KR100349611B1 - Method of preparing water-purifying agent supported with silver - Google Patents

Abstract

The present invention relates to a method for producing silver containing purified water, comprising the step of adding a chlorine salt and an alcohol to a carrier, and adding a silver salt and an alcohol to a mixture of the carrier, the chlorine salt and the alcohol. In this method, the silver is insoluble in AgCl form in the carrier, so when the water is purified by the water purifier, the silver is hardly eluted in the water, and the water purification effect is very high due to the sterilizing effect of silver.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a water purifying agent,

[Industrial Applications]

The present invention relates to a method for producing a purified water containing silver and, more particularly, to a method for producing a water purification agent supported so as not to release silver, which has a bactericidal growth inhibiting ability and a sterilizing effect.

BACKGROUND ART [0002]

Contrary to the civilization benefits of industrial development in the modern age, serious problems such as environmental pollution are emerging. Especially, in most households, most households avoid tap water to boil tap water, or use tap water instead of tap water, ground water, Tap water, ground water or spring water is purified with a water purifier to be consumed. In recent years, the use of water purifiers has been increasing.

The water purifier can be classified into an adsorption filtration type water purifier, a natural filtration type water purifier, a reverse osmosis water purifier, an ionizer or a hollow fiber membrane type water purifier according to a purification method. Among them, the adsorption filtration type water purifier is a water purification agent using activated carbon as a water purification agent, which removes chlorine components and organic substances in the water by utilizing the strong adsorption performance of activated carbon, but has a problem that bacteria can not be removed. In particular, this adsorption / filtration type water purifier is difficult to store for a long period of time because the filtered water will lose the sterilizing power due to the removal of chlorine when passing through the water purifier.

Recently, in order to solve the problems of the activated carbon used in the adsorption filtration type water purifier, a method of supporting silver on activated carbon has been studied. Conventionally, a method of supporting silver on activated carbon is a method in which activated carbon, which is a carrier, is immersed in an aqueous solution of silver acetate, or an aqueous solution of silver acetate is added to activated carbon.

It is an object of the present invention to provide a method for manufacturing a silver-containing water purification agent capable of effectively supporting silver having an effect of inhibiting the growth and sterilization of germs.

Another object of the present invention is to provide a method of manufacturing a silver-containing water purification agent capable of retaining sterilizing power even after filtration and capable of filtering water to enable storage for a long period of time, .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of water-feeding experiments using purified water prepared according to the methods of Examples 9 and 11 and Comparative Example 26 of the present invention.

FIG. 2 is a graph showing the results of water-feeding experiments using purified water prepared according to the methods of Examples 10 and 12 and Comparative Example 27 of the present invention.

FIG. 3 is a graph showing the results of water-feeding experiments using purified water prepared according to the methods of Examples 5 and 7 and Comparative Example 25 of the present invention.

FIG. 4 is a photograph of a medium for determining antimicrobial activity against distilled water Escherichia coli as a standard solution (AgNO ₃ ).

FIG. 5 is a photograph of a medium for determining antimicrobial activity against Pseudomonas aeruhinosa , a standard solution of distilled water (AgNO ₃ ) and a control solution.

FIG. 6 is a photograph of the result of conducting an experiment of pre-water agar plate of a coral sands purification agent prepared by the method of Example 5 to examine the antimicrobial activity against Escherichia coli .

FIG. 7 is a photograph of the result of an agar plate experiment after the passage of the silver-supported coral sands purification agent prepared by the method of Example 10 to examine the antimicrobial activity against Escherichia coli .

FIG. 8 is a photograph of a culture medium showing a result of conducting an agar plate experiment of water-containing coral sludge purification agent prepared by the method of Example 10 to examine the antimicrobial activity against Pseudomonas aeruhinosa .

FIG. 9 is a photograph of a culture medium showing the result of conducting an agar plate experiment of water-borne coral sand prepared by the method of Comparative Example 25 to examine the antimicrobial activity against Pseudomonas aeruhinosa .

10 is a graph showing the results of experiments of distilled water of Example 5 (before water washing), Example 10 (before and after water washing) and Comparative Example 5 in order to examine the antibacterial activity against Escherichia coli .

In order to accomplish the object of the present invention, the present invention provides a method for producing a water-soluble activated carbon, comprising: adding an aqueous chlorine salt alcohol solution to activated carbon as a carrier; Drying said mixture; And a step of adding a silver salt and an aqueous alcohol solution to the dried product.

Further, the present invention relates to a method for producing a chalcogenide compound, And a step of adding a silver salt aqueous solution to the mixture. When a coral sand is used as a carrier, a silver salt aqueous solution may be added first, and a chlorine salt aqueous solution may be added.

Hereinafter, the present invention will be described in more detail.

The production method of the present invention is a method of effectively supporting silver on a support. As the carrier, active carbon or a coral sand may be used. The activated carbon is a porous carbon body having a large specific surface area and has a strong adsorption force and is generally used for filtering contaminants in water such as pesticides, carcinogens, heavy metals, organic compounds, odors, pigments, residual chlorine or detergents. The coral sand is a material rich in structure-forming materials and serves to maintain a weakly alkaline physiologically good state of water.

In this way, the activated carbon or the coral sand itself is excellent in the water purifying function of the water itself, but the bacteria can not be removed. In particular, when the chlorine is removed from the water, the water disinfecting power is lost and the water retained in the activated carbon or the coral sand is stored There is a problem that can not be done.

