KR101173213B1 - Method for manufacturing functional materials for adsorption of polluant and functional materials manufactured by the same - Google Patents

Abstract

The present invention comprises the steps of: i) mixing the zeolite precursor or zeolite powder, binder and water to form a zeolite coating solution; Ii) coating the zeolite coating solution on the surface of the material to be coated; And iii) a method for preparing a pollutant adsorption material comprising the step of immobilizing a coated zeolite on the target surface, a pollutant adsorption material prepared by the method, and a method for adsorbing pollutants using the same. According to the present invention, by using a conventional construction material and the like, the zeolite coating solution diluted with zeolite precursor or zeolite powder on the surface of the thin film can be coated by a simple method to exhibit high efficiency of adsorption and removal of contaminants. It is possible to provide a material for adsorbing pollutants.

Zeolite, Pollutant, Heavy Metal, Material, Nonpoint Source

Description

METHOD FOR MANUFACTURING FUNCTIONAL MATERIALS FOR ADSORPTION OF POLLUANT AND FUNCTIONAL MATERIALS MANUFACTURED BY THE SAME}

The present invention relates to a method for producing a material for adsorption of pollutants and a functional material for adsorption of contaminants prepared according to the present invention. More particularly, pollutants such as heavy metals included in air, soil, water, etc. act as serious environmental hazards. It relates to a functional material and a method for producing the same that can be adsorbed and removed with high efficiency.

Recently, due to the advancement and diversification of industrial development, environmental pollution such as soil, air, and water generated by various wastewater, slugs, wastes, etc., which are inevitably discharged from factories and workplaces, becomes more and more serious.

In particular, the nonpoint source is leaked by rainfall, and the pollutants not only deteriorate the water quality, but also enter the ecosystem and cause serious toxicity to various aquatic plants and animals. If these pollutants enter the water system, it will cause eutrophication of the water system and cause fatal damage to the ecosystem and living environment due to heavy metals and hardly degradable organic substances.

In addition, on the surface of the impervious layer at the beginning of the rainfall, the load of pollutants increased due to the initial washing effect, and the concentration of heavy metals also increased. In particular, these heavy metals are not only difficult to remove biologically, but also accumulate in living organisms and ecosystems, causing serious dangers.

In order to solve the environmental pollution problem, various researches are being conducted, and as a part, non-point source reduction technologies currently applied at home and abroad can be classified into storage type, infiltration type, vegetation type, device type, and treatment type. . Most of these technologies focus on reducing organic pollutants, which are not suitable for treating pollutants such as heavy metals accumulated in the ecosystem as described above.

Existing methods for removing or reducing contaminants such as heavy metals include a method of adsorbing and removing contaminants such as heavy metals using a medium having an adsorption function or an adsorbent. However, such an adsorption method has a disadvantage that the price of the media is not only expensive but also difficult to recycle, and it is difficult to be practical, such as an additional device for fixing the media.

Accordingly, there is still a need for materials for adsorption and removal of contaminants with high physical and chemical stability while maintaining good contaminant adsorption and removal efficiency.

On the other hand, the zeolite used as a material having adsorption functionality has a loosely bonded crystal of atoms, so that the skeleton remains intact even when the water filling the space is released at a high temperature, so that other particulate matter can be adsorbed. It is known to be big. However, since zeolite is used as a powder or refined pellet, etc., it is difficult to be used as a construction material in terms of bonding strength and strength.

The present invention is to solve the above problems, by coating the zeolite coating liquid formed by diluting the zeolite precursor or the zeolite powder with a thin film on the surface of the existing material can exhibit excellent adsorption efficiency of pollutants such as heavy metals, pollution It is an object of the present invention to provide a method for preparing a material for adsorption of substances, a material for adsorption of pollutants thus prepared and a method for adsorbing pollutants using the same.

The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention, which are not mentioned above, can be understood by the following description, and will be more clearly understood by the embodiments of the present invention. It will also be readily apparent that the objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

One embodiment of the present invention for achieving the above object is iii) mixing the zeolite precursor or zeolite powder, binder and water to form a zeolite coating solution; Ii) coating the zeolite coating solution on the surface of the material to be coated; And iii) immobilizing the zeolite coated on the target surface.

Another embodiment of the present invention provides a material for adsorbing contaminants prepared according to the manufacturing method.

Another embodiment of the present invention provides a pollutant adsorption method comprising contacting the pollutant adsorption material with a pollutant-containing medium.

According to the present invention, it is possible to impart the functionality of the adsorption and removal of contaminants such as heavy metals by using a conventional construction material and the like through the zeolite coating on the surface. In particular, by using the filter medium, curb around the road, sidewalk blocks, etc. used in the existing non-point pollutant treatment apparatus, it is possible to efficiently remove the non-point pollutants generated on the road surface of the impermeable layer.

