KR20080087952A - Filter for water purifier including organic germanium and thereof method - Google Patents

Abstract

A filter for water purifier comprising organic germanium is provided to allow users to drink water comprising organic germanium by heating a porous adsorbent to expand pores of the adsorbent, adsorbing organic germanium onto the expanded pores, coating ethyl cellulose on the organic germanium-adsorbed adsorbent, and using the resulting adsorbent in the filter for the water purifier, thereby eluting organic germanium into purified water, and a manufacturing method of the filter is provided. A filter for water purifier comprising organic germanium comprises organic germanium adsorbed onto a porous adsorbent and coated with an insoluble polymer. A manufacturing method of a filter for water purifier comprising organic germanium comprises: an adsorption process for adsorbing organic germanium onto a porous adsorbent, the adsorption process comprising steps of (1) heating a porous adsorbent at 70 to 150 deg.C for 1 to 2 hours, (2) dissolving organic germanium into distilled water, (3) mixing the organic germanium-dissolved water of the step(2) with the heated porous adsorbent of the step(1), and (4) drying the organic germanium-dissolved water mixed in the step(3) at 25 to 100 deg.C for 12 to 24 hours; and a coating process comprising the steps of (5) dissolving an insoluble polymer into ethyl alcohol and adding distilled water into the dissolved solution to prepare an insoluble polymer coating solution, (6) coating the organic germanium-adsorbed porous adsorbent of the step(4) with the insoluble polymer coating solution, and (7) drying the coated porous adsorbent of the step(6) at 70 to 80 deg.C for 12 to 24 hours. Further, the porous adsorbent is one selected from activated carbon, zeolite, silica, activated alumina and clay.

Description

Filter for water purifier containing organic germanium and a method of manufacturing the filter {Filter for water purifier including organic germanium and pretty method}

1 is a view showing a manufacturing process of the filter for water purifiers containing organic germanium according to the present invention.

The present invention relates to a filter for water purifier containing organic germanium and a method for producing the filter.

In recent years, as the speed of industrial development increases rapidly, industrial wastewater generated from various plant facilities, etc., is introduced into a drinking water source, thereby degrading water quality. Normally, tap water supplied to each household is withdrawn from the water system of each stream through the intake station, and the contaminated water from the reservoir is supplied through the water pipe through the pollution and water purification process, but as a result of using a large amount of disinfectant in the water purification process If you drink without any treatment, problems with odor occurs. Accordingly, the tendency to make drinking water or purified water edible is common. However, bottled or purified water is easily contaminated by microorganisms and generates off-flavor.

Therefore, in order to solve the above problems and the like, a water tank is formed of a synthetic resin and uses a water purifier purified by a fine filter. The water purifier as described above is not only able to further activate the beneficial components such as minerals, but also has a problem that harms the health by very poor E. coli removal and sterilization and deodorizing action.

Patent No. 10-0360283 has been invented to solve the various problems as described above is laminated bamboo activated carbon filtration layer, oak activated carbon filtration layer, activated carbon filtration layer of pine, ganban stone filtration layer and germanium ore filtration layer in multiple stages, Disclosed is an active water purification device using a filter prepared by mixing the above materials at a constant ratio.

The water purification device as described above has the advantage of removing harmful substances in the water and preventing the second pollution of the river water, but the filtration filter is formed in multiple stages, the process of treating each material with a filtration layer is required, formed in multiple stages as described above The problem is that the beneficial minerals contained in the water are also filtered through several layers of filtration.

An object of the present invention for solving the above problems is to filter the water purifier and the organic water purifier comprising an organic germanium, characterized in that the organic germanium is adsorbed on the porous adsorbent in order to elute the organic germanium at the purified water It is to provide a method for producing a filter for.

The present invention for achieving the above object relates to a filter for a water purifier containing an organic germanium and a method for producing the filter for water purifiers.

More specifically, it characterized by a filter for water purifiers containing organic germanium, characterized in that the organic germanium is adsorbed on the porous adsorbent and coated with an insoluble polymer.

In another aspect, the present invention comprises the step of heating the porous adsorbent at 70 ~ 150 ℃ for 1 to 2 hours;

⑵ dissolving organic germanium in distilled water;

Mixing water in which the organic germanium is dissolved in step iv with the porous adsorbent heated in step iii; And

An adsorption process of adsorbing the organic germanium on the porous adsorbent, which comprises drying the mixed water of the organic germanium mixed in the step ⑷ 에서 at 25 to 100 ° C. for 12 to 24 hours,

단계 preparing an insoluble polymer coating solution by dissolving insoluble polymer in ethyl alcohol and then adding distilled water;

Coating a porous adsorbent on which the organic germanium is adsorbed in the step ⑹ ⑹ with an insoluble polymer coating solution; And

Characterized in that the method for producing a filter for water purifier comprising an organic germanium, characterized in that it comprises a coating process comprising the step of drying the coated porous adsorbent in step ⑺ 70 at 70 ~ 80 ℃ 12 to 24 hours.

In addition, the present invention is characterized in that any one selected from activated carbon, silica, activated alumina, zeolite and filad clay as the porous adsorbent.