In the present invention, in order to prevent the propagation of bacteria, silver was supported on activated carbon or a chorale sand. Silver is effective in inhibiting the propagation and growth of bacteria and is a substance used to prevent bacterial infection in swimming pools or a substance that can adversely affect the human body if it exceeds a certain concentration. Therefore, when silver is simply supported on a carrier, excess silver may be eluted into purified water. In view of the fact that AgCl is insoluble in the present invention, silver is supported on the carrier in the form of AgCl so that the silver is less than or less than the tolerance. Generally, the amount of silver is specified to be less than 50 ppb in the US Public Health Service.

Hereinafter, silver supporting method of the present invention will be described by distinguishing the case of using activated carbon as carrier and the case of using coral sand.

1) When using activated carbon

The activated carbon which is a carrier may be used as it is, but it is preferable to wash it with water and dry it at 50 to 150 ° C in an oven to facilitate the development of micropores of activated carbon and widen the surface area of the carrier to activate it.

The obtained activated carbon is added to a solution of hydrochloric acid salt alcohol. Chloride salt Aqueous solution of alcohol is prepared by dissolving a chloride salt in a mixed solution of water and alcohol. The mixed solution of water and alcohol preferably contains 90 to 70% by volume of water and 10 to 30% by volume of alcohol. If the amount of the alcohol is less than 10 vol%, the chloride salt is difficult to dissolve in the aqueous alcohol solution. If the amount of the alcohol is more than 30 vol%, the affinity of the solvent for the activated carbon decreases and the supporting ratio may decrease. The use of ethanol as the alcohol is preferable because it is harmless to the human body and the silver elution amount can be reduced.

The chloride salt may be NaCl. The amount of the salt to be used is preferably 1.2 to 2 times, more preferably 1.2 to 1.5 times the amount of silver to be supported. (NaCl + AgNO ₃ → AgCl + NaNO ₃ ), and when the amount of the chloride salt is more than 2 times, the conversion rate to the desired form of AgCl is lowered The reaction with AgCl occurs and AgCl is easily released from the activated carbon, which is not preferable.

At this time, either an evaporation method in which an aqueous alcohol solution is used in excess of the saturation volume of the activated carbon may be performed, or an incipient wetness method in which an alcohol aqueous solution is used only in a saturated volume of activated carbon There is also water. The distillation method and the incipient wet method will be described in more detail. First, the distillation method is a method in which an aqueous solution of hydrochloric salt alcohol is added to activated carbon and mixed well, followed by vacuum distillation. In the case of the incipient wet method, And then mixed well. According to this process, chlorine (Cl ^- ) ions are inserted into the pores of the activated carbon.

Then, the mixture of the obtained activated carbon and the aqueous hydrochloric acid salt solution is dried to volatilize the alcohol aqueous solution as a solvent to prepare a carrier in which chloride ions (Cl ^- ) ions are inserted into the pores.

The activated carbon having the chlorine ion inserted therein may be washed with flowing water to remove only the NaCl adhering to the surface of the activated carbon.

The silver chloride aqueous solution is added to the activated carbon into which the obtained chlorine ion is inserted. As the silver salt, AgNO ₃ or Ag acetate can be used. The silver salt is used in an amount of 0.1 to 0.4% by weight based on the weight of the activated carbon as a starting material. If the amount of salt used is less than 0.1 wt% of the weight of the activated carbon, the antimicrobial effect of the silver-supported carrier is deteriorated, and if it is more than 0.4 wt%, it is not economical and toxicity to purified water may be increased.

At this time, the distillation method and the incipient method can be used. As a result, the silver salt reacts with the Cl ^- ions inserted into the pores of the activated carbon to produce a water purification agent containing AgCl, which is insoluble in the pores. Then, a drying process may be performed to volatilize the alcohol aqueous solution as a solvent. Since the supported AgCl is insoluble, when water is purified by using the obtained water purification agent, AgCl is hardly eluted into water to be purified and harmless to the human body, so that the propagation and growth inhibition effect of bacteria which is the original property of silver can be obtained.

Then, the obtained water purification agent may be further subjected to heat treatment at 200 to 350 ° C for 2 to 3 hours. The AgNO ₃ remaining unreacted in this heat treatment process is converted to AgO, and the converted AgO is insoluble, so it does not dissolve in water when it is watered. If the heat treatment temperature is lower than 200 ° C, there is a problem that AgNO ₃ is difficult to be converted to AgO. When the heat treatment temperature is higher than 350 ° C, the mass of activated carbon may be drastically reduced. If the heat treatment time is shorter than 2 hours, the salt form conversion rate is lowered, and if it is longer than 3 hours, the weight of activated carbon is decreased, which is not preferable.

2) When using a coral sand

It is preferable that the carrier is used as it is, but it is preferably washed with water and dried at 50 to 150 ° C in an oven to facilitate the development of micropores of the coral sand and to widen the surface area of the carrier to activate it.

An aqueous chloride salt solution is added to the obtained chorale sand. At this time, the incipient wetness method is used in which water as a solvent is used only in a saturated volume of the coral sand. According to this process, Cl ^- ions are inserted into the pores of the coral sand. The chloride salt may be NaCl. The amount of the salt to be used is preferably 1.2 to 2 times, more preferably 1.2 to 1.5 times the amount of silver to be supported. (NaCl + AgNO ₃ ? AgCl + NaNO ₃ ) is lowered when the amount of the salt to be used is smaller than 1.2 times the amount of silver to be supported, and when the amount of the salt is more than 2 times, To AgCl, which is not preferable because AgCl is easily separated from the chorale sand.

The obtained coral sand and the aqueous chloride salt solution are mixed well and then dried. The drying process may be carried out to remove all of the water as a solvent or to remove only a part of the solvent so that the coral sand is in a wet state.