The functional material according to the present invention can exhibit high efficiency of adsorption and removal of contaminants such as heavy metals, and has excellent physical and chemical properties, and thus is useful for extracting and removing contaminants such as heavy metals accumulated in soil, water or air. Can be applied.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 shows a process flow diagram of a method of manufacturing a contaminant adsorption material according to an embodiment of the present invention.

Referring to Figure 1, the manufacturing method of the material for adsorption of contaminants according to an embodiment of the present invention comprises the steps of: i) mixing the zeolite precursor or zeolite powder, binder and water to form a zeolite coating solution; Ii) coating the zeolite coating solution on the surface of the material to be coated; And iii) immobilizing the coated zeolite on the target surface.

According to the present invention, the zeolite coating solution formed by diluting either the zeolite precursor or the zeolite powder can be coated with a thin film on a material to be coated, for example, various conventional construction materials, to impart functionality of adsorption and removal of contaminants. Can be.

In the step iii), the zeolite coating liquid may be formed using either zeolite precursor or zeolite powder.

When the zeolite coating solution is formed using the zeolite precursor, the zeolite precursor may be prepared by mixing silica (SiO ₂ ) source material, alumina (Al ₂ O ₃ ) source material and water.

The silica (SiO ₂ ) source material and the alumina (Al ₂ O ₃ ) source material serve to form a skeleton of the zeolite. As the silica (SiO ₂ ) source material that can be used in the present invention, sodium silicate (Na ₂ CO ₃ ) is preferable, and as the alumina (Al ₂ O ₃ ) source material, sodium aluminate (NaAlO ₂ ) is preferable.

In one embodiment, the zeolite precursor comprises 10-20 wt.% Silica (SiO ₂ ) source material, 10-15 wt.% Alumina (Al ₂ O ₃ ) source material and the balance water, based on the total weight. do.

When the content of the silica (SiO ₂ ) source material and the alumina (Al ₂ O ₃ ) source material is less than the above range, there is a possibility that the economic efficiency is very low due to a decrease in yield, and when the content exceeds the above range, the precursor is reduced due to the decrease of the solvent. Gel formation may be difficult.

It is preferable that water is distilled water.

In one embodiment, the zeolite precursor may further comprise a molten salt. Molten salt replaces the role of a solvent in the zeolite synthesis, and ions can be transported in the molten state.

The molten salt is preferably used in consideration of the melting temperature of the molten salt and the heat treatment temperature in the subsequent immobilization step. For example, when the heat treatment is generally performed at a high temperature of 300 ° C. or higher in the immobilization step, it is preferable to add molten salt to the zeolite precursor to facilitate zeolite synthesis and immobilization. However, when the heat treatment temperature is generally less than 300 ° C., the addition of molten salt may interfere with the zeolite synthesis in the precursor.

Molten salts that can be used in the present invention are potassium chloride (KCl), potassium fluoride (KF), potassium iodide (KI), sodium chloride (NaCl), sodium iodide (Nal), sodium carbonate (Na ₂ CO ₃ ) and sodium sulfate (Na ₂ It is preferably at least one selected from the group consisting of SO ₄ ).

In one embodiment, the zeolite precursor is based on the total weight of 10 to 20% by weight of silica (SiO ₂ ) source material, 10 to 15% by weight of alumina (Al ₂ O ₃ ) source material, 5 to 10 parts by weight Molten salt and the balance of water.

If the content of the molten salt is less than the above range it may be difficult to fully play the role of the solvent, if it exceeds the above range may interfere with the zeolite synthesis rather there is a fear that the recovery of the final product is reduced.

In one embodiment, the silica (SiO ₂ ) source material, alumina (Al ₂ O ₃ ) source material, water, and optionally the molten salt is mixed and stirred, then left to stand at room temperature for 8 to 48 hours to mature It may further include.

When forming a zeolite coating liquid using a zeolite powder, a zeolite powder can use what is marketed.

In step iii), the zeolite coating solution is formed by mixing zeolite precursor or zeolite powder, binder and water.

Zeolite precursor or zeolite powder is preferably contained 5 to 50% by weight based on the total weight of the zeolite coating liquid.

When the content of the zeolite precursor or the zeolite powder is less than the above range, the concentration of the zeolite may be lowered, so that the coating may not be performed at a sufficiently high efficiency. When the zeolite precursor or the zeolite powder is exceeded, the viscosity may be excessively increased so that the coating workability may decrease. have.

