KR20210124775A - Manufacturing method of porous body using natural mineral resources and preparation of porous body using same - Google Patents

Abstract

The present invention relates to a method for manufacturing a porous body using natural mineral resources and manufacturing a porous body using the same. The present invention enables a ceramic porous to be manufactured from natural mineral resources through a simple aging and recrystallization process that does not require high-temperature/high-pressure devices or a complicated procedure, thereby having an advantage in terms of manufacturing energy. To this end, the present invention comprises: 1) a step for pulverizing natural minerals; 2) a step for adding a solvent and alkali to the mineral pulverized in step 1 and allowing a ripening reaction to proceed; 3) a step for crystallizing the reactant obtained in step 2 by adding distilled water thereto; and 4) a step for obtaining a porous body by washing and drying the crystals obtained in step 3.

Description

Method for manufacturing a porous body using natural mineral resources and manufacturing a porous body using the same

The present invention relates to a method for manufacturing a porous body using natural mineral resources and to manufacturing a porous body using the same.

In general, a natural layered mineral is a mineral in which an aluminum octahedral layer is combined and laminated in a certain form on the upper and lower portions of the two-dimensionally developed silica tetrahedral layer. It is classified as a type or 1:1 type structure.

Typical layered minerals with a 2:1 structure include mica, vermiculite, and montmorillonite, and minerals with a 1:1 structure include serpentine and kaolin.

Among them, kaolin (kaolin) is a mineral whose demand is rapidly increasing worldwide for paper and ceramics. Since ore is being discarded, it is urgent to develop technology to utilize it.

On the other hand, in the field of ceramics manufacturing, layered minerals are mainly used as raw materials for silica and alumina. Since these layered minerals are stable and inactive, in most cases, they are calcined at a high temperature or after giving activity through acid or alkali treatment, It is used as raw material.

In particular, since the conventional layered mineral has a chemical composition similar to that of zeolite, it is widely used to synthesize a zeolite porous body through hydrothermal synthesis with alkali.

However, the method of synthesizing zeolite using the layered mineral as a raw material as described above is known to be possible only when the reaction conditions are very strict and generally react for a long time under high temperature and high pressure conditions of 100° C. or more. In addition, the manufacturing technology requires expensive equipment or complicated equipment, and since the process is complicated, it is also a problem in terms of economy.

Accordingly, natural lamellar minerals are limitedly used only in fields using their unique powder properties, and are unsuitable for use as raw materials for products requiring strict manufacturing conditions of high temperature and high pressure, such as zeolite.

Therefore, there is a need for research on a method that can achieve high added value by manufacturing a ceramic porous body by a simple method without the need for a high-temperature/high-pressure device or complicated process from an unprocessed low-cost natural mineral resource.

1. Republic of Korea Patent Registration 10-1869394 (2018.06.21. Announcement)

It is an object of the present invention to provide a method for manufacturing a ceramic porous body from natural mineral resources in a simple manner without the need for high-temperature/high-pressure devices or complicated processes.

In addition, another object of the present invention is to provide a porous body manufactured by the above method and having superior properties than conventional zeolites.

In order to achieve the above object, the present invention comprises the steps of pulverizing natural minerals (first step); The step of aging reaction by adding a solvent and alkali to the mineral pulverized in the first step (second step): crystallizing by adding distilled water to the reactant of the second step (third step); and washing and drying the crystals of the third step to obtain a porous body (fourth step); It provides a method for manufacturing a porous body using natural mineral resources, including

In addition, the present invention provides a porous body utilizing a natural mineral resource, characterized in that manufactured by the method for manufacturing a porous body utilizing the natural mineral resource.

The present invention can manufacture a ceramic porous body from natural mineral resources through a simple aging and recrystallization process, and there is no need for a high-temperature/high-pressure device or a complicated process, which is advantageous in terms of manufacturing energy.

In addition, the porous body prepared through the above method has a higher specific surface area than conventional zeolite and has excellent ion exchange properties, so that it can be usefully used as a catalyst, an adsorbent, a molecular sieve, an ion exchanger, and a membrane material.

In addition, since kaolin, which is a low-cost natural mineral resource that has not been processed, can be used as a raw material, it is possible to not only improve the added value of mineral resources but also to create demand for new raw materials in the ceramic field.