An aqueous silver salt solution is added to the product. The incipient wet method is also used at this time. As the silver salt, AgNO ₃ or Ag acetate can be used. The silver salt is used in an amount of 0.1 to 0.4% by weight based on the weight of the starting material, coral sand. If the amount of salt used is less than 0.1 wt% of the weight of the coral sand, the antibacterial effect of the silver-supported carrier is deteriorated, and if it is more than 0.4 wt%, it is not economical and toxicity to purified water can be increased. As a result, the silver salt reacts with the Cl ^- ions inserted into the pores of the chorale sand, thereby preparing a water purification agent carrying AgCl which is insoluble in the pores. Subsequently, a drying process may be performed to volatilize the water as a solvent.

Then, the obtained water purification agent may be further subjected to heat treatment at 400 to 600 ° C for 2 to 3 hours.

Since the surface area of the coral sand is small and the pore volume is small, the same effect can be obtained by changing the order of addition of the chloride salt and the silver salt.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

(Examples 1 to 4 and Comparative Examples 1 to 24)

1. Silver supported activated carbon purification agent

Activated carbon, which is a carrier having the following physical properties, was first washed with water and dried in an oven at 100 ° C. to facilitate the development of micropores and activate the surface area of the activated carbon.

(BET area: 846.7 m < 2 > / g) or 30 x 85 (BET area: 820.1 m &

The apparent bulk volume of the carrier: 1.2 ml / g

An activated carbon purification agent was prepared by supporting silver on the activated support using the silver supporting sample, the solvent and the supporting method shown in Table 1 below. As shown in the following Table 1, in order to compare the effects of the conventional method with the water purification agent using NaCl, AgNO ₃ and ethanol in addition to the method using the aqueous solution of Ag acetate, a method using AgNO ₃ alone A method using NaCl, AgNO ₃ and methanol was also used to produce an activated carbon purification agent.

division Supporting reagent / solvent Method of carrying Method of carrying Comparative Example AgNO ₃ / H ₂ O heat treatment distillation AgNO ₃ aqueous solution was added to the carrier and mixed for about 2 hours. After distillation under reduced pressure, the mixture was subjected to heat treatment at 250 ° C for 2 hours AgNO ₃ / H ₂ O distillation The AgNO ₃ aqueous solution was added to the carrier and mixed for about 2 hours. The mixture was distilled under reduced pressure and dried Incipient AgNO ₃ aqueous solution was added to the carrier and mixed for about 2 hours and dried (amount of solution: saturation volume) Ag acetate / H ₂ O distillation Ag acetate solution was added to the carrier and mixed for about 2 hours. The mixture was distilled under reduced pressure and dried Incipient Ag acetate solution was added to the carrier and mixed for about 2 hours and dried (amount of solution: saturation volume) NaCl + AgNO ₃ / H ₂ O distillation NaCl aqueous solution was added to the carrier and mixed for about 6 hours. After drying, AgNO ₃ aqueous solution was added thereto, followed by mixing for 6 hours, followed by distillation under reduced pressure NaCl + AgNO ₃ / methanol distillation NaCl and methanol were added to the carrier and mixed for about 6 hours. After drying, AgNO ₃ and methanol were added thereto, followed by mixing for 6 hours. After distillation under reduced pressure, Washing with NaCl + AgNO ₃ / methanol NaCl distillation NaCl and methanol were added to the carrier and mixed for about 6 hours. After volatilization and drying, only the NaCl on the surface of the carrier was washed with running water. AgNO ₃ and methanol were added to the carrier and mixed for 6 hours. Example NaCl + AgNO ₃ / (ethanol: H ₂ O = 9: 1) distillation NaCl aqueous ethanol solution was added to the carrier and mixed for about 6 hours. After drying, an aqueous solution of AgNO ₃ ethanol was added thereto, and the mixture was stirred for 6 hours. NaCl + AgNO ₃ / (ethanol: H ₂ O = 9: 1) heat treatment distillation NaCl aqueous ethanol solution was added to the carrier and mixed for about 6 hours. Then, an aqueous solution of AgNO ₃ ethanol was added thereto, and the mixture was stirred for 6 hours. After distillation under reduced pressure, the mixture was heat-treated at 250 ° C. for 2 hours

(1) Leaching experiment

Silver concentration was measured in purified water after 1 hour, 3 hours, 5 hours and 7 hours while passing 0.5 liter of water per minute to 15 g of activated carbon purification agent prepared by the method shown in Table 1 (WHSV Space velocity of water per weight = 2000h ^-1 ). The results are shown in Tables 2-4 below.

Supporting reagents and solvents Loading Method of carrying Activated carbon type division time The concentration (ppb) AgNO ₃ / H ₂ O 0.4 wt% Incipient 30 x 85 Comparative Example 1 1h 119 3h 131 5h 68 16 x 35 Comparative Example 2 1h 169 3h 122 5h 113 distillation 30 x 85 Comparative Example 3 1h 72 3h 95 5h 146 16 x 35 Comparative Example 4 1h 104 3h 133 5h 84 0.1 wt% Incipient 30 x 85 Comparative Example 5 1h 133 3h 111 5h 132 16 x 35 Comparative Example 6 1h 171 3h 97 5h 107 distillation 30 x 85 Comparative Example 7 1h 74 3h 66 5h 76 16 x 35 Comparative Example 8 1h 111 3h 130 5h 69

