KR101536937B1 - Method for removal of antibiotics in water using steam activated biochar derived from burcucumber(Sicyos angulatus L.) - Google Patents

Abstract

[0001] The present invention relates to a method for removing an antibiotic substance from a water vapor using a vapor activated bacterium, and more particularly, to a method for removing an antibiotic substance from a vapor activated bacterium by using a steam activated bacterium, The present invention relates to a method for removing an antibiotic substance from water by using a steam-activated visible-light biochip capable of removing the antibiotic substance from water by adding the antibiotic substance to the water containing antibiotic substance and adsorbing the antibiotic substance on the vapor- will be.

Description

[0001] The present invention relates to a method for removing an antibiotic substance from water using steam activated activated carbon microbes (Sicyos angulatus L.)

[0001] The present invention relates to a method for removing an antibiotic substance from a water vapor using a vapor activated bacterium, and more particularly, to a method for removing an antibiotic substance from a vapor activated bacterium by using a steam activated bacterium, The present invention relates to a method for removing an antibiotic substance from water by using a steam-activated visible-light biochip capable of removing the antibiotic substance from water by adding the antibiotic substance to the water containing antibiotic substance and adsorbing the antibiotic substance on the vapor- will be.

Antibiotics used for the treatment and prevention of diseases of animals and the promotion of growth are only used about 10 to 20% after they are administered to animals, and most of them are released to the outside of animals.

Exhausted antibiotics are introduced into soil, water, and other environments through various routes such as excreta and urine. The introduction of such antibiotics into the environment causes problems such as bacterial resistance, which is resistant to antibiotics, Health and environmental health can be a threat to health.

In fact, antibiotic residues are reported in environments such as soils, groundwater, and rivers in the vicinity of places where animals such as cows, pigs, chickens and goats are raised in large quantities.

In order to remove antibiotics, activated carbon is used as an adsorbent to adsorb antibiotics on activated carbon to remove antibiotics. However, due to problems such as cost of treating activated carbon, activated carbon as an adsorbent for removing antibiotics It is necessary to develop other substitute components.

Burcucumber ( Sicyos angulatus L. ) is a perennial plant originating in northern america. It spreads widely using tendrils to inhibit the light conditions of surrounding plants. It spreads its distribution area to general cropland with rapid propagation and decreases crop yield And native ecosystem disturbances.

As a result, on June 1, 2009, the Ministry of the Environment designated the plant as an ecosystem disturbing plant and has been working on the elimination of visible specks nationwide.

However, since the amount of visible light removed due to the large distribution area of the visible light and the rapid reproductive force is increased, the cost of the incineration treatment is increased when the visible light is removed.

Recently, biomass such as algae and plant resources such as trees, grasses, branches, leaves, roots, and fruits of crops have been pyrolysis by heating under anaerobic atmosphere or pyrolysis by heating under inert gas It has been reported that biochar produced through pyrolysis has excellent efficiency in adsorption removal of organic and inorganic contaminants due to inherent physical and chemical properties.

The inventors of the present invention conducted research on removing antibiotics in water by using a visible thin film, and found that the vapor-activated thin-film bio-tea obtained by carbonizing the thin film and activating the thin film bio- The present inventors have found that the antibiotic substance can be removed by adsorbing the antibiotic substance on the vapor-activated caustic biochip by adding it to the water containing the substance, thereby completing the present invention.

The present invention is a useful technique that can effectively recycle residues of foreign plants, as well as effective removal of antibiotics contained in the environment, particularly in water.

As a prior art related to the removal of antibiotics, Korean Patent Application No. 2007-0061226 discloses a method for preventing and growing antibiotics contained in feeds for the prevention and growth of diseases in livestock and aquaculture, , Beta-lactamase, which degrades antibiotic substances having a beta lactam ring, is rapidly removed from the living body of edible livestock, poultry, and aquaculture by administering to the live livestock (fish) before slaughter or shipment There is a way.

However, the present invention and the prior art are different from each other in the technical features of the invention and are different from each other in the invention.

It is an object of the present invention to provide a method for removing antibiotics from water containing antibiotics.