1 is a view schematically showing a method for manufacturing a porous body using natural mineral resources according to the present invention.
2 is a view showing the result of analyzing the microstructure change of the porous body prepared according to the present invention by FE-SEM.
3 is a view showing the results of XRD analysis comparing the crystal structure of the porous body prepared according to the present invention with that of sodalite.
4 is a view showing the results of XRD analysis comparing the crystal structure of the porous body prepared according to the present invention with the crystal structure of zeolite and sodalite.
5 is a view showing a specific surface area analysis result of a porous body prepared according to the present invention.
6 is a view showing the cation exchange capacity analysis results according to the experimental conditions (Experiment 1 (a) to Experiment 3 (c)) of the porous body prepared according to the present invention.

Hereinafter, the present invention will be described in detail.

The present inventors have identified an optimal manufacturing method capable of manufacturing a ceramic porous body from unprocessed low-cost raw material kaolin through simple aging and recrystallization without the need for high-temperature/high-pressure equipment or complicated processes (FIG. 1), the method The present invention has been completed by revealing that the porous body produced through zeolite has a higher specific surface area than conventional zeolites and has excellent ion exchange properties, which can be usefully used as catalysts, adsorbents, molecular sieves, ion exchangers, and membrane materials.

The present invention comprises the steps of pulverizing natural minerals as shown in FIG. 1 (first step); The step of aging reaction by adding a solvent and alkali to the mineral pulverized in the first step (second step): crystallizing by adding distilled water to the reactant of the second step (third step); and washing and drying the crystals of the third step to obtain a porous body (fourth step); It provides a method for manufacturing a porous body using natural mineral resources, including

The natural minerals are pumice, mica, vermiculite, montmorillonite, bentonite, serpentine, kaolin, muscovite, ilealite (Anorthite) and At least one may be selected from the group consisting of mesolithic stone (Andesine), preferably kaolin (kaolin), but is not limited thereto.

In addition, the alkali is at least one selected from the group consisting of NaOH, KOH and BaOH, and preferably NaOH may be used, but is not limited thereto.

In addition, in the second step, the mineral, the solvent, and the alkali are each added in a mass ratio of 1: (0.05 to 2): (0.5 to 30), and the solvent is ethylene glycol, isopropyl alcohol ( Isopropyl alcohol) and at least one may be selected from the group consisting of distilled water, and preferably, ethylene glycol may be used, but is not limited thereto.

In addition, the aging reaction of the second step may be performed at 30 to 100° C. for 2 to 10 hours, preferably at 50° C. for 4 hours, but is not limited thereto.

In addition, distilled water may be added so that the alkali concentration becomes 1 to 15M in the third step, and distilled water may be added so that the alkali concentration is preferably 3M, but is not limited thereto.

In addition, the crystallization of the third step may be performed at 50 to 150° C. for 5 to 20 hours, preferably at 90° C. for 12 hours, but is not limited thereto.

In addition, drying in the fourth step may be performed at 50 to 150° C. for 10 to 30 hours, preferably at 80° C. for 24 hours, but is not limited thereto.

At this time, if the aging, crystallization and drying conditions as described above, the mass ratio conditions of minerals, solvents and alkalis, and the alkali concentration conditions according to the addition of distilled water are exceeded, the porous body according to the present invention is not properly formed, resulting in excellent specific surface area and ion exchange characteristics. It may not be possible to have it, or the yield of the target product may be significantly lowered, which may cause uneconomical problems.

In addition, the present invention provides a porous body utilizing a natural mineral resource, characterized in that manufactured by the method for manufacturing a porous body utilizing the natural mineral resource.

The porous body prepared according to an embodiment of the present invention has a specific surface area more than 10 times higher than that of a conventional reagent-grade zeolite (Zeolite 4A (Manufacturer: Wako)) porous body, and has excellent ion exchange capacity characteristics. It can be used in various fields such as molecular sieves, ion exchangers, and membrane materials.

Therefore, the present invention can convert kaolin, a low-cost mineral resource, into a raw material without the need for high-temperature/high-pressure equipment or complicated processes, so it is possible to not only improve the added value of mineral resources but also create demand for new raw materials in the ceramic field. .

Hereinafter, the present invention will be described in more detail through examples. These examples are only for explaining the present invention in more detail, and it is to those of ordinary skill in the art to which the present invention pertains that the scope of the present invention is not limited by these examples according to the gist of the present invention. it will be self-evident

< Example 1> Manufacture of porous body using kaolin

1. crush

As a step for controlling the particle size of kaolin, particles of unprocessed kaolin (Sancheong, Gyeongsangnam-do) were pulverized using zirconia balls.

