44 mmol) 0.4130g (3.56 mmol) Manufacturing Example 6 AlFS12 0.0566g (0.48 mmol) 0.4083g (3.52 mmol) Manufacturing Example 7 AlFS13 0.0614 g (0.52 mmol) 0.4037 g (3.48 mmol) Manufacturing Example 8 AlFS15 0.0730g (0.62 mmol) 0.3900 g (3.40 mmol) Manufacturing Example 9 AlFS20 0.0944g (0.80 mmol) 0.3700g (3.20 mmol) Comparative Preparation Example 1 AlF 0 0.4600g (4.00 mmol)

Organic or inorganic Nanoporous Decision confirmation

The organic-inorganic nanoporous bodies prepared in Preparation Example and Comparative Preparation Example were analyzed through X-ray diffraction analysis, and the results are shown in FIG. 1.

Referring to FIG. 1, it can be seen that crystals were well formed in both the Preparation Example and the Comparative Preparation Example.

Organic/inorganic nano Specific surface area Measure

The specific surface area of the organic-inorganic nanoporous body prepared in Preparation Example and Comparative Preparation Example was measured using a nitrogen adsorption isotherm, and the results are shown in FIGS. 2 and 2.

Sample name V _p (cm ³ g ^-1 ) d _p (nm) S _BET (m ² g ^-1 ) Manufacturing Example 1 AlFS5 0.4917 0.7 1182 Manufacturing Example 2 AlFS7 0.5006 0.7 1217 Manufacturing Example 3 AlFS9 0.5032 0.7 1223 Manufacturing Example 4 AlFS10 0.4834 0.7 1167 Manufacturing Example 5 AlFS11 0.4890 0.7 1198 Manufacturing Example 6 AlFS12 0.4808 0.7 1166 Manufacturing Example 7 AlFS13 0.4785 0.7 1170 Manufacturing Example 8 AlFS15 0.4830 0.7 1147 Manufacturing Example 9 AlFS20 0.4615 0.7 1083 Comparative Preparation Example 1 AlF 0.4547 0.7 1100

Referring to Table 2, it can be seen that the organic-inorganic nanoporous body according to the Preparation Example generally exhibits a higher specific surface area compared to the organic-inorganic nanoporous body of the Comparative Production Example. It can be seen that it shows a lower specific surface area.

Organic/inorganic nano Moisture absorption summary

In order to confirm the moisture adsorption amount of the organic-inorganic nanoporous materials prepared in Preparation Example and Comparative Preparation Example, moisture adsorption isotherm analysis was performed at 25° C., and the results are shown in Table 3 and FIG. 3.

Referring to FIG. 1, it can be seen that when succinic acid is contained in 7 to 15% by weight, moisture absorption is higher than that of conventional fumaric acid alone.

Sample P/P ₀ H ₂ O uptake (mg/g) AlF 0.1 10.42 416.0 0.3 426.37 AlFS 5 0.1 9.67 406.4 0.3 416.04 AlFS 7 0.1 13.20 420.0 0.3 433.22 AlFS 9 0.1 15.03 432.8 0.3 447.83 AlFS 10 0.1 10.78 432.1 0.3 442.91 AlFS 11 0.1 14.32 429.3 0.3 443.61 AlFS 12 0.1 14.33 435.9 0.3 450.22 AlFS 13 0.1 11.10 429.3 0.3 440.38 AlFS 15 0.1 18.41 401.8 0.3 420.19 AlFS 20 0.1 8.01 410.6 0.3 418.61

Claims (10)

Aluminum precursor; An acid mixture comprising fumaric acid and succinic acid; And a first step of preparing an organic-inorganic nanoporous material precursor by mixing water. And
Including; a second step of crystallizing the organic-inorganic nanoporous material precursor,
The acid mixture comprises 7 to 14% by weight of succinic acid and the balance of fumaric acid,
A method for manufacturing an organic-inorganic nanoporous body, characterized in that it has an amount of moisture adsorption of 420 mg or more per 1 g in a range of 0.1 to 0.3 of a driving pressure (P/P0). The method of claim 1,
The aluminum precursor is aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and one or more organic-inorganic nanoporous bodies selected from hydrates thereof Way. The method of claim 1,
The acid mixture is a method for producing an organic-inorganic nanoporous body comprising 3 to 25% by weight of succinic acid. The method of claim 1,
The aluminum precursor: the molar ratio of the acid mixture is 1: 1 to 6, the organic-inorganic nanoporous body manufacturing method. The method of claim 1,
The organic-inorganic nanoporous body precursor is an organic-inorganic nanoporous body manufacturing method further comprising an element. The method of claim 5,
The aluminum precursor: the molar ratio of the urea is 1:1 to 5 organic-inorganic nanoporous body manufacturing method. The method of claim 1,
The second step is a method of manufacturing an organic-inorganic nanoporous body performed at 100 to 200 °C for 12 to 60 hours. An adsorbent comprising the organic-inorganic nanoporous material according to any one of claims 1 to 7. The method of claim 8,
The adsorbent comprises an organic-inorganic nanoporous material that is a moisture adsorbent. delete

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