KR20110114761A

KR20110114761A - White clay adsorbed metal having anti-bacteria and preparing methods thereof

Info

Publication number: KR20110114761A
Application number: KR1020100034078A
Authority: KR
Inventors: 김성문; 임경천
Original assignee: 강원도 양구군
Priority date: 2010-04-14
Filing date: 2010-04-14
Publication date: 2011-10-20

Abstract

The present invention relates to the synthesis of special carriers having excellent ion exchange ability, strong heat, acid, and alkali by adding illite to the clay as a main raw material, and a method for producing an antimicrobial agent in which an antimicrobial metal is ion exchanged to the carrier.
The special carrier according to the present invention has excellent sterilization and adsorption ability, and thus can be usefully used in the related fields. In particular, by using a special carrier that is resistant to heat and does not change its properties even in an acid and alkali solution, it is used to replace the antibacterial metal of the antimicrobial agent. By suppressing the degeneration of metal ions can extend the life of the antimicrobial agent, there is an advantage that can be applied to various applications.

Description

Manufacturing method of antimicrobial agent ion-exchanged antibacterial metal based on white clay {WHITE CLAY ADSORBED METAL HAVING ANTI-BACTERIA AND PREPARING METHODS THEREOF}

The present invention relates to the synthesis of a special carrier having excellent ion exchange ability, resistant to heat, acid and alkali, and a method for producing an antimicrobial agent in which an antimicrobial metal is ion-exchanged on a carrier, based on clay and natural zeolite. It relates to an invention for imparting functions such as antibacterial and deodorant to phosphorus clay and natural zeolite.

White clay is called “kaolin” of legal minerals in Korea, and its chemical name is Montmorillonite clay mineral. White clay). In addition, through the various processes such as standard, research, investigation, deep light management, and activation condition (acid heating time) of clay minerals (raw minerals), the characteristic value is identified, and uniform acidic clay (active clay) is manufactured and supplied for each type. have.

The clay has the property of selectively adsorbing the thermopolar material from the multicomponent mixture, so that a small amount of clay can give the maximum decolorizing effect in a short time. Silica-alumina is the main component and is a kind of clay mineral having iron, magnesium, calcium and sodium components.

In the clay structure, the solid acid substituted between the double-sided and octahedral layers enhances the chemisorption effect, and the decolorizing power is remarkably changed according to the acidity. The clay is uniformly adjusted to the acidity according to the retention of the refining agent, and the surface area of the clay can be improved by dissolving the soluble substance in the structure by acid treatment to enlarge the surface area to improve the discoloration effect. Part of the cation is replaced by hydrogen ions by the activation process, and the amount thereof is about 10-30 m.e / 100 g (cationic exchange capacity), which shows chemical properties that are not present in other adsorbents. Adsorption of the surface of activated clay is selective, and it has the characteristic of having selective adsorption to polar materials, unsaturated materials and aromatic materials in the state where several kinds of materials coexist.

The term sericite, also called chorus, is derived from the Greek word for silk, belonging to the monoclinic system, and have a pearlescent appearance of white or off-white. Originally referred to as the dominant mineral of crystalline schist rock, especially chorionic schist rock, today it refers to clay-like fine muscovite formed by hydrothermal action. The chemical composition is almost the same as that of the mica, but in general the potassium K is less than the mica and the moisture H ₂ O is somewhat higher. It is produced as a secondary alteration such as feldspar, cordierite, and red tin stone, and is the most common constituent mineral of feldspar slate or stony rock subjected to light power metamorphism. The potter's stone is caused by the alteration of volcanic rock, which is composed of quartz (70%) and biotite (30%). Cicada is used as a mixing material for ceramics and firebrick, and has various uses such as paints, electrical insulators, active materials, and cosmetics.