Specifically, kaolin powder was prepared by dry grinding kaolin, 10 mm zirconia balls, and 20 mm zirconia balls in a weight ratio of 1:1:1 using table ball milling for 24 hours.

2. ripening

As a step for forming the seed of the porous body, ethylene glycol, NaOH, and the pulverized kaolin powder were mixed/dispersed.

Specifically, 120 g of ethylene glycol solvent, 21 g of kaolin, and 24 g of NaOH were added to a 500 ml wide-mouth bottle made of polyethylene (Poly Ethylene, PE) as shown in Table 1 below under conditions of 50 °C and 150 rpm. The aging process was performed by stirring for 4 hours.

3. Crystallization

As a step for crystallization of the porous seed formed in the aging process, distilled water was added to the mixture prepared in the aging step to adjust the concentration of NaOH in the solution.

Specifically, as shown in Table 1 below, the concentration of distilled water and NaOH in the mixture was 12 M (input distilled water amount: 50 g, hereinafter 'Experiment 1'), 6 M (input distilled water amount: 100 g, hereinafter 'Experiment 2') ), 3 M (input distilled water amount: 200 g, hereinafter 'Experiment 3') was controlled to be added, and crystallization was performed for 12 hours at 90° C. and 200 rpm.

4. Wash and dry

After the crystallization process is performed, as a step for washing and drying the reactants, after collecting the crystallized sample, ultrasonic washing is performed for 15 minutes using distilled water 3 times, and the washed sample is placed on a sus tray ) and dried at 80 °C for 24 hours.

< Experimental example 1> FE- SEM measurement analysis

The samples of Experiments 1 to 3 prepared in Example 1 and kaolin untreated were subjected to morphological analysis using a Mira3 (FE-SEM) scanning electron microscope of Tescn at an acceleration voltage of 20 kV.

As a result, it was confirmed that spherical fine particles of about 700 nm were formed in Experiments 1 to 3 compared to kaolin without any treatment. In addition, as the concentration of NaOH decreased as the amount of distilled water was increased, it was confirmed that a spherical shape of a smooth shape was formed (FIG. 2).

However, it was confirmed that when the amount of distilled water input in the crystallization step was 300 g or more, the synthesis of the porous body became impossible.

< Experimental example 2> EDS analysis

Component analysis of the samples of Experiments 1 to 3 was performed by point scan using EDS (Energy Dispersive X-ray Spectroscopy) equipment attached to the FE-SEM equipment.

As a result, each sample obtained the composition shown in Table 2 below, and it was confirmed that the ratio of Si/Al of each sample was about 1 as shown in Table 3.

Composition (atomic) % ) sample name O Na Al Si K Ca Ti Fe Cu Experiment 1 47.80 7.37 20.33 22.94 - - - 0.83 1.1 Experiment 2 70.82 4.67 8.23 13.64 2.54 - - 0.035 0.07 Experiment 3 67.26 8.39 11.79 11.70 0.09 0.12 0.05 0.45 0.12

sample name Si /Al Experiment 1 1.12 Experiment 2 1.67 Experiment 3 0.99

This was confirmed to be similar to the chemical formulas of the porous bodies of Sodalite and Zeolite A reported previously as shown in Table 4 below.

Porous body name chemical formula structure Zeolite 4A Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ Cubic Zeolite 4A
(K-exchanged, dehydrated) K ₃ Na ₉ Al ₁₂ Si ₁₂ O ₄₈ Cubic Hydro Sodalite Na ₈ H ₆ Al ₆ O ₂₈ Si ₆ Cubic Sodalite basic Na ₈ H ₆ Al ₆ O ₂₈ Si ₆ Cubic

< Experimental example 3> XRD analysis

For the samples 1 to 3 prepared in <Example 1>, XRD (X-Ray Diffraction) analysis was performed with Cu Kα x-rays of 40 kV and 40 mA under the conditions of a scan speed of 0.007 °/S and a step size of 0.028 °. As a result, it was confirmed to have a peak (peak) similar to that of sodalite.

However, the samples of Experiments 1 to 3 showed a crystal structure different from that of sodalite when it was observed that peaks were generated at positions of 8.9, 32.5, 34.4, 34.8, 42.5, 43.1, 51.7, 58.0, 69.3, and 77.9°, unlike sodalite. In particular, it was confirmed that the intensity of the peaks located at 8.9, 34.8, and 43.1° was changed as the concentration of NaOH decreased as the amount of distilled water added was increased, especially in the crystallization step (FIG. 3).