In addition, the present invention is characterized in that any one selected from ethyl cellulose, cellulose nitrate, cellulose acetate and cellulose propionate as the insoluble polymer.

In addition, the present invention is characterized in that the addition amount of the insoluble polymer is 15 to 25 g.

In addition, the present invention is characterized in that the addition amount of the porous adsorbent is 5 ~ 10 kg.

In addition, the present invention is characterized in that the addition amount of the organic germanium is 5 ~ 10 g.

In addition, the present invention is characterized in that the addition amount of the ethyl alcohol is 5 ~ 10L.

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

The present invention facilitates the adsorption of organic germanium by expanding the pores of activated carbon by heating the porous adsorbent at 70 ~ 150 ℃ for 1 to 2 hours, which is heated to adsorb germanium to the activated carbon than at room temperature This is because it is preferable to reduce the initial germanium elution amount so that the organic germanium is continuously eluted at the time of purification.

In order to adsorb the organic germanium to the porous adsorbent, a solid organic germanium is dissolved in 5 to 15 L of distilled water to prepare a liquid phase.

The present invention is to dry the mixture of the porous adsorbent and organic germanium for 12 to 24 hours at 25 ~ 100 ℃, this step is carried out to stabilize the organic germanium adsorbed on the porous adsorbent and remove moisture. Preferably, it is preferably dried at 70 ° C., which may be desirable to shorten the drying time and to reduce the pores of the expanded adsorbent by heating the porous adsorbent at 110 ° C.

The present invention adds ethyl alcohol, ethyl cellulose and distilled water when preparing an insoluble polymer coating solution, wherein the amount of ethyl alcohol is 5-10 L, the amount of insoluble polymer is 15-25 g, and the amount of distilled water is 1 ˜8 L.

The present invention is heated for 12 to 24 hours at 70 ~ 80 ℃ to remove the alcohol from the mixture of the porous adsorbent and ethyl cellulose adsorbed organic germanium. It is preferably heated at 60 ° C., which is a step of completely drying the porous organic adsorbent coated with ethyl cellulose to be used as a filter. If excessive temperature is maintained, ignition of alcohol may occur, and at room temperature When drying by heating, there is a disadvantage in that the drying time is long, it was confirmed that drying by heating at 60 ℃.

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

Example 1

7 kg of activated carbon was heated at 110 ° C. for 1 hour and 30 minutes to expand pores of the activated carbon, and 7 g of organic germanium was dissolved in 11 L of distilled water. 11 liters of water in which organic germanium was dissolved was mixed with the heated activated carbon. The mixed organic germanium-dissolved water was dried at 70 ° C. for 24 hours to adsorb the expanded pores of activated carbon.

Comparative Example 1

In the above embodiment was carried out in the same manner as in Example 1 except that the activated carbon is adsorbed at room temperature without heating the activated carbon to 110 ℃.

Experimental Example 1

After filling the filter of the domestic water purifier with 70 g of the activated carbon adsorbed to each organic germanium carried out in Example 1 and Comparative Example 1, 1 L, 20 L, 100 L, 300 L, 500 L, 1000 L and 1500 L was passed through to compare the elution of germanium.

The organic germanium elution amount according to Experimental Example 1 is shown in Table 1 below.

Sample 1 ℓ 20 ℓ 100 ℓ 300 ℓ 500 ℓ 1000 ℓ 1500 ℓ Example 1 16264 448 161 115 121 71 42 Comparative Example 1 11056 1676 388 294 254 129 98 Organic Germanium Elution Unit: ppb

As shown in Table 1, in Example 1 according to the present invention, when 1 L of distilled water was heated at 110 ° C. in a water purifier and then passed through a filter in which organic carbon was adsorbed, the organic germanium was adsorbed at room temperature. The amount of organic germanium eluted was less than that of the case, but the amount of organic germanium eluted increased as the amount passed through the filter increased.

These results can be inferred to be due to the expansion of pores by heating the porous adsorbent at a high temperature, ie, 110 ° C., rather than adsorbing organic germanium to the porous adsorbent at room temperature, thereby adsorbing the organic germanium into the enlarged pores of the porous adsorbent. there was.

Example 2

7 kg of activated carbon was heated at 110 ° C. for 1 hour and 30 minutes to expand pores of the activated carbon, and 7 g of organic germanium was dissolved in 11 L of distilled water. 11 liters of water in which organic germanium was dissolved was mixed with the heated activated carbon. The mixed organic germanium-dissolved water was dried at 70 ° C. for 24 hours to adsorb the expanded pores of activated carbon. After dissolving 21 g of ethyl cellulose in 8.5 L of ethyl alcohol, 4.5 L of distilled water was added to prepare 13 L of an ethyl cellulose coating solution. 11 l of an ethyl cellulose coating solution was coated on the activated carbon to which the organic germanium was adsorbed, and dried at 75 ° C. for 20 hours.

Comparative Example 2

The same procedure as in Example 2 was repeated except that 7 g of ethyl cellulose was used.

Comparative Example 3

Except for using 35 g of ethyl cellulose in Example 2 was carried out in the same manner as in Example 2.