Supporting reagents and solvents Loading Method of carrying Activated carbon type division time The concentration (ppb) AgNO ₃ / H ₂ O heat treatment 0.4 wt% distillation 30 x 85 Comparative Example 9 1h 35 3h 40 5h 47 7h 45 16 x 35 Comparative Example 10 1h 34 3h 37 5h 38 7h 34 Ag acetate / H ₂ O 0.4 wt% Incipient 30 x 85 Comparative Example 11 1h 112 3h 147 5h 160 16 x 35 Comparative Example 12 1h 128 3h 161 5h 158 distillation 30 x 85 Comparative Example 13 1h 123 3h 145 5h 156 16 x 35 Comparative Example 14 1h 152 3h 95 5h 114 0.1 wt% Incipient 30 x 85 Comparative Example 15 1h 102 3h 172 5h 243 16 x 35 Comparative Example 16 1h 110 3h 123 5h 92 distillation 30 x 85 Comparative Example 17 1h 128 3h 119 5h 129 16 x 35 Comparative Example 18 1h 166 3h 114 5h 123 NaCl + AgNO ₃ / H ₂ O 0.4 wt% distillation 30 x 85 Comparative Example 19 1h 134 3h - 5h 61 16 x 35 Comparative Example 20 1h 48 3h 59 5h 38

Supporting reagents and solvents Loading Method of carrying Activated carbon type division time The concentration (ppb) NaCl + AgNO ₃ / methanol 0.4 wt% distillation 30 x 85 Comparative Example 21 1h 105 3h 36 5h 53 7h 43 16 x 35 Comparative Example 22 1h 58 3h 61 5h 57 7h 37 Washing with NaCl + AgNO ₃ / methanol NaCl 0.4 wt% distillation 30 x 85 Comparative Example 23 1h 36 3h 38 5h 52 7h 53 16 x 35 Comparative Example 24 1h 86 3h 83 5h 42 7h 47 NaCl + AgNO ₃ / (ethanol / H ₂ O = 9) 0.4 wt% distillation 30 x 85 Example 1 1h 36 3h 48 5h 44 7h 87 16 x 35 Example 2 1h 88 3h 44 5h 45 7h 43 NaCl + AgNO ₃ / (ethanol / H ₂ O = 9) heat treatment 0.4 wt% distillation 30 x 85 Example 3 1h 39 3h 35 5h 98 7h 37 16 x 35 Example 4 1h 47 3h 37 5h 34 7h 36

As shown in Tables 2 to 4, when water was purified by using the activated carbon purification agent prepared by the method of Example 1-4, the water purification efficiency was higher than that of the activated carbon purification agent prepared by the method of Comparative Example 1-24, It can be seen that the concentration of silver eluted in the purified water is low. Therefore, it can be seen that the activated charcoal purifying agent prepared by the method of Example 1-4 can be purified water harmless to the human body more than the activated charcoal purifying agent of Comparative Example 1-24. In more detail, the concentration of silver eluted with the activated carbon purifying agent of Examples 1 and 2 using ethanol was less than that of the activated carbon purification agents of Comparative Examples 21 and 22 using methanol. It can also be seen that the activated carbon purifying agent of Example 3-4 subjected to the heat treatment was less soluble than the activated carbon purifying agent of Example 1-2 in which heat treatment was not carried out.

(2) is a digestion confirmation experiment,

The amount of silver supported on the activated charcoal purified water before and after passing water was measured and the results are shown in Tables 5 to 6, respectively. The amounts of silver supported on the activated charcoal purified water before and after the water were measured by eluting the loaded silver in the activated carbon purification agent by boiling it for a long time, .

Concentration of activated carbon water purification agent Supporting reagents and solvents Loading Method of carrying division Activated carbon type Actual loading [%] NaCl + AgNO ₃ / methanol 0.4 wt% distillation Comparative Example 21 30 x 85 28.63 Comparative Example 22 16 x 35 32.27 Washing with NaCl + AgNO ₃ / methanol NaCl 0.4 wt% distillation Comparative Example 23 30 x 85 43.19 Comparative Example 24 16 x 35 49.38 NaCl + AgNO ₃ / (ethanol / H ₂ O = 9) 0.4 wt% distillation Example 1 30 x 85 62.46 Example 2 16 x 35 72.25

Concentration of activated carbon water purification agent Supporting reagent Loading Method of carrying division Activated carbon type Actual loading [%] NaCl + AgNO ₃ / methanol 0.4 wt% distillation Comparative Example 21 30 x 85 10.63 Comparative Example 22 16 x 35 11.50 Washing with NaCl + AgNO ₃ / methanol NaCl 0.4 wt% distillation Comparative Example 23 30 x 85 25.50 Comparative Example 24 16 x 35 38.39 NaCl + AgNO ₃ / (ethanol / H ₂ O = 9) 0.4 wt% distillation Example 1 30 x 85 47.25 Example 2 16 x 35 62.50

(3) Antimicrobial activity experiment

1) Test bacteria

Escherichia coli IFO 3972 (Escherichia coli)

Enterococcus faecalis IFO 12964 ( Enterococcus faecalis )

2) Test medium

NA Badge: Medium agar medium (Song Yeon Chemical Co., Ltd.)

SCDLPA badge: SCDLPA agar medium (Japan Pharmaceutical Co., Ltd.)

3) Preparation of Fungus Solution

The test bacteria were cultured in NA medium at 35 짹 1 属 C for 20 to 24 hours, then inoculated again in NA medium, and cultured at 35 짹 1 属 C for 16 to 20 hours. After culturing, the bacterial cells obtained were homogeneously dispersed in sterilized liquid crystal water so that the number of bacteria per 1 ml was about ¹⁰⁷ , to prepare a broth.