Sericite is called sericite because its surface has silky luster and is white or light brown in color. The chemical composition is K ₂ Al ₄ (Si ₅ Al ₂ ) O ₂₀ (OH) _{4, which} is the intermediate between mica and illite. Dehydrated unit cell is slightly expanded at 600 ~ 700 ℃, and dehydrated unit cell is decomposed at around 1050 ~ 1100 ℃ to produce mullite, and at higher temperature, it forms glassy phase and has high forming strength and melted glassy viscosity. Because of this, the load softening temperature is high.

In addition, since it plays the role of feldspar that plays the role of a plastic material clay and a flux, when preparing chamomile refractory brick, when crushing about 5% of the clay containing sericite and blending it into the raw material, the firing temperature It can be reduced to about 30 ~ 40 ℃, which is very helpful for saving fuel, sintering is good, and the load softening temperature is hardly lowered. And, since the clay is white, it can be used in various applications.

Conventionally, the invention using the clay is Republic of Korea Patent No. 0355570 relates to a multifunctional inorganic antimicrobial product manufacturing method and a product containing a photocatalyst, in particular, natural minerals zeolite, bentonite, sericite, diatomaceous earth is a special process An inorganic antimicrobial photocatalyst made of rutile type titanium dioxide composited to obtain an antimicrobial, deodorizing and adsorptive function using titanium dioxide having a rutile type crystal structure having good heat resistance and durability And a method of preparing a porous body by a special method after sufficiently stirring an appropriate amount to obtain an inorganic antimicrobial agent mixed with a photocatalyst in a slurry state, and then injecting the same into a mold of a desired form.

In addition, the Republic of Korea Patent No. 0428248 relates to a method for manufacturing a ceramic filter and a ceramic filter produced by the same, in detail, the ganbanite having a properly adjusted weight percent, sericite and zeolite powder by mixing with water The present invention relates to a method for preparing a ceramic filter, and a ceramic filter manufactured according to the present invention.

However, the Patent No. 0255570 relates to a method for preparing a porous body by using a natural mineral and a suitable mixing of a photocatalyst having an antimicrobial function, but the porous body may have antimicrobial properties, but the natural mineral and the photocatalyst are mixed. However, it has a limit of exhibiting antimicrobial properties only when there is a light source.

In addition, the ring manufactured using the elvan and the sericite and zeolite powder of the Patent No. 0428248 is valuable as a ceramic filter, but there is a disadvantage that there is no antibacterial.

Therefore, there is a need for the development of a carrier having excellent ion exchange ability, heat resistance, and strong acid and alkali resistance. In addition, while the production method is simple, it is also necessary to develop inorganic antibacterial and deodorant that can have a continuous antibacterial and deodorizing power.

In order to solve the above problems, the present invention relates to the synthesis of a special carrier having excellent ion exchange ability, resistant to heat, acid and alkali, and to the production of antimicrobial agents ion-exchanged antimicrobial metal on the carrier, as a raw material of clay, natural zeolite The present invention relates to an invention that provides functions such as antibacterial and deodorization to environmentally friendly materials that are widely used, such as clay, sericite and natural zeolite.

In order to achieve the above object, the present invention provides a synthetic special carrier combined with an antimicrobial metal.

In addition, the present invention comprises the steps of 1) mixing the clay with purified water, and neutralizing the mixed solution to prepare a primary mixture; 2) preparing a secondary mixture by adding and reacting an antimicrobial metal to the primary mixture; And 3) adding an antioxidant to the secondary mixture and reacting to prepare a final product.

In addition, the final product of step 3) may further comprise the step of centrifuging and drying it.

In the production method of the present invention, the clay is not particularly limited in step 1), but preferably 25 to 1000 mesh powder can be used. In addition, the antimicrobial metal of step 2) may be used Ag, Fe, Zn, Cu, etc., Preferably, the antimicrobial metal may be used metal ions prepared by electrolysis. At this time, the method of adding the antimicrobial metal can be used to add the metal in the ionic liquid state to the primary mixed solution, and after the addition, so that the concentration of metal ions in the solution is 10 ~ 200 ppm.