In the present invention, the zeolite coating solution formed by diluting the zeolite precursor or the zeolite powder in this way can be coated with a thin film on an existing construction material or the like to produce a material having high efficiency of adsorption and removal of contaminants by a practical method.

The binder may form a zeolite coating layer by immobilizing the coated zeolite when the zeolite coating liquid is coated on the object.

The binder that can be used in the present invention is preferably at least one selected from the group consisting of tetraethylorthosilicate (TEOS), water glass, polyethyleneglycol (PEG) and epoxy resin.

When forming a zeolite coating liquid using a zeolite precursor, tetraethyl orthosilicate (TEOS) is preferably used as a binder in terms of enhancing physical properties and improving workability.

In addition, the binder is preferably appropriately selected in consideration of the coated zeolite immobilization method described below.

The binder is preferably contained 5 to 15% by weight based on the total weight of the zeolite coating liquid.

When the content of the binder is less than the above range, there is a concern that the coated zeolite may not be immobilized to a sufficient extent. When the content of the binder exceeds the above range, the mixing of the binder and the zeolite precursor or the zeolite powder becomes difficult, resulting in deterioration of coating workability. There is.

The zeolite coating liquid is formed by mixing the zeolite precursor or zeolite powder, the binder and the balance of water. Mixing methods and times can be carried out by appropriate selection as known in the art.

In the present invention, by coating the zeolite coating solution on the surface of the existing material it is possible to form a functional material having the ability to adsorb pollutants such as heavy metals.

The material to be coated is not particularly limited, and examples thereof include various shaped articles, media for pollutant treatment devices, curbs or sidewalk blocks around roads, and the like.

In addition, the shape or size of the material to be coated is not particularly limited, and spherical or flat surfaces are preferable in terms of coating efficiency.

As such, by using a variety of existing materials, it is possible to form a functional material that can be used to remove non-point pollutants, which are efficient and have enhanced properties in an easy manner.

In step ii), the zeolite coating liquid may be coated on the material to be coated by a method such as dip coating or spray coating.

The coating method may be appropriately selected depending on the surface area of the material to be coated, the form of the material, and the viscosity of the zeolite coating liquid.

For example, if the surface area of the material to be coated is small or the viscosity of the coating liquid is high, the dip coating method may be appropriate. If the material is not spherical, the spray coating may be appropriate if the surface is uneven. .

After coating, the method may further include drying the zeolite coating liquid coated on the material surface.

Next, in step iii), the zeolite coated on the material surface is immobilized.

The step of immobilizing the zeolite may be carried out by heat treatment or drying.

Zeolite immobilization by heat treatment or drying may be appropriately selected depending on the properties of the coated material and the molten salt contained in the zeolite precursor.

In one embodiment, in particular, when the zeolite coating liquid formed by using a zeolite precursor including a molten salt is coated, zeolite synthesis and immobilization may be simultaneously performed by heat treatment.

The heat treatment temperature is preferably 300 ~ 600 ℃ in terms of the melting temperature of the molten salt contained in the zeolite precursor, the heat treatment time is preferably 0.2 to 10 hours.

As described above, by simultaneously performing zeolite synthesis and immobilization by heat treatment, the process can be simplified and energy can be saved, thereby having an excellent economical effect.

In another embodiment, the coated zeolite can be immobilized by drying at room temperature for 2 to 24 hours.

For example, when heat treatment is impossible due to the properties of the coated material, the zeolite may be immobilized by drying. In this case, it is preferable to use a binder that can be immobilized by drying when forming the zeolite coating solution.

The pollutant adsorption material prepared according to the above method can maintain excellent physical and chemical properties while exhibiting high efficiency of adsorption of contaminants such as heavy metals by the zeolite surface coating while using existing construction materials or the like.

In addition, the pollutant adsorption method according to another embodiment of the present invention includes contacting the pollutant adsorption material with a pollutant-containing medium.

According to the pollutant adsorption method, the pollutant can be adsorbed and removed with high efficiency by contact with a pollutant-containing medium such as heavy metal, that is, soil, water or air contaminated with heavy metal.

Hereinafter, the present invention will be described in more detail with reference to Examples.

However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

Example  One

After completely dissolving 67.6 g of Na ₂ AlO ₃ in 420 ml of distilled water, 112.2 g of Na ₂ SiO ₃ was slowly added to prepare a zeolite precursor, and aged for 1 day at room temperature. A zeolite coating solution was prepared by mixing 20 ml of the precursor, 20 ml of tetraorthoethylsilicate (TEOS), and 160 ml of distilled water.

The zeolite coating solution thus prepared was spray coated on a spherical carbide molded body, and then dried. The dried material was heat-treated at 350 ° C. for 10 hours to fix the coated zeolite to prepare a material for adsorbing contaminants.