4) Preparation of Test Solution

2.5 g and 5 g of the activated carbon purifying agent of Examples 1 and 2, which were dry heat sterilized liquid (180 占 폚, 30 minutes), were taken in an Erlenmeyer flask (100 ml). 50 ml of sterilized purified water was added to each of them to prepare 5% and 10% test solutions. Sterilized purified water not containing the activated carbon water purification agent was used as a control test liquid.

5) Experimental method

To each test solution was added 0.5 ml of each of the above mycelial solutions, and the mixture was stirred at 25 ± 1 ° C (revolutions of about 100 rpm). After stirring for 24 hours, the number of viable cells of the test solution was measured by a sticky plate culture method (35 ± 1 ° C for 2 days) using SCDLPA medium, and the results are shown in Table 7 below. The viable cell count immediately after addition of the bacterial solution to the test solution was measured, and the results are shown in Table 7 below.

Test bacteria Test solution Viable cell count (/ ml) Early After 24 hours Escherichia coli Example 1: Addition of 5% 7.2 × 10 ⁶ 40 Example 1: Addition of 10% 7.2 × 10 ⁶ 1.6 x 10 ² Example 2: Addition of 5% 7.2 × 10 ⁶ <1 ^* Example 2: Addition of 10% 7.2 × 10 ⁶ 1.2 × 10 ³ Control group 7.2 × 10 ⁶ 1.0 × 10 ⁵ Enterococci Example 1: Addition of 5% 2.6 x 10 ⁶ 8 Example 1: Addition of 10% 2.6 x 10 ⁶ One Example 2: Addition of 5% 2.6 x 10 ⁶ <1 Example 2: Addition of 10% 2.6 x 10 ⁶ <1 Control group 2.6 x 10 ⁶ 1.7 x 10 ⁴

* <1: Not measured.

As shown in Table 7, it can be seen that the activity of the activated carbon purification agent of Example 1-2 is very excellent.

(Examples 5 to 8 and Comparative Examples 25 to 26)

2. Coral sand water purification agent

The carrier having a surface area measured by BET of 0.1 m &lt; 2 &gt; / g and an apparent pore volume of 0.25 ml / g was thoroughly washed with water and dried at about 100 DEG C in an oven to facilitate the development of micropores and to activate the surface of the carrier.

Using this carrier, silver was supported so as to carry 0.03 g of silver per 10 g of the carrier to prepare a coral sand purification agent. The supporting method was carried out by slightly changing the in-plane wet method shown in Table 8 below.

Sample number Supporting reagent Method of carrying Example 5 AgNO ₃ wetting NaCl AgNO ₃ aqueous solution was added to the carrier and mixed for about 2 hours. The carrier was dried in a wet state, and then an aqueous NaCl solution was added thereto, followed by drying, followed by heat treatment at 500 ° C Example 6 AgNO ₃ dry NaCl AgNO ₃ aqueous solution was added to the carrier and mixed for about 2 hours. After drying, NaCl aqueous solution was added thereto, followed by heat treatment at 500 ° C Example 7 NaCl wetting AgNO ₃ NaCl aqueous solution was added to the carrier and mixed for about 2 hours. The resultant was dried in a wet state on the carrier, and then an AgNO ₃ aqueous solution was added thereto. Example 8 NaCl dry AgNO ₃ NaCl aqueous solution was added to the carrier, mixed for about 2 hours, dried, and then an AgNO ₃ aqueous solution was added thereto, followed by heat treatment at 500 ° C

5 g of the purified water prepared by the above-mentioned method was taken, washed with 100 ml of distilled water, and the washed water was measured by ICP. No silver was found in the washed water.

(1) Leaching experiment

Each of the purified agents of Examples 5-8 was washed with 20 ml of water per 1 g, and 5 g of each of the purified agents was added to 100 ml of distilled water, followed by elution test using a magnetic stirrer. The theoretical value of silver supported on 5 g of the carrier was 0.015 g, and the amount obtained from the dissolution experiment was calculated as a percentage with respect to the theoretical value, and the results are shown in Table 9 below.

Sample number Conditions (loading: 0.3% by weight) Time elapsed (hr) ICP measurement (ppm) Estimated amount of elution (%) Example 5 AgNO ₃ wetting NaCl One 0.82 0.547 5 0 0 10 0 0 24 0 0 48 0 0 72 0 0 Example 6 AgNO ₃ dry NaCl One 0.86 0.573 5 0 0 10 0.075 0.05 24 0 0 48 0 0 72 0 0 Example 7 NaCl wetting AgNO ₃ One 0.09 0.06 5 0 0 10 0 0 24 0 0 48 0 0 72 0 0 Example 8 NaCl dry AgNO ₃ One 0.595 0.393 5 0 0 10 0 0 24 0 0 48 0 0 72 0 0

In this experiment, each sample after 72 hours was agitated by stirring the magnetic stirrer to adsorb the silver component in the solution, and silver was not detected after one hour.

(Comparative Example 25)

AgNO ₃ aqueous solution and chorale sand were mixed and calcined at 500 ° C for 2 hours to carry AgNO ₃ onto the carrier to prepare a coral sand purification agent. At this time, the loading amount of Ag was 0.3% by weight of the carrier.

50 g of the purified water of the chalcogen sand of Comparative Example 25 was placed in 600 ml of distilled water and maintained at 40 캜 without stirring, and the silver concentration with time was measured. The results are shown in Table 10 below.