Experimental Example 2

After filling the filter with 15 g of the activated germanium-adsorbed activated carbon prepared in Example 2, Comparative Example 2 and Comparative Example 3, the amount of organic germanium elution was passed when 1 L, 20 L and 1000 L of each distilled water were passed through the filter. Measured.

The organic germanium elution amount according to Experimental Example 2 is shown in Table 2 below.

Sample 1 ℓ 20 ℓ 1000 ℓ Example 2 846 661 42 Comparative Example 2 1229 477 4.79 Comparative Example 3 234 167 1.80 Organic Germanium Elution Unit: ppb

As shown in Table 2, Comparative Example 2 using 7 g of ethyl cellulose as a coating agent coating a porous adsorbent on which organic germanium is adsorbed in Example 2 according to the present invention has an organic germanium elution of 1229 ppb when 1 liter of distilled water is passed. As a result, large amounts of organic germanium were eluted, and the amount of organic germanium eluted was drastically reduced when passed through 1000 L. On the contrary, Comparative Example 3 using 35 g of ethyl cellulose showed less elution of organic germanium at 234 ppb when 1 liter of distilled water was passed, but very small amount of organic germanium elution at 1.80 ppb when 1000 liter of distilled water was passed. If thick, it could be inferred that organic germanium is difficult to continuously elute.

Therefore, the organic germanium elution amount of Example 2 according to the present invention showed that the elution amount of the organic germanium is continuously maintained in comparison with Comparative Examples 2 and 3 even when passing 1000 L of distilled water.

The present inventors are currently defined in Korea to determine whether the water passed through the domestic water purifier using a filter coated with an ethyl cellulose porous organic adsorbent adsorbed organic germanium is suitable for the water quality test of drinking water prescribed in Korea and Total colony counts, Total Coliforms, Fercal Streptococcus , Pseudomonas aeruginosa ), Salmonella Typhi , Shigella , Spore Forming Sulfite Reducing Anaerobes and Yersinia I would like to.

Experimental Example  1: Total colony counts

1. Standard Agar Badge

To 1.0 ℓ of water, tryptone 5.0 g, yeast extract 2.5 g, glucose 1.0 g and agar 15.0 g were dissolved by heating. After adjusting the pH to 7.0 ± 0.2, divided into 10 ~ 12 ㎖ in a test tube at 121 ℃ High pressure steam sterilization for 15 minutes.

2. Phosphate buffer diluent

Dissolve 34 g of potassium dihydrogen phosphate in 500 ml of water, adjust the pH to 7.2 ± 0.2 at room temperature with sodium hydroxide solution (0.5N), add water to make 1 liter, and use it as a stock solution for preservation. 1.25 ml of this stock solution and 81.1 g of magnesium chloride (hexahydrate) are dissolved in 1 L of water, and 5.0 ml of magnesium chloride solution is added to make 1 L with water to form a phosphate buffer diluent. Phosphate-buffered diluent was divided into dilution bottles or test tubes with a screw cap so that 99 ± 2 ml was autoclaved at 121 ° C. for 15 minutes.

3. Appliances and Devices

Pipettes or automatic pipettes (with sterilized volumetric pipettes of 1 to 5 ml or with automatic pipettes (including plastic tips)), petri dishes (approximately 9 cm in diameter, 1.5 cm in height) or 1 Sterilized with disposable plastic products (57 cm 2)), constant temperature water bath (uses water temperature maintained at 45 ± 0.5 ° C), incubator (uses culture temperature maintained at 21 ± 1.0 ° C) ), Colony counter (use a magnifier and lighting device attached and partitioned with 1 cm 2 on the plate on which the petri dish is placed to facilitate the colony counting)

4. Test Method

end. Preparation and Testing

Water purified in a water purifier using a filter according to the present invention (hereinafter abbreviated as "inspection") should be refrigerated so as not to freeze below 4 ° C, even in this case, analysis should be started within 12 hours. If the analysis cannot be started within 12 hours, the normal bacteria of the purified water are not tested.

I. Dilute the test to 10% dilution using phosphate buffered dilution or peptone dilution to an appropriate concentration (concentration of 30 to 300 bacteria per 1 ml) and add 1 ml of each dilution to at least 2 sterile petri dishes. Put it in.

All. 10 to 12 ml of R2A medium sterilized in advance and maintained at 45 ± 0.5 ° C are aseptically divided into petri dishes containing the sample solution, and then rotated side to side to mix well with the medium.

la. Once the medium has solidified, count the number of colonies formed by incubating 72 ± 3 hours at 21 ± 1.0 ° C.

hemp. Dilute solution sterilized by the control test was carried out in the same manner as the above method as a control.

bar. The operation time from dilution of the inspection to dividing the plate medium into the petri dish shall not exceed 20 minutes.

5. Calculation of bacterial colonies

end. In principle, the colony should be counted by using a colony counter immediately after incubation and having no colony and having 30 to 300 colonies per 1 flat plate.