The present invention relates to a process for the removal of antibiotics in water using a vapor-activated spiked bio-car, which can be removed by adsorbing the antibiotic to the vapor-activated spiked bio-car by adding the steam-activated spiked bio- ≪ / RTI >

The method of the present invention for removing an antibiotic substance from water using a steam activated biofilm of the present invention is a method for removing antibiotics from water by adding a biocide obtained by drying a dried bark of water and a bark of a bark obtained by carbonizing the bark, Compared to adsorbing substances, the adsorbing ability of antibiotics is high, which is very effective for the purification of water containing antibiotics.

In addition, the present invention can be applied not only to the treatment of visible bark, which is an ecosystem disturbing material, but also to the treatment cost of activated carbon (US $ 1,500 / day) used as an adsorbent in the treatment of antibiotics in water, ($ 246 / ton) is consumed as compared with the case where the amount of antibiotics in the water is reduced.

The present invention shows a method for removing an underwater antibiotic using a steam-activated visible-light bio-car.

 The present invention relates to a process for the production of a steam-activated, viscous, bio-tea, comprising the steps of adding a vapor-activated, viscous bio-tea to water containing antibiotics to adsorb and remove the antibiotic on a vapor- Describes the material removal method.

In the above, 0.1-1 g of steam-activated caustic bioassay was added to an aqueous solution of 2.5 to 50 mg of antibiotic dissolved in 1 liter of water, and the antibiotic was adsorbed for 3 to 48 hours on a vapor- To remove antibiotics.

The temperature of the water containing the antibiotic substance can be maintained at 25 캜 or lower when the vapor-activated caustic biochar of the above is added to water containing antibiotics.

The temperature of the water containing the antibiotic substance can be maintained at 4 to 25 캜 when the steam-activated caustic biochore is added to the water containing antibiotics.

The temperature of the antibiotic-containing water can be maintained at 20 to 25 占 폚 when the vapor-activated caustic biochore is added to water containing antibiotics.

Wherein the vapor-activated visible-light biochain is obtained by carbonizing the visible light to obtain a visible-light biochip; And a step of treating the visible thin-film bio-tea with steam.

Wherein the vapor-activated visible-light biochain is obtained by carbonizing the visible light at a pressure of 0.1 to 0.9 atm and at a temperature of 300 to 900 ° C for 1 to 5 hours to obtain a visible-light biochip; Treating the visible thin-film biochar with the water vapor of 80 to 120 캜 for 10 minutes to 3 hours may be used.

In the above, the vapor-activated visible-light biocha is obtained by carbonizing the visible film at a pressure of 1.0 atm and at 300 ° C for 3 hours to obtain a viscous bio-tea; Treating the visible thin-film biochar with the steam of 100 캜 for 30 minutes may be used.

In the above, the vapor-activated visible-light biochain is obtained by carbonizing the visible light at a pressure of 1.0 atm and at 700 ° C for 3 hours to obtain a visible-visor biochannel; Treating the visible thin-film biochar with the steam of 100 캜 for 30 minutes may be used.

The antibiotics contained in the above water may be any one or more selected from sulfamethazine, sulfamethoxazole, tetracycline, chlorotetracycline, and oxytetracycline.

The antibiotic contained in the above water may be sulfamethazine.

In order to achieve the object of the present invention, the method of removing the water-in-water antibiotic using the steam-activated visible-light biocha of the present invention was carried out under the conditions mentioned above, It is desirable to provide a method for removing antibiotics.

Hereinafter, the content of the present invention will be described in detail through Production Examples, Examples and Test Examples. However, these are for the purpose of illustrating the present invention in more detail, and the scope of the present invention is not limited thereto.

PREPARATION EXAMPLE 1 Preparation of Steam-Activated Visible Peptide Bio-Tea (SA-BC700)

The visible film was subjected to a carbonization treatment at a pressure of 1.0 atm and at 700 ° C for 3 hours to obtain a viscous bio-tea, and then the viscous bio-tea was treated with steam at 100 ° C for 45 minutes, (SA-BC700) was prepared.

PREPARATION EXAMPLE 2 Preparation of Visible Pellets (BC300)

The visible film was subjected to a carbonization treatment at a pressure of 1.0 atm and at a temperature of 300 캜 for 3 hours to prepare a viscous bacterium BC300.

≪ Preparation Example 3 > Preparation of visible pouch biocha (BC700)

Visible foil was carbonized at a pressure of 1.0 atm and at 700 캜 for 3 hours to prepare a viscous bamboo tea (BC700).