Time elapsed (hr) ICP measurement (ppm) Estimated amount of elution [%] One 0.888 0.35 5 0.955 0.38

As shown in Tables 9 and 10, silver was not detected from 1 hour after the stirring process of Example 5-8, and in Comparative Example 25, silver was not eluted for a long time due to no stirring process . However, when the elution amounts of the whole are compared, it can be understood that the silver elution of Examples 5-8 is less than that of Comparative Example 25.

(2) is a digestion confirmation experiment,

4 g of the coral sludge purified water prepared by the method of Example 5-8 was heated with 50 ml of nitric acid. Was prepared so that the amount of silver eluted when the added amount of 3% by weight of the sample was carried on a 100% carrier was 240 ppm. Actually, the amount of silver supported on the coral-sands water purification agent was measured, and the results are shown in Table 11 below.

Conditions (silver loading: 0.03 g per 10 g carrier) ICP measurements Experimental value (ppm) Theoretical value Carrying amount [%] Example 5 AgNO ₃ wetting NaCl After 72 hours elution 49.2 20.05 Example 6 AgNO ₃ dry NaCl After 72 hours elution 49.1 20.458 Example 7 NaCl wetting AgNO ₃ After 72 hours elution 52.2 21.75 Example 8 NaCl dry AgNO ₃ After 72 hours elution 46.6 19.417

(3) Flow test

(Examples 9-10)

Was carried out in the same manner as in Example 5 except that the amounts of silver supported were changed to 0.03 and 0.1 wt%, respectively.

(Examples 11-12)

Was carried out in the same manner as in Example 7, except that the amount of silver supported was changed to 0.03 and 0.1 wt%, respectively.

(Comparative Examples 26-27)

The same procedure as in Comparative Example 25 was carried out except that the firing step was conducted at 500 占 폚 for 3 hours and the amount of silver supported was changed to 0.03 and 0.1 wt%, respectively.

The coral sand purifying agent prepared by the method of Examples 9-10 shows the original carrier color as it is, and the coral sand purifying agent prepared by the method of Comparative Examples 25-27 shows soil brown.

50 g of the purified water of the coral sand obtained by the method of Example 9-12 and Comparative Example 25-27 was put into a bed of 50 mm in diameter and water was passed at a flow rate of 2 L / (Ppb) was measured by ICP and the results are shown in Table 12 below.

0.03 wt% Ag 0.1 wt% Ag 0.3 wt% Ag Quantity of water Example 11 Example 9 Comparative Example 26 Quantity of water Example 12 Example 10 Comparative Example 27 Quantity of water Example 5 Example 7 Comparative Example 25 10 2 13 9 10 40 23 54 100 28 30 53 20 7 8 34 20 29 6 44 200 13 17 39 40 15 3 25 30 28 0 41 300 24 19 39 60 19 11 22 60 8 8 32 400 13 13 30 80 12 7 3 90 23 7 26 500 21 10 28 100 9 13 3 120 78 2 24 600 11 20 27 120 9 34 9 150 17 5 20 700 7 - - 160 7 6 8 180 11 5 18 800 18 - - 180 13 0 7 210 10 8 16 200 One 0 7 240 9 - 23

The elution tendency of the coral sand purifying agents of Examples 9 and 11 and Comparative Example 26 (silver loading theoretical value: 0.03% by weight, 0.015 g) according to running water is shown in Fig. 1, Fig.

In addition, 200 liters of the coral sand purification agent (0.03 wt%, theoretical value of Ag loading: 0.015 g) of Examples 9 and 11 and Comparative Example 26 were passed through the column, and the amount of eluted Ag and the amount of Ag for each sample were measured, The results are shown in Table 13 below.

sample Amount of Ag Ag Residual Ag amount × 10 ^-6 g % % Example 9 2130 14.2 85.80 Example 11 1995 13.03 86.97 Comparative Example 26 2370 15.8 84.20

As shown in FIG. 1 and Table 13, it can be seen that the silver halide water purifier of Examples 9 and 11 has a smaller silver elution amount than that of the coral sand purifying agent of Comparative Example 26.

In addition, 50 g of the purified water (theoretical silver loading value: 0.1% by weight, 0.05 g) of Examples 10 and 12 and Comparative Example 27 was passed through at a flow rate of 2 L / min to measure the dissolution tendency And the results are shown in Fig. 2, Fig.

The amount of eluted Ag and the amount of Ag for each sample were measured after passing 240 liters of the purified agent (theoretical value of the Ag loading: 0.1 weight%, 0.05 g) of Examples 10 and 12 and Comparative Example 27, Respectively.

sample Amount of Ag Ag Residual Ag amount × 10 ^-6 g % % Example 10 1482 2.96 97.04 Example 12 5795 11.59 88.41 Comparative Example 27 6225 12.45 87.55

As shown in FIG. 2 and Table 14, it can be seen that the silver halide water purifying agent of Examples 10 and 12 has a smaller silver elution amount than that of the coral sand purification agent of Comparative Example 27.

The elution tendency was measured by passing water at a flow rate of 2 L / min using 50 g of the coral sand purifying agent (theoretical loading value of silver: 0.3% by weight, 0.15 g) of Examples 5 and 7 and Comparative Example 25. The results are shown in Fig.

The amount of eluted Ag and the amount of residual Ag were measured for each sample after 600 liters of the coral sand purification agent (theoretical loading value of silver: 0.3 wt%, 0.15 g) of Examples 5 and 7 and Comparative Example 25 were passed through the column, Respectively.

sample Amount of Ag Ag Residual Ag amount × 10 ^-6 g % % Example 5 10665 7.11 92.89 Example 7 11810 7.87 92.13 Comparative Example 25 22410 14.94 85.06

As shown in FIG. 3 and Table 15, it can be seen that the silver halide water purifier of Examples 5 and 7 has a smaller silver elution amount than that of the coral sand purifying agent of Comparative Example 25.