I. When more than 300 colonies are formed per plate, the most representative plate is selected and the number of colonies is calculated according to the dense plate measurement method. In the calculation method, when a glass petri dish with an inner diameter of 9 cm is used, the colony number averaged by counting 13 colonies within 1 cm 2 is multiplied by 65, and when a disposable plastic petri dish is used, it is multiplied by 57.

All. When less than 30 colonies are formed per plate, the colonies of the plate inoculated with the stock solution are counted and averaged, and the substrate is necessarily called CFU (Colony Forming Unit) in ml.

la. If there are no plates with 30 to 300 colonies and more than one plate with 300 or more colonies is present, the colonies of the nearest 300 plates are counted.

hemp. The calculation method is to measure the number of colonies in each plate used for the corresponding dilution factor, add them, divide them by the number of plates used, calculate the average number of colonies per plate, and multiply the corresponding dilution factor by the low temperature general bacterial count. Described as CFU. In all counting procedures, when the low temperature general bacterial count is 100 or more, three or less steps are rounded off from the high unit number, and the effective number is cut in two steps, and the number less than 0 is the general bacterial count in 1 ml. In this case, the number discarded by the decimal point shall be written as the general number of bacteria in 1 ml.

Experimental Example  2: total coliform group (Total Coliforms )

1.Lactose lactose medium after double concentration (medium for estimation test)

Add 6.0 g of beef extract, 10.0 g of peptone, and 10.0 g of lactose to 1 l of water, dissolve by heating, adjust the pH to 6.9 ± 0.2, and divide 10 ml into a heavy test tube containing a Dharam test tube. Autoclaved for minutes.

2.BGLB (Brilliant Green Lactose Bile) medium (determination test medium)

To 1 liter of water, add 20.0 g of bovine bile, 10.0 g of peptone, 10.0 g of lactose, and 0.0133 g of brilliant green, dissolve by heating, adjust the pH to 7.2 ± 0.2, and add 10 ml to a small test tube containing a Dharam test tube. Dividing and autoclaving at 121 ℃ for 15 minutes.

3. Appliances and Devices

Pipette (use sterilized pipettes or auto pipettes with a capacity of 5-10 ml), test tubes (small test tubes (16 mm in diameter, 150 mm in height)) and heavy test tubes (18 mm in diameter, 180 mm in height) It can be plugged with cotton (plastic or metal lid can also be used) and can be sterilized under high pressure steam), Dharam test tube (with internal diameter 6 mm, height 30 mm), and can be autoclaved with high pressure. Platinum (use platinum rings with a ring diameter of about 3 mm) and incubators (use one that can maintain the culture temperature at 35 ± 0.5 ° C.)

4. Test

⑴ Estimation test

추정 The preliminary test for drinking water was inoculated with 10 ml of the test in 10 heavy test tubes (10 test tubes containing Dharam test tube) containing 10 ml of double lactose medium or lauryl trypsin medium at 35 ± 0.5 ℃. After 24 ± 2 hours of incubation, if the gas is generated, the test is considered positive and the definitive test is carried out (20 ml of the test may be inoculated into 5 large test tubes containing 10 ml of 3-fold enriched medium).

가스 If no gas is generated in any of the test tubes after 24 ± 2 hours of incubation, incubate up to 48 ± 3 hours under the same conditions. If there is still no gas, the test is judged negative. Conduct the test.

⑵ Confirmation test

가스 When gas is generated in the estimation test, 1 ml of platinum solution is taken from all the test tubes in which the gas is generated, and each plate is inoculated into a test tube containing 10 ml of BGLB medium (a test tube containing a squid test tube), and then 48 ± 35 ± 0.5 ° C. Incubate for 3 hours.

㈏ At this time, if no gas is generated, it is determined to be negative for total coliform group confirmation test. If gas is observed, it is determined to be positive for total coliform group.

Experimental Example  3: Fecal Streptococcus ( Fecal streptococcus )

1. Triple Concentration Azide Glucose Medium (Estimate Test Medium)

Add 13.5 g of beef, 15.0 g of tryptone, 45.0 g of glucose, 22.5 g of sodium chloride, 22.5 g of sodium chloride, and 0.6 g of sodium azide, and dissolve the mixture at a temperature of 7.2 ± 0.2 at room temperature. Dividing and autoclaving at 121 ℃ for 15 minutes.

2. Pieza enterococci agar medium (determination test medium)

1 L of water, 17.0 g of peptone C, 3.0 g of Fenton B, 5.0 g of yeast extract, 10.0 g of bacteriological bile powder, 5.0 g of sodium chloride, 1.0 g of sodium citrate, 1.0 g of escrine, 0.5 g of ferric ammonium citrate, azide Add 0.25 g of sodium and 15.0 g of agar, heat dissolve, adjust pH to 7.1 ± 0.2 at room temperature, autoclave at 121 ° C for 15 minutes, cool to 50-55 ° C, and add about 15 ml to sterile petri dish. Aseptically divide and solidify to prepare a flat medium.

3. Appliances and Devices

Apparatus and equipment shall be the same as those for E. coli testing.