In addition, conventionally known porous zeolite [Zeolite A (manufacturer: Wako), Zeolite Na-Y (Uytterhoeven, JB; van den Bossche, E.; Mortier, WJ, Zeolites , 4, 41 - 44 (1984)), Zeolite Na- X (Ibrahim, TK; Hawa, AIF; Evmerides, NP; Dwyer, J.; Beagley, B., Kristallografiya , 24, 461 - 468 (1979)), Zeolite ZSM-10 (Dorset, DL, Zeitschrift) future Kristallographie (1979-2010), 21, 260 - 265 (2006))] and it was confirmed that the intensity and position of the peak were different in the XRD comparison analysis result (FIG. 4).

Therefore, it was confirmed that the new porous bodies having a crystal structure similar to that of sodalite were synthesized in Experiments 1 to 3 porous bodies prepared in <Example 1>.

< Experimental example 4> specific surface area ( Brunauer Emmett Teller; BET) analysis

Experiments 1 to 3 samples prepared in <Example 1> were treated at 350° C. for 480 minutes to completely evaporate organic matter and moisture, and then the specific surface area was analyzed using a specific surface area analyzer using nitrogen adsorption. Compared with reagent grade zeolite (Zeolite 4A (manufacturer: Wako)), it was confirmed that the specific surface area was improved as shown in Table 5 and FIG. 5 below.

In particular, it was confirmed that the specific surface area was further improved as the concentration of NaOH was decreased by increasing the amount of the input distilled water controlled in the crystallization step.

sample name BET specific surface area (Surface Area)(m) ³ /g) Zeolite 4A 1.04 Experiment 1 4.8735 Experiment 2 6.8976 Experiment 3 10.6147

< Experimental example 5> Cation exchange capacity

0.2M concentration of MgCl ₂ After preparing an aqueous solution, it was stirred with the samples of Experiments 1 to 3 for 30 minutes to perform cation exchange, and then recovered and XRD analysis was performed.

As a result, it was confirmed that the peak intensity of 31.8 and 45.6°, which is the main peak of NaCl, increased, which means that Cl ^- in the aqueous solution and Na ⁺ of the porous body react with the cation exchange reaction to form NaCl (Fig. 6a-c).

Therefore, it was confirmed that the porous bodies 1 to 3 prepared in <Example 1> had cation exchange ability.

Claims (10)

pulverizing natural minerals (first step);
The step of aging reaction by adding a solvent and alkali to the mineral pulverized in the first step (second step);
crystallizing by adding distilled water to the reactant of the second step (third step); and
washing and drying the crystals of the third step to obtain a porous body (fourth step); A method for manufacturing a porous body using natural mineral resources, including The method of claim 1,
The natural minerals are pumice, mica, vermiculite, montmorillonite, bentonite, serpentine, kaolin, muscovite, ilealite (Anorthite) and A method for manufacturing a porous body using natural mineral resources, characterized in that at least one selected from the group consisting of andesine. The method of claim 1,
The alkali is a method for producing a porous body using natural mineral resources, characterized in that at least one selected from the group consisting of NaOH, KOH and BaOH. The method of claim 1,
In the second step, the mineral, the solvent, and the alkali are each added in a mass ratio of 1: (0.05 to 2): (0.5 to 30). A method for producing a porous body using natural mineral resources. The method of claim 1,
In the second step, the solvent is at least one selected from the group consisting of ethylene glycol, isopropyl alcohol, and distilled water. A method for manufacturing a porous body using natural mineral resources. The method of claim 1,
A method for producing a porous body using natural mineral resources, characterized in that the aging reaction of the second step is performed at 30 to 100° C. for 2 to 10 hours. The method of claim 1,
A method for producing a porous body using natural mineral resources, characterized in that distilled water is added so that the alkali concentration becomes 1 to 15M in the third step. The method of claim 1,
The third step of crystallization is a method for producing a porous body using natural mineral resources, characterized in that it is carried out at 50 to 150 ℃ for 5 to 20 hours. The method of claim 1,
Drying in the fourth step is a method for manufacturing a porous body using natural mineral resources, characterized in that it is performed at 50 to 150 ℃ for 10 to 30 hours. A porous body using a natural mineral resource, characterized in that it is manufactured by the method for manufacturing a porous body using the natural mineral resource according to any one of claims 1 to 9.

Images