(4) Antimicrobial activity experiment

[1] The standard is the antibacterial test of the solution (AgNO ₃ )

1) Experimental strain

Escherichia coli KCTC (Korean Collection for Type Culture) 1039 (E. coli) Escherichia coli

Pseudomonas aeruginosa KCTC 2004 (P. aeruginosa): Pseudomonas aeruginosa

2) Experimental method

Each strain was inoculated into Tryptic Soy (TS) broth and cultured at 30 DEG C for 15-18 hours. The culture was centrifuged to obtain cells, washed with sterile distilled water, and suspended again in sterile distilled water. The standard of sterilization of the strain suspension with membrane filter (φ = 0.2 μm) was inoculated to a solution (50 ppb) and distilled water (0 ppb) at a final bacterial concentration of 10 ⁶ cells / ml. The inoculated standard was prepared by dissolving the solution and distilled water at 30 ° C. at predetermined time intervals, diluting 10 times, and spreading plate counting on TS agar medium. The number of colonies (microorganism colonies) formed after culturing spreaded TS agar plates at 30 ° C for 24-48 hours was calculated in terms of the number of bacteria. The same experiment was repeated twice and averaged.

3) Experimental results

The results of the experiment using Escherichia coli are shown in FIG. 4, and the results of the experiment using Pseudomonas aeruginosa are shown in FIG. Table 16 shows the results of decreasing the number of bacteria by time. In Table 16, the values represent the standard deviation (SD) ± average of the two measured values, respectively, and cfu represents the colony forming unit. As shown in Figs. 4-5 and 16, neither of the bacteria showed any change in the antibiotic effect for 24 hours.

Distilled water (0 ppb) The standard is a solution (50 ppb) Time (hr) Log cfu / ml 占 S.D % decrease Log cfu / ml 占 S.D % decrease 0 6.08 ± 0.05 0.00 6.06 + 0.04 0.00 6 6.02 ± 0.08 12.90 6.06 ± 0.06 0.00 12 6.10 ± 0.09 -4.71 6.20 ± 0.05 -38.03 24 6.05 ± 0.01 4.50 6.12 ± 0.05 -14.82

[2] Antimicrobial activity of coral sand supported with silver

(A) agar plate test

1) Experimental strain

Escherichia coli KCTC ( E. coli ) Escherichia coli

Pseudomonas aeruginosa KCTC ( P. aeruginosa ): Pseudomonas aeruginosa

2) Experimental method

Each strain was inoculated into Tryptic Soy (TS) broth and cultured at 30 DEG C for 15-18 hours. 5 占 퐇 of the culture solution was inoculated on a TS soft agar (5 ml) at 45 占 폚 and suspended, followed by coating on a TS agar plate. Approximately 0.5 g of each carrier was placed on the surface of the agar plate. The agar plate on which the carrier was placed was incubated at 30 DEG C for 18 hours. The inhibition zone around the growth inhibition zone around the coral sands purification agent (Example 5) carrying the carrier silver was confirmed.

3) Experimental results

① Escherichia coli

A) a coral-sand remover (Fig. 6 (a), Fig. 7 (a)

Growth inhibition zone does not appear.

(B) (c) of FIG. 6 and (e) and (g) of FIG. 7)

FIG. 6C shows the results of the pre-watering test of the coral-sand remediation agent of Example 5, and FIG. 6D shows the experimental results of the coral-sand remediation agent of Example 10 after water-feeding. In addition, the results of the pre-water test of the coral sand remedial agent of Example 10 and the results of the pre-water test of the coral sand remedial agent of Comparative Example 25 are shown in FIG. 7, respectively.

6 and 7, the growth inhibition zone was not observed in the coral sand purification agent without silver, and the growth inhibition zone was confirmed around the coral sand in both the coral sand purification agents of Examples and Comparative Examples, I could confirm.

② P. aeruginosa

A) (Fig. 8 (a) and Fig. 9 (a)) in which silver is not supported,

Growth inhibition zone does not appear.

(B) (c) and (d) of FIG. 8 and (e) and (g)

FIG. 8C shows the results of the pre-watering test of the coral-sand remedial agent of Example 5, and FIG. 8D shows the experimental results of the coral-sand remedial agent of Example 10 after passing the water. In addition, the results of the pre-water test of the coral sand remedial agent of Example 10 and the pre-water test results of the coral sand remedial agent of Comparative Example 25 are shown in FIG. 9, respectively.

8 and 9, the growth inhibition zone was not observed in the coral sand purification agent without silver, and the growth inhibition zone was confirmed around the coral sand in all of the coral sand purification agents of Examples and Comparative Examples, I could confirm.

As shown in Fig. 6-9, the growth inhibitory effect of the coral sands water purifying agent supported on the borehole was found to be larger than that of E. coli on the growth of P. aeruginosa .

In addition, the results of decreasing the number of bacteria in time were measured in Examples 5, 10 and Comparative Example 25 and in the non-supported coral sand remover and distilled water, and the results are shown in Tables 18-20.