In addition, the antioxidant of step 3) can be used without limitation as long as it is a material for preventing oxidation of the antibacterial metal. Preferably, zinc, tocopherol, propyl gallate , thioether , or the like can be used. At this time, the antioxidant may be added to the secondary mixture to have a concentration of 4 ~ 200 ppm. The final product may be prepared by stirring the antioxidant and the secondary mixture. The final product is a form in which the antibacterial metal is bound to sericite and forms a suspension state. The clay is of a large size in which the particles cannot be completely dissolved in water, so that the clay in suspension can be obtained in a constant manner. As a preferred method of obtaining, the clay may be obtained by rotating at 200-3000 rpm by centrifugation.

The clay according to the present invention can be used as a disinfectant, water purifier, odor and toxic gas adsorption, deodorization, decomposition agent, active oxygen generator. In addition, the use of an antioxidant also has the effect of suppressing the degeneration of the antimicrobial metal ions and extending the life of sericite. In addition, there is an advantage that the production method of the clay is simple and can be easily produced in large quantities.

There are many uses of clay, but typical uses include cosmetics, soap, toothpaste, clothing, feed, fertilizer, environment, construction, health products, broadcasting, satellite, aerospace, ceramics, welding, and other pigments. It is used in a variety of applications such as paints, medicines and food additives.

In the present invention, to give an additional function by mixing with the antimicrobial material to the clay, an antimicrobial material can be added. The antimicrobial material may be used without limitation as long as it is a material that can be used in the art, and preferably a metal having antibacterial property, and more preferably Ag, Fe, Zn, Cu, or the like may be added. The metal may exert a function of inhibiting the metabolism of strains that cause disease and strains that cause odors, thereby sterilizing.

The present invention provides a method for producing clay which is combined with an antimicrobial metal.

First, step 1) is to prepare a primary mixture in suspension using clay.

Although the said sericite is not specifically limited, Preferably what is 25-1000 mesh powder can be used. The mesh is a unit representing the particle size of the abrasive or abrasive. The lower the mesh value, the larger the particle size. The higher the mesh value, the smaller the particle size. If the sericite is less than 25 mesh, the particle size is large, and it is difficult to prepare the sericite in suspension, so that the adsorption with the metal is lowered. The adsorption rate no longer increases.

The purified water used in this step is not particularly limited, and distilled water may be preferably used. The amount of the clay added to the purified water is not particularly limited, and preferably, 100 ml of purified water may be prepared by mixing 0.5-20 parts by weight of sericite. When the clay is dissolved in purified water, pH 5.0-8.2, it is necessary to adjust the pH to neutral for constant reactivity. In order to adjust the pH of the purified water in which the clay is dissolved, the pH may be adjusted using an acidic solution or a basic solution. The acidic solution may use both strong and weak acids, and the basic solution may use both strong and weak bases.

Next, step 2) is a step of reacting by adding antimicrobial metal ions.

The antimicrobial metal may be used without limitation so long as it is a metal that can be used in the art, and preferably Ag, Fe, Zn, Cu, or the like may be used. The metal is preferably added in the form of ions, and more preferably, the antimicrobial metal may use metal ions prepared by electrolysis. At this time, the method of adding the antimicrobial metal can be used to add the metal in the ionic liquid state to the primary mixed solution, and after the addition, so that the concentration of metal ions in the solution is 10 ~ 200 ppm. When the concentration of the metal ion is less than 10 ppm, it is difficult to exhibit the antibacterial and deodorizing effect, when it exceeds 200 ppm, compared to the addition amount, it is difficult to expect improved antibacterial and deodorizing effect.

In addition, the present invention is to add the antimicrobial metal in the ionic liquid state, when the antimicrobial metal is added as a powder, the size of the metal particles is large, the adsorption force is reduced to the soil, the adsorbed metal may have the disadvantage that the reactivity is inferior. In addition, there is a disadvantage that the amount of metal added to the soil to increase the expected effect of antibacterial and deodorizing power. However, when adding the antimicrobial metal, when added in the form of metal ions, it may have the advantage that the amount of the added metal is small.