4. Test

⑴ Estimation test

Inoculate 50 ml of the test into a large test tube containing 25 ml of five 3-fold enriched azide glucose medium and incubate at 35 ± 0.5 ° C for 24 ± 2 hours. If no clouding is observed, extend the culture to 48 ± 3 hours. do. After culture, observe the media turbidity. In any test tube, the medium does not become cloudy, the estimated test is negative, and in one or more test tubes, it is determined that the estimated test is positive regardless of bacterial growth or mixing of the sample. Is carried out.

⑵ Confirmation test

Take 1 platinum each from all the test tubes that have confirmed cloudy in the presumptive test, and stir each of the P. aureus selective agar medium and incubate for 24 ± 2 hours at 35 ± 0.5 ℃. After culturing, colonies were observed to have a brownish brown colony with a brown rim, which is positive for positive test, i.e., positive for streptococcus, and negative for positive test if no typical colonies were observed.

Experimental Example  4: Pseudomonas aeruginosa ( pseudomonas aeruginosa )

1.3 times rich asparagine medium (estimated test medium)

Into 1 liter of water, 9.0 g of asparagine DL, 3.0 g of potassium monohydrogen phosphate, and 1.5 g of magnesium sulfate (7) must be dissolved by heating to adjust the pH to 7.0 ± 0.2 at room temperature. Sterilize by autoclaving at 121 ° C. for 15 minutes.

2. Acetamide medium (determination test medium)

To 1 liter of water, 10.0 g of acetamide, 5.0 g of sodium chloride, 1.39 g of potassium dihydrogen phosphate, 0.73 g of potassium dihydrogen phosphate, 0.5 g of magnesium sulfate (hexahydrate), and 0.012 g of phenol red were added and dissolved in heat. After adjusting to ± 0.2, divide 10 ml into small test tubes and autoclave at 121 ℃ for 15 minutes.

3. Tryptic soy enrichment medium

To 1 liter of water, add 17.0 g of casein pancreatic lysate, 3.0 g of soybean powder papain lysate, 5.0 g of sodium chloride, 2.5 g of dipotassium phosphate, and 2.5 g of glucose. Sterilize by autoclaving at 121 ° C. for 15 minutes and aseptically dispense about 15 ml into a sterile Petri dish and harden.

4. Appliances and Devices

The same as the coliform bacterium test is used. In addition, an ultraviolet lamp (long wavelength 365 nm irradiation) and ultraviolet protective glasses are required.

5. Test method

⑴ Estimation test

50 ml of the test is inoculated in 5 test tubes containing 3 ml of asparazine medium and 3 ml of each. Asparazine medium inoculated with the test was incubated at 35 ± 0.5 ℃ for 24 ± 2 hours, and then put on UV protection glasses in the dark room and irradiated with long wavelength ultraviolet rays (near 365 nm) with an ultraviolet lamp to observe the presence of green fluorescence. If fluorescence occurs, the test is positive. However, if no clear fluorescence is found, continue incubation for up to 48 ± 3 hours. At this time, green fluorescence is not confirmed in the test tube. If green fluorescence is detected in the test tube, the test is positive, and the following definite test is continued to confirm the presence of Pseudomonas aeruginosa.

⑵ Confirmation test

In all test tubes where green fluorescence was confirmed in the estimation test, three times (approximately 0.1 ml) were taken from the upper layer of the positive medium using platinum immediately and evenly transplanted to the slope of each acetamide medium. Incubate for 36 hours. If there is no significant color change in the medium after incubation, it is negative for Pseudomonas aeruginosa. However, even one test tube exhibiting reddish purple color is determined as positive test positive.

⑶ Confirmation test

After pure separation of definite positive colonies, incubate at 41.5 ± 0.5 ℃ for 48 hours in tryptic soy enrichment medium or similar medium to observe growth. Non-growing colonies are determined to be Pseudomonas aeruginosa (N. aeruginosa) negative and grown colonies are Gram-negative bacterium, followed by gram staining, followed by microscopic observation. If it is identified as Pseudomonas aeruginosa in a biochemical identification test, it is determined to be Pseudomonas aeruginosa positive.

Experimental Example 5: Spore Forming Sulfite Reducing Anaerobes

1.2x rich DRCM medium

To 1 liter of water, add 6.0 g of yeast extract, 20.0 g of beef extract, 20.0 g of trycase, 20.0 g of glucose, 10.0 g of sodium chloride, 2.0 g of soluble starch, 1.0 g of cysteine (hydrochloride), 6.0 g of sodium acetate, and 0.5 g of agar. Heat dissolve to adjust the pH to 6.8 ± 0.2 at room temperature. Dispense 10 ml into a heavy test tube with a spiral plug and autoclave at 121 ° C for 15 minutes. In the test, 0.4 ml of a mixture of 4% ferric citrate and 7% sodium sulfite in equal amounts was added to each test tube.

2. Appliances and Devices

The apparatus and equipment are the same as those for the E. coli group test and additionally require a constant temperature bath (which can maintain a water temperature of 75 ± 1.0 ° C).

3. Test method

⑴ Apoptosis test

Each 10 ml of the test is aseptically placed in a test tube with five spiral plugs, and then allowed to stand for 10 minutes in a constant temperature bath maintained at 75 ± 1.0 ° C. At this time, all the bacteria that can not form apo will die and live only the bacteria that can form apo.