2 shows a SEM photograph (10,000 times magnification) of the contaminant adsorption material. As shown in FIG. 2, it was confirmed that zeolite crystals were attached to and formed on the surface of the carbonized body.

Example  2

10 g of three commercially available zeolite powders were slowly mixed in 160 ml of distilled water, and then 20 ml of tetraorthoethyl silicate (TEOS) was injected and mixed again to prepare a zeolite coating solution.

The zeolite coating solution thus prepared was coated on a 50 * 170 * 10 (mm) size specimen using a dip coater, and then dried at room temperature for 30 minutes. The dried specimen was heat-treated at 400 ° C. for 1 hour to fix the coated zeolite to prepare a material for adsorbing contaminants.

Test Example  One

The heavy metal adsorption capacity of the pollutant adsorption material prepared in Example 1 was evaluated using copper.

After putting 5.0 g of the pollutant adsorption material prepared in Example 1 into a 200 ml beaker, 100 ml of an artificial waste solution prepared with an initial concentration of 10 mg / L of copper was injected. It was sampled over time with shaking at 150 rpm. The collected samples were solid-liquid separated by centrifugation, filtered through a 0.25 μm membrane filter, and analyzed for the concentration of copper.

The analysis result is shown in FIG. As shown in FIG. 3, after about 300 minutes had elapsed, it was confirmed that all 10 ppm of copper was adsorbed.

Test Example  2

The contaminant adsorption material prepared in Example 2 was placed in a reactor, and 50 ml of an artificial waste solution prepared with a copper concentration of 1 mg / l was injected. The reactor was fixed to a shaker and shaken at 150 rpm for 1 hour. After 1 hour, the artificial waste solution was removed from the reactor and the concentration of copper was measured.

The analysis results are shown in FIG. 4. As shown in FIG. 4, although the amount of adsorption varies depending on the zeolites A, B, and C commercially available, it can be seen that copper is adsorbed.

1 is a process flow diagram illustrating a method of manufacturing a functional material for adsorption of contaminants according to one embodiment of the present invention.

Figure 2 is a SEM photograph of the functional material for adsorption of contaminants prepared in Example 1.

3 is a graph showing the results of adsorption on copper obtained in Test Example 1. FIG.

4 is a graph showing the results of adsorption on copper obtained in Test Example 2. FIG.

Claims (15)

Iii) mixing the zeolite precursor, tetraethylorthosilicate (TEOS) and water to form a zeolite coating solution; Ii) coating the zeolite coating solution on the surface of the material to be coated; And Iii) immobilizing the coated zeolite on the target surface; The zeolite precursor is prepared by mixing 10-20% by weight of silica (SiO ₂ ) source material, 10-15% by weight of alumina (Al ₂ O ₃ ) source material and the balance of water based on the total weight of the zeolite precursor. felled Method for producing pollutant adsorption material. The method of claim 1, The silica (SiO ₂ ) source material is sodium silicate (Na ₂ CO ₃ ), and the alumina (Al ₂ O ₃ ) source material is sodium aluminate (NaAlO ₂ ). Method for producing pollutant adsorption material. The method of claim 1, The zeolite precursor further comprises a molten salt Method for producing pollutant adsorption material. The method of claim 3, The molten salt is a group consisting of potassium chloride (KCl), potassium fluoride (KF), potassium iodide (KI), sodium chloride (NaCl), sodium iodide (Nal), sodium carbonate (Na ₂ CO ₃ ) and sodium sulfate (Na ₂ SO ₄ ) More than one selected from Method for producing pollutant adsorption material. The method of claim 3, The zeolite precursor is 10 to 20% by weight of the silica (SiO ₂ ) source material, 10 to 15% by weight of alumina (Al ₂ O ₃ ) source material, 5 to 10% by weight relative to the total weight of the zeolite precursor Prepared by mixing molten salt and the balance of water Method for producing pollutant adsorption material. The method of claim 1, In step iii), the zeolite precursor is mixed with 5 to 50 wt% of the zeolite precursor, 5 to 15 wt% of tetraethylorthosilicate, and the balance of water to form a zeolite coating solution. Method for producing pollutant adsorption material. The method of claim 1, Step ii) is performed by dip coating or spray coating Method for producing pollutant adsorption material. The method of claim 1, The step iii) is performed by heat treatment or drying Method for producing pollutant adsorption material. 9. The method of claim 8, The heat treatment is performed at a temperature of 300 ~ 600 ℃, 0.2 to 10 hours Method for producing pollutant adsorption material. 9. The method of claim 8, The drying is carried out for 2 to 24 hours at room temperature Method for producing pollutant adsorption material. delete delete delete delete delete

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