≪ Example 1 >

After adding 50 mg of sulfamethazine as an antibiotic to 1 liter of water (L), 1 g of the activated vaporizable activated carbon (SA-BC700) prepared in Preparation Example 1 as an adsorbent was added, and the mixture was stirred for 48 hours Antibiotics were adsorbed.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light biocha (SA-BC 700) was introduced.

≪ Comparative Example 1-1 >

After adding 50 mg of sulfamethazine as an antibiotic substance to 1 liter of water (L), 1 g of Kashibak biocha (BC300) prepared in Preparation Example 3 was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous bacterium BC300 was added.

≪ Comparative Example 1-2 >

After adding 50 mg of sulfamethazine as an antibiotic to 1 liter of water (L), 1 g of the viscous bacterium (BC700) prepared in Preparation Example 4 was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

In the above, the temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous bacterium BC 700 was added.

≪ Comparative Example 1-3 >

After adding 50 mg of sulfamethazine as an antibiotic to 1 liter of water, 1 g of Visible biomass (BM) was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

≪ Test Example 1 > Measurement of antibiotic adsorption amount

The degree of adsorption of sulfamethazine, an antibiotic substance, to each adsorbent in Example 1 and Comparative Examples 1-1 to 1-3 was measured by the Langmuir adsorption model equation, and the results are shown in Table 1 below Respectively.

Antibiotic adsorption amount measurement result Item Maximum adsorption (mg / g) Adsorption constant (K _L ) The coefficient of determination (R ² ) Example 1 32.191 9.532 x 10 ^-1 0.927 Comparative Example 1-1 15.656 4.513 × 10 ^-2 0.959 Comparative Example 1-2 18.776 7.940 × 10 ^-1 0.883 Comparative Example 1-3 6.669 1.066 x 10 ^-2 0.940

* The adsorption constant (K _L ) and the determination coefficient (R ² ) in the results of Table 1 are the numerical values indicating how well each adsorbent suits the adsorption mechanism of sulfamethazine by the Langmuir adsorption model, The closer to 1 the coefficient (R ² ), the better fit.

As shown in the above Table 1, the degree of adsorption of sulfamethazine, the antibiotic substance, was determined by the adsorption amount of the vapor-activated visible-field biochar (SA-BC700) in Example 1> Adsorption amount > The adsorption amount of visible thin film biocide (BC300) of Comparative Example 1-1> adsorption amount of visible thin film biomass (BM) of Comparative Example 1-3, It was found that the adsorbability of antibiotics in water was superior to that of Chaga garbage biocham and thorn leaf biomass.

In particular, the amount of antibiotic adsorbed on the steam activated baculovirus (SA-BC700) was 4.82 times as much as the amount of antibiotic adsorbed on visible biomass (BM), 2.06 times as much as the amount of antibiotic adsorbed on the bacillus biocar (BC300) (BC700), which is 1.71 times higher than the amount of antibiotic adsorbed by Kashipak biocha (BC700). Therefore, the vapor treatment of Kashipak biocha Method.

PREPARATION EXAMPLE 4 Preparation of Vapor-Activated Thin Film Bio-Tea (SA-BC300)

The visible film was subjected to carbonization treatment at a pressure of 1.0 atm and at 300 ° C for 3 hours to obtain a viscous bio-tea, and then the viscous bio-tea was treated with steam at 100 ° C for 45 minutes, (SA-BC300).

≪ Example 2-1 >

After adding 30 mg of sulfamethazine as an antibiotic to 1 liter of water (L), 0.5 g of the vapor-activated caustic bioaccumulator (SA-BC300) prepared in Preparation Example 4 was added as an adsorbent, The antibiotics were adsorbed for a while.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light bio-car (SA-BC300) was introduced.

≪ Example 2-2 >

30 mg of sulfamethoxazole was added as an antibiotic to 1 liter of water and then 0.5 g of vapor activated caustic bioassay (SA-BC300) prepared in Preparation Example 4 was added as an adsorbent. After 48 hours The antibiotics were adsorbed for a while.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light bio-car (SA-BC300) was introduced.

≪ Example 2-3 >

After adding 30 mg of tetracycline as an antibiotic to 1 liter of water (L), 0.5 g of the activated vaporized activated carbon (SA-BC300) prepared in Preparation Example 4 was added as an adsorbent, and the mixture was stirred for 48 hours Antibiotics were adsorbed.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light bio-car (SA-BC300) was introduced.