⑵ Culture and sulfite reduction test

After cooling the test tube with five helix plugs, which have been allowed to stand for 10 minutes in a 75 ± 1.0 ° C constant temperature bath, immediately cools to around 20 ° C, and adds 10 ml of each of the two-packed DRCM medium prepared in advance. After mixing the inspection and the medium to prevent bubbles, put the sterilized liquid paraffin into the surface of the medium aseptically every 2-3 ml and close the cap tightly. Incubate at 48 ± 3 hours at 35 ± 0.5 ° C. When the medium turns black after incubation, the sulfurous acid is reduced and is determined to be positive for sulfite-reduced anaerobic spore-forming bacteria, and it is determined that any one of five test tubes is positive.

Experimental Example  6: Salmonella ( Salmonella Typhi )

1. Triple enriched selenite liquid enrichment medium

Dissolve 15.0 g of tryptone, 12.0 g of lactose, 12.0 g of selenite, and 30.0 g of sodium phosphate in 1 L of water, dissolve it at 60∼70 ° C without boiling, and sterilize 25 ml of each in a sterile tube. The prepared medium is stored at 2-8 ℃.

2. Bismuth sulfite selective medium -For estimation test

1 l of peptone, 1 g of beef, 5.0 g of beef, 5.0 g of glucose, 4.0 g of sodium hydrogen phosphate, 0.3 g of ferrous sulfate, 8.0 g of bismuth sulfite, 0.025 g of brilliant green and 20.0 g of agar were dissolved and heated to 50-55. Cool to ºC and dispense into a sterile Petri dish to solidify. Do not boil for more than 1 ~ 2 minutes when heated. Prepared medium is stored at 2 ～ 8 ℃ and not stored for more than 4 days.

3. Apparatus and equipment are the same as those used for E. coli testing and additionally require refrigerator (2 ~ 5 ℃), optical microscope, gas burner, alcohol lamp and slide glass.

4. Test

⑴ Estimation test

50 ml of the test is inoculated into five test tubes containing 25 ml of three times enriched selenite enrichment medium. Inoculated selenite medium is incubated at 37 ℃ for 18-24 hours. If the incubation time is delayed, other bacteria such as Escherichia coli grow, so strictly observe the incubation time. Using platinum, take the enrichment medium from all the tubes and inoculate the bismuth agar selection medium. Observe colonies after incubation at 35 ° C. for 24 hours, incubate again, and re-observe after 48 hours, presuming that the black and shiny colonies with white rims at the edges are positive for Salmonella. If there is no typical benign colony and a green colony is produced, the colony is also tested for identification.

⑵ Confirmation test

㈎ Biochemical identification test: Colonies that are positive in the presumptive test are purely separated and transferred to selective medium. After Gram staining, confirm that it is Gram negative and bacillus by microscopic observation and use API 20E kit. If identified as Salmonella by biochemical confirmation, it is determined to be Salmonella positive. The experiment ends with a positive determination and if more informed about pathogenicity and epidemiology, further identification of species and serotypes should be performed through serological tests.

㈏ Serological tests: The bacteria identified as Salmonella in the biochemical test are grouped according to the A, B, C, D and E group antiserum corresponding to Salmonella O antiserum, and tested with single factor antiserum belonging to the group. If there is agglutination only in the Vi antiserum, check whether it is Salmonella typhi, and boil the bacterial suspension at 100 ° C. to destroy the Vi antigen, and then determine the group by viewing the O antiserum aggregation. Test the flagellar antigens Phase I and II with H-serum and determine the Salmonella species by combining the O-antigens and flagellar antigens. In addition, if you want to know more specifically Salmonella species, such as species (species) or antigen (serotype), please refer to the National Institutes of Health Salmonella Center for final identification. In the present invention, it is determined only whether the Salmonella species is suitable for the number of drinking water bacteria in Korea.

Experimental Example  7: Shigella Shigella )

1. Triple-fold selenite liquid enrichment medium is prepared in the same manner as Salmonella enrichment medium.

2. XLD (Xylose Lysine Deoxycholate) agar selection medium (for estimation test)

1 liter of water, 3.0 g of yeast extract, 5.0 g of L-lysine, 3.75 g of gyros, 7.5 g of lactose, 7.5 g of sucrose, 2.5 g of sodium desoxycholate, 0.8 g of ferric ammonium citrate, 6.8 g of sodium thiosulfate, Add 5.0 g of sodium chloride, 15.0 g of agar and 0.08 g of phenol red and heat until complete dissolution. After cooling to 55 ～ 60 ℃, aliquot into sterile Petri dishes to solidify. The prepared medium is stored at 2-8 ℃.

3. Apparatus and devices are the same as in Salmonella test.

4. Test

The process of enrichment of the putative test is identical to that of Salmonella. The cultured enrichment medium is taken as platinum, and inoculated into XLD agar selective medium in the same manner as Salmonella, followed by incubation at 35 ° C for 24 hours to form a red colony.