Next, step 3) is a step of adding an antioxidant to maintain the reactivity of the clay of the present invention.

The antioxidant can be used without limitation so long as it is a material for preventing oxidation of the antibacterial metal. Preferably, phenyl-β-naphthylamine, zinc, tocopherol, propyl gallate , thioether and the like can be used. In this case, the antioxidant may be added to the secondary mixture to be used at a concentration of 4 ~ 200 ppm. The final product may be prepared by administering and stirring the antioxidant to facilitate the reaction. If the amount of the antioxidant is less than 4 ppm, the antioxidant cannot be sufficiently combined. If the amount of the antioxidant is more than 200 ppm, the antioxidant effect is not increased compared to the amount of the antioxidant, and the utility is inferior.

The final product is in the form of a combination of the antimicrobial metal and antioxidant to the clay, and forms a suspension. Since the sericite is of a large size that the particles cannot be completely dissolved in water, it is possible to obtain a suspended clay in the usual manner in the art. As a preferred method of obtaining, sericite can be obtained by rotating at 200-3000 g by centrifugation.

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

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example 1> silver adsorbed Serisite Produce

1 g of sericite was stirred in 10 to 50 ml of distilled water to be sufficiently dispersed to prepare a suspension, which was neutralized to pH 7.0 with 0.1 to 3.0 sodium hydroxide solution and nitric acid. To 100 ml of the neutralized suspension was added a silver ionic liquid obtained by electrolysis so as to have a silver ion concentration of 10 to 200 ppm, followed by stirring at room temperature for 6 to 36 hours. The silver ion-added suspension prepared by stirring was centrifuged at 500 g to obtain a clay deposit. The obtained clay was dried in air at 25-120 ° C. for 2 hours, thereby preparing clay having silver ions adsorbed thereon.

< Example 2> iron adsorbed Serisite Produce

Except for using iron ions in the same manner as in Example 1 was prepared clay adsorbed iron.

< Example 3> copper adsorbed Serisite Produce

Except for using copper ions in the same manner as in Example 1 was prepared iron adsorbed clay.

Experimental Example 1

Experimental Example 1 shows the results of an antibacterial test for E. coli in 100 ml of sample solution using 5 g of 3 mm balls prepared from clay. It can be seen that one million bacteria are killed after 30 minutes in 1 ml of the initial bacterial count.

Experimental Example 2

Experimental Example 2 shows the results of the antimicrobial test against rust rust in 100ml of sample solution using 5g of 3mm ball prepared from clay. It can be seen that 10.1 million bacteria survived in 60 minutes of reaction time in 1 ml of the initial bacterial count.

< Experimental Example 3>

Experimental Example 3 shows the results of the antimicrobial test against antistaining Staphylococcus aureus in 100ml of sample solution using 5g of 3mm ball prepared from clay. It can be seen that one million bacteria are killed after 60 minutes in 1 ml of initial bacteria.

Experimental Example 4

Compound Substituent: Substituted silver ion with silver ion

Experimental Example 4 shows the results of the ammonia deodorization experiment for silver ion exchange between Yanggu white clay and Yanggu white clay. The deodorizing power is not good in the case of using only Yanggu clay, but the deodorizing power reaches 100% after 60 minutes in the case of using the compound substitute.

Claims

The first step is to mix the clay with purified water, and neutralize the mixture to prepare a primary mixture. The second step is to add an antimicrobial metal ion to the primary mixture and to react to prepare a secondary mixture 3 Adding an antioxidant to the secondary mixture in a step, and reacting to prepare a final product.

The method of claim 1, further comprising the step of centrifuging the final product of step 3 and drying it.

The method of claim 2, wherein the antimicrobial metal ions of step 2 are at least one selected from the group consisting of Ag, Fe, and Cu.