<Example 2-4>

After adding 30 mg of chlorotetracycline as an antibiotic to 1 liter of water (L), 0.5 g of the vapor-activated caustic bioaccumulator (SA-BC300) prepared in Preparation Example 4 was added as an adsorbent, The antibiotics were adsorbed for a while.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light bio-car (SA-BC300) was introduced.

<Example 2-5>

After adding 30 mg of oxytetracycline as an antibiotic to 1 liter of water (L), 0.5 g of the vapor-activated caustic bioaccumulator (SA-BC300) prepared in Preparation Example 4 was added as an adsorbent, The antibiotics were adsorbed for a while.

The temperature of the water to which antibiotics were added was maintained at 25 캜 when the steam-activated visible-light bio-car (SA-BC300) was introduced.

&Lt; Comparative Example 2-1 >

After adding 30 mg of sulfamethazine as an antibiotic substance to 1 liter of water, 0.5 g of Vasikobiocha (BC300) prepared in Preparation Example 2 was added as an adsorbent, and the antibiotic was adsorbed for 48 hours .

The temperature of the water to which the antibiotic substance was added was maintained at 25 占 폚 when the viscous bacillus (BC300) prepared in Preparation Example 2 was added.

&Lt; Comparative Example 2-2 &

30 mg of sulfamethoxazole was added as an antibiotic to 1 liter of water and then 0.5 g of Kashibak Biocha (BC300) prepared in Preparation Example 2 was added thereto as an adsorbent, and the antibiotic was adsorbed for 48 hours .

The temperature of the water to which the antibiotic substance was added was maintained at 25 占 폚 when the viscous bacillus (BC300) prepared in Preparation Example 2 was added.

&Lt; Comparative Example 2-3 >

After adding 30 mg of tetracycline as an antibiotic to 1 liter of water (L), 0.5 g of the viscous bacterium BC300 prepared in Preparation Example 2 was added as an adsorbent, and the antibiotic was adsorbed for 48 hours .

The temperature of the water to which the antibiotic substance was added was maintained at 25 占 폚 when the viscous bacillus (BC300) prepared in Preparation Example 2 was added.

&Lt; Comparative Example 2-4 &

30 mg of chlorotetracycline was added as an antibiotic to 1 liter of water and then 0.5 g of Kashipak biocha (BC300) prepared in Preparation Example 2 was added thereto as an adsorbent, and the antibiotic was adsorbed for 48 hours .

The temperature of the water to which the antibiotic substance was added was maintained at 25 占 폚 when the viscous bacillus (BC300) prepared in Preparation Example 2 was added.

&Lt; Comparative Example 2-5 &

After adding 30 mg of oxytetracycline as an antibiotic to 1 liter of water (L), 0.5 g of Kashipak biocha (BC300) prepared in Preparation Example 2 was added as an adsorbent and the antibiotic was adsorbed for 48 hours .

The temperature of the water to which the antibiotic substance was added was maintained at 25 占 폚 when the viscous bacillus (BC300) prepared in Preparation Example 2 was added.

&Lt; Comparative Example 2-6 >

After adding 30 mg of sulfamethazine as an antibiotic to 1 liter of water, 0.5 g of Visible biomass (BM) was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

<Comparative Example 2-7>

After adding 30 mg of sulfamethoxazole as an antibiotic to 1 liter of water, 0.5 g of Visible biomass (BM) was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

&Lt; Comparative Example 2-8 &

After adding 30 mg of tetracycline as an antibiotic to 1 liter of water, 0.5 g of potassium bicarbonate (BM) as an adsorbent was added and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

&Lt; Comparative Example 2-9 &

After adding 30 mg of chlorotetracycline as an antibiotic to 1 liter of water, 0.5 g of Visible biomass (BM) was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

&Lt; Comparative Example 2-10 &

After adding 30 mg of oxytetracycline as an antibiotic to 1 liter of water, 0.5 g of Visible Biomass (BM) was added as an adsorbent and the antibiotic was adsorbed for 48 hours.

The temperature of the water to which the antibiotic substance was added was maintained at 25 캜 when the viscous biomass (BM) was added.

In the above, Visible Biomass (BM) was dried at 60 ° C for 48 hours, cut into 0.5-1 mm size and sieved to 1 mm size.

Test Example 2 Measurement of antibiotic adsorption amount

The adsorption amounts of antibiotics to the respective adsorbents in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-10 were measured, and the results are shown in Table 2 below.