⑵ Confirmation test

㈎ Biochemical Confirmation Test: The same test as for Salmonella.

㈏ Serological tests: If you want to know the species of strains identified as Shigella in the biochemical identification test, Shigella O antiserum aggregation test.

Experimental Example  8: Yexinia ( Yersinia )

1. CIN Agar Badge

The components of Yexinia selective agar base medium are yeast extract 2g, peptone 17g, protose peptone 3g, mannitol 20g, sodium desoxycholate 0.5g, sodium chlorate 0.5g, sodium chloride 1g, sodium pyribate 2 g, 10 mg of magnesium sulfate (hexahydrate), 13.5 g of agar, 30 mg of neutral red, 1 mg of crystal violet, 4 mg of irgasan, and 1 L of water.

The constituents of the CIN cycinia antimicrobial supplement are 4 mg of cefsulodin, 2.5 mg of novobiocin and 10 ml of water. Yeastia selective agar base medium is autoclaved at 121 ℃ for 15 minutes, then cooled to 45 ~ 50 ℃ and added CN Yexinia antimicrobial supplement.

2. Mekongki Agar Badge

17 g of peptone, 3 g of proteos peptone, 10 g of lactose, bile salt No. 3 1.5 g, sodium chloride 5 g, agar 13.5 g, neutral red 0.03 g, crystal violet 0.001 g and 1 L of water (final pH (25 ° C) 7.1 ± 0.2)

3. mMC medium

10 g / l of D-sorbitol, 4.0 mg / l of irgasan and 2.5 mg / l of Novobiocin are added to the Mekongi agar base described above.

4. 0.288% potassium hydroxide solution

8.5 g of sodium chloride, 2.88 g of potassium hydroxide and 1 L of water are mixed.

5. Appliances and Devices

Filtration membrane (Use a sterilized filtration membrane with a grid of 0.45 μm in diameter and 47 mm diameter for microbial analysis.), Filtering device (A device for filtering by inserting a filtration membrane is used. .), Circular absorption pad (Use thick pad or sponge or glass fiber filtration membrane to sterilize 47mm diameter circular pad.), Petri dish (approximately 5.5 cm in diameter, 1.2 cm in height, small product (24 ㎠) Tweezers are blunt and wide, and do not physically damage the membrane when picking up the membrane.

6. Test

㈎ Estimation test

2 l of the test is taken immediately using a sterile container and tested immediately. If it cannot be tested immediately, it shall be transported in refrigerated condition and tested within a short time. 1 L of the collected inspection was passed through a sterilized filter (membrane filter, 0.22㎛ pore size) using a sterile filtration device, and then continuously filtered 20-30 ml of 0.288% potassium hydroxide solution within 20 seconds completely. Put this filter paper on the CIN medium and incubate for 48 hours at 25 ~ 28 ℃. The remaining 1 L is incubated in Mekongki medium (or mMC medium) through the same procedure. In CIN medium, small colonies that are not mucus and have a deep red in the center are avoided in Mekongki medium (or mMC), avoiding red or slime colonies (small 1 ~ 2 mm in diameter), and take flat colorless or pale pink colonies. Transfer to Brain Heart Infusion Agar.

㈏ Preliminary Identification

Preliminary experiments are done by inoculating TSI medium, urea medium and kinetic medium. In preliminary experiments, colonies that do not exhibit the characteristics of yeast strains are determined as negative yeast strains, and separated colonies with yeast strains are negative when Gram staining is performed. Y. enterocolitica decomposes sucrose and yellows at the bottom and slope, while Y. pseudotuberculosis is yellow at the slope and the bottom is not yellowed. No gas and hydrogen sulfide are generated. In urea medium, it shows a positive red color. The motility test was inoculated in two kinetic media and incubated separately at 37 ° C. and 25 ° C., respectively.

㈐ Identification test

Biochemical identification uses the API 20E Kit.

Table 3 below shows whether the purified water passing through the water purifier using the organic germanium-adsorbed porous adsorbent according to the present invention tested in Experimental Examples 1 to 8 meets the Korean drinking water standard.

General bacteria Total coliform group Fecal Coliform Escherichia Coli Pseudomonas aeruginosa Salmonella Shigella Sulfurous acid reduction base spore forming bacteria Yexinia standard 100 or less / 1ml ND / 50ml ND / 250ml ND / 250ml ND / 250ml ND / 250ml ND / 50ml ND / 2 ℓ Example 2 fitness ND ND ND ND ND ND ND ND: No Detectable

As shown in Table 3, the water passing through the filter according to the present invention was found to meet the Korean standard when compared with the example according to the present invention and the Korean standard. Therefore, it was proved that organic germanium did not affect the degree of contamination of the water purifier due to the adsorbent and ethyl cellulose.

In addition, the Korean standard further includes E. coli and F. coli, but the present invention does not test E. coli and F. coli in the total E. coli.

In addition, the present inventors lead, fluorine, arsenic, selenium, and mercury, which are defined as health hazards in Korea's drinking water standards when water is passed through an organic germanium adsorbent and a water purifier including a filter containing ethyl cellulose. The contents of, cyanide, ammonia nitrogen, hexavalent chromium, nitrate nitrogen, cadmium and boron were measured.