Uncoated Example 5 Time (hr) Log cfu / ml 占 S.D % decrease Log cfu / ml 占 S.D % decrease 0 7.28 ± 0.05 0.00 7.31 ± 0.10 0.00 5 7.27 ± 0.02 2.28 5.16 ± 0.30 99.29 10 7.20 ± 0.02 16.82 0.99 ± 0.49 99.99 15 7.18 ± 0.01 20.56 - -

Example 10 (after passing through water) Example 10 (Before water supply) Time (hr) Log cfu / ml 占 S.D % decrease Log cfu / ml 占 S.D % decrease 0 7.32 + 0.02 0.00 7.28 ± 0.05 0.00 5 7.01 ± 0.01 51.02 4.29 ± 0.23 99.90 10 6.48 0.31 85.55 1.30 ± 0.00 99.99 15 6.02 + 0.49 94.99 - -

Comparative Example 25 Distilled water Time (hr) Log cfu / ml 占 S.D % decrease Log cfu / ml 占 S.D % decrease 0 7.29 + 0.04 0.00 7.31 ± 0.03 0.00 5 5.40 0.35 98.71 7.29 ± 0.05 2.28 10 1.54 + 0.02 99.99 7.28 ± 0.05 4.50 15 7.01 ± 0.01 - 7.25 ± 0.05 10.88

As shown in Table 18-20, almost all of the bacteria were killed by 50% or more within 5 minutes when the silver impregnated coral-sand remover was used. However, when silver was not coated, distilled water and 20% Of the total number of deaths.

(B) distilled water experiment

1) Experimental strain: Escherichia coli KCTC 1039 ( E. coli )

2) Experimental method

Each strain was inoculated into Tryptic Soy (TS) broth and cultured at 30 ° C for 15-18 hours. The culture broth was centrifuged to obtain cells, washed with sterile distilled water, and suspended in sterile distilled water to prepare an inoculum. (Example 5 (before water supply), Example 10 (after water supply), Example 10 (before water supply) and Comparative Example 25) containing the silver-containing water and the silver- (0.25 g of purified water: 24.75 g of distilled water) was inoculated so that the final bacterial concentration was 10 ⁷ cells / ml.

The inoculated product was kept at room temperature (25 캜), taken at regular intervals, diluted 10-fold and spread-rate counted on a TS agar medium. Bacterial counts were calculated by counting the number of colonies (microbial colonies) formed after spreading TS agar plates cultured at 30 ° C for 24 hours to 48 hours. The same experiment was repeated twice and averaged.

3) Experimental results

The results of the experiment are shown in Fig. The results are as follows, which is divided into the coral sands purification agent with silver not supported and the coral sands purification agent with silver support.

1) silver impregnated coral sand purification agent (Fig. 10 , a)

There was no change in bacterial counts for 15 minutes. The change in bacterial counts with time of the water purification agent of coral sand is also shown in Table 21 below.

2) silver supported coral sand remover (Example 5 (before water supply) (Fig. 10 , c), Example 10 (before water supply) (Fig. 10 , e) and Comparative Example 25 (before water supply) (Fig. 10 , g)

The rate of death was about 99% after 5 minutes, and the remaining number of bacteria after 10 minutes was very low, about 0-10 cells / ㎖. The difference in the effect of each of the coral sand removers appeared to be little, but it was judged that the coral sand remover of Example 10 (before water) was slightly superior.

3) Silver impregnated coral sand remover (Example 10 (after watering) (Fig. 10 , d)

After 15 minutes, it decreased to 95%, but it was weaker than the other three species.

As described above, the water purification agent of the present invention can effectively purify water owing to the germicidal effect of silver because the silver is hardly eluted and harmless to the human body.

Claims (14)

Adding an aqueous solution of hydrochloric acid salt to the carrier; Drying said mixture; To the dried product is added a silver salt and an aqueous solution of an alcohol &Lt; / RTI &gt; wherein the method comprises the steps of: The process according to claim 1, wherein the carrier is activated carbon and the aqueous alcohol solution is an aqueous ethanol solution. The method according to claim 1, wherein the amount of the alcohol aqueous solution used is at least the saturation volume of the carrier. The method according to claim 1, wherein the alcohol aqueous solution is a mixed solution of 10 to 30% by volume of alcohol and 90 to 70% by volume of water. The method according to claim 1, wherein the silver salt is added in an amount of 0.1 to 0.4% by weight based on the weight of the carrier. The method according to claim 1, further comprising a step of heat-treating the mixture of the carrier, the chloride salt, the silver salt and the alcohol at 200 to 350 ° C for 2 to 3 hours after the step of adding the silver salt and the aqueous alcohol solution Gt; (Fixed) Adding an aqueous solution of a chloride salt to the carrier; Adding an aqueous silver salt solution to the mixture; The obtained mixed solution is subjected to heat treatment &Lt; / RTI &gt; wherein the method comprises the steps of: 8. The method according to claim 7, wherein the carrier is a coral sand, and the amount of the aqueous solution of the chloride salt and the aqueous solution of silver salt is the saturation volume of the carrier. The method according to claim 7, wherein the silver salt is added in an amount of 0.1 to 0.4% by weight based on the weight of the carrier. (Fixed) 8. The method according to claim 7, wherein the heat treatment is performed at 200 to 350 DEG C or 400 to 600 DEG C for 2 to 3 hours. (Fixed) Adding an aqueous silver salt solution to the carrier; Adding an aqueous chloride salt solution to the mixture; The obtained mixed solution is subjected to heat treatment &Lt; / RTI &gt; wherein the method comprises the steps of: 12. The method according to claim 11, wherein the carrier is a coral sand, and the amount of the silver salt aqueous solution and the aqueous chloride salt solution used is the saturated volume of the carrier. 12. The method according to claim 11, wherein the silver salt is added in an amount of 0.1 to 0.4% by weight based on the weight of the carrier. (Fixed) 12. The method according to claim 11, wherein the heat treatment is performed at 200 to 350 DEG C or 400 to 600 DEG C for 2 to 3 hours.