Antibiotic adsorption amount measurement result Item Adsorption amount Example 2-1 100 Example 2-2 100 Example 2-3 100 Examples 2-4 100 Example 2-5 100 Comparative Example 2-1 86 Comparative Example 2-2 85 Comparative Example 2-3 85 Comparative Example 2-4 86 Comparative Example 2-5 87 Comparative Example 2-6 75 Comparative Example 2-7 74 Comparative Example 2-8 75 Comparative Example 2-9 74 Comparative Example 2-10 73

* Values for adsorption amounts for Comparative Examples 2-1 to 2-10 in the results of Table 2 are shown in Table 2-1, Example 2-2, Example 2-3, Example 2- 4 and Example 2-5, when the value of the amount of antibiotic adsorbed on the adsorbent is taken as 100, the higher the value, the higher the amount of antibiotic adsorbed on the adsorbent.

As shown in the above Table 2, the degree of adsorption to the antibiotics sulfamethazine, sulfamethoxazole, tetracycline, chlorotetracycline, and oxytetracycline was significantly higher than that of the non-vapor-activated (SA-BC300) (BC700) and Visible-Biomass (BM), the vapor-activated visible-light biochain of the present invention is superior to the visible-light biocide and visible-light biomass in adsorbability to water antibiotics Could know.

While the present invention has been described with reference to the preferred embodiments, examples and test examples, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. It will be understood that various modifications and changes may be made thereto without departing from the spirit and scope of the invention.

The method of the present invention for removing an antibiotic substance from water using a steam activated biofilm of the present invention is a method for removing antibiotics from water by adding a biocide obtained by drying a dried bark of water and a bark of a bark obtained by carbonizing the bark, Compared to adsorbing substances, the adsorbing ability of antibiotics is high, which is very effective for the purification of water containing antibiotics. In addition, the present invention can be applied not only to the treatment of visible bark, which is an ecosystem disturbing material, but also to the treatment cost of activated carbon (US $ 1,500 / day) used as an adsorbent in the treatment of antibiotics in water, ($ 246 / ton) is consumed as compared with the case of the conventional method.

Claims (8)

The method of claim 1, wherein the steam activated spiked bacillus is added to water containing antibiotics to adsorb antibiotics on a vapor-activated spakey biochain,
Wherein the vapor-activated visible-light biochain is obtained by carbonizing the visible light to obtain a visible-light biochip;
And a step of treating the visible-light bio-car with the steam. delete The method according to claim 1,
0.1 to 1 g of vapor-activated caustic bioassay is added to an aqueous solution of 2.5 to 50 mg of antibiotics per liter (L) of water and the antibiotic is adsorbed for 3 to 48 hours on a vapor-activated caustic biochore A method for removing antibiotics in water using a vapor activated activated carbon biochar. The method according to claim 1,
Wherein the temperature of the water containing the antibiotic substance is 20 to 25 占 폚 when the steam-activated caustic bio-tea is added to the water containing the antibiotic substance. The method according to claim 1,
Activating the activated vapor-phase bio-tea is a step of carbonizing the activated carbon at a pressure of 0.1 to 1.0 atm and at a temperature of 300 to 900 ° C for 1 to 5 hours to obtain a viscous bio-tea;
Treating the visible thin-film biochar with the steam of 80 to 120 ° C for 10 minutes to 3 hours. The method according to claim 1,
Activation of the steam activated bacterium The bacterium is carbonized at 300 ° C for 3 hours under a pressure of 1.0 atm to obtain a viscous bacterium;
Treating the visible thin-film bio-tea with water vapor at 100 ° C for 30 minutes. The method for removing antibiotic substances from water using the vapor activated thin-film bio-tea. The method according to claim 1,
Activation of the activated vapor-phase biocham is a step of obtaining a visible vapor phase by carbonizing the visible vapor at a pressure of 1.0 atm and at 700 ° C for 3 hours;
Treating the visible thin-film bio-tea with water vapor at 100 ° C for 30 minutes. The method for removing antibiotic substances from water using the vapor activated thin-film bio-tea. The method according to claim 1,
Wherein the antibiotic substance is at least one selected from the group consisting of sulfamethazine, sulfamethoxazole, tetracycline, chlorotetracycline, and oxytetracycline. Removal method of underwater antibiotic using bio - tea.