The experimental method of the following Experimental Examples 9-19 using Example 2 of this invention is based on the test method of the drinking-water quality process of the Ministry of Environment notification 2002-91 (revised on June 21, 2002).

Experimental Example  9: Pd; lead

Ministry of Environment Notice 2002-91 To comply with the test method 2-2-2-1 of drinking water quality process.

Experimental Example  10: Fluoride

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-1-1.

Experimental Example  11: Arsenic

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-2-2.

Experimental Example  12: selenium (Se; Selenium)

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-2-3.

Experimental Example  13: mercury (Hg; Mercury)

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-2-4.

Experimental Example  14: Cyan ( CN ; Cyanide)

According to the notification of the Ministry of Environment, No. 2002-91, Test Method of Drinking Water Quality Process 2-2-1-2.

Experimental Example  15: Ammonia nitrogen  ( NH ₃ -N, Ammonium-Nitrogen)

Ministry of Environment Notice 2002-91 To comply with the test method 2-2-1-3 of drinking water quality process.

Experimental Example  16: hexavalent chromium ( Cr ^{6 +} ; Hexachromium )

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-2-5.

Experimental Example  17: nitrate nitrogen ( NO ₃ -N; Nitrate Nitrogen)

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-1-4.

Experimental Example  18: Cd; Cadmium

According to the Ministry of Environment Notification No. 2002-91 Test Method of Drinking Water Quality Process 2-2-2-6.

Experimental Example  19: Boron

Ministry of Environment Notice No. 2002-91 Test method for drinking water quality 2-2-2-12 Inductively coupled plasma-atomic emission method.

Table 4 below shows whether or not the test results for Experimental Examples 9 to 19 meet Korean drinking water standards.

Pb F As Se Hg CN NH ₃ -N Cr ^{6 +} NO ₃ -N CD B standard 0.05 or less 1.5 or less 0.05 or less 0.01 or less 0.001 or less 0.01 or less 0.5 or less 0.05 or less below 10 0.01 or less 0.3 or less Example 2 fitness fitness fitness fitness fitness fitness fitness fitness fitness fitness fitness

As shown in Table 4, the present invention has proved that water containing organic germanium can be safely consumed without affecting the health effects of inorganic substances even when the porous sorbent coated with organic germanium is used as a filter. .

Although the present invention has been described with reference to the above embodiments, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. . Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

As described in detail above, according to the present invention, the porous adsorbent is heated to enlarge pores to adsorb organic germanium to the enlarged pores, and the organic germanium adsorbent is coated with ethyl cellulose to be used for water purifier filters. Organic germanium is continuously eluted, and water containing organic germanium can be routinely drunk.

Claims (13)

A filter for water purifiers comprising organic germanium, wherein the organic germanium is adsorbed on a porous adsorbent and coated with an insoluble polymer. The filter of claim 1, wherein the porous adsorbent is selected from any one of activated carbon, zeolite, silica, activated alumina, and filad clay. The water filter according to claim 1 or 2, wherein the insoluble polymer is selected from ethyl cellulose, cellulose nitrate, cellulose acetate and cellulose propionate. The filter for water purifiers containing organic germanium according to claim 1, wherein the amount of the porous adsorbent is 5 to 10 kg. The filter for water purifiers containing organic germanium according to claim 1, wherein the amount of the insoluble polymer is 15 to 25 g. The method of claim 1, wherein the amount of the organic germanium added is in the range of 5 to 10 g. ⑴ heating the porous adsorbent at 70-150 ° C. for 1-2 hours; ⑵ dissolving organic germanium in distilled water; Mixing water in which the organic germanium is dissolved in step iv with the porous adsorbent heated in step iii; And An adsorption process of adsorbing the organic germanium on the porous adsorbent, which comprises drying the mixed water of the organic germanium mixed in the step ⑷ 에서 at 25 to 100 ° C. for 12 to 24 hours, 단계 preparing an insoluble polymer coating solution by dissolving insoluble polymer in ethyl alcohol and then adding distilled water; Coating a porous adsorbent on which the organic germanium is adsorbed in the step ⑹ of the insoluble polymer coating solution; And Method of producing a filter for water purifier comprising an organic germanium, comprising a coating process comprising the step of drying the coated porous adsorbent in step ⑹ at 70 ~ 80 ℃ 12 to 24 hours. The method of claim 7, wherein the porous adsorbent is selected from one of activated carbon, zeolite, silica, activated alumina, and filad clay. The method of claim 7, wherein the insoluble polymer is selected from any one of ethyl cellulose, cellulose nitrate, cellulose acetate, and cellulose propionate. 10. The method of claim 7, wherein the amount of the porous adsorbent is 5 to 10 kg. The method for producing a water filter according to any one of claims 7 to 9, wherein the amount of the insoluble polymer is 15 to 25 g. The method for producing a water filter according to any one of claims 7 to 9, wherein the amount of the organic germanium added is 5 to 10 g. 10. The method according to any one of claims 7 to 9, wherein the ethyl alcohol is added in an amount of 5 to 10 L.

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