KR100865974B1 - Ag impregnated porous antibiosis adsorbent and a process of preparing the same - Google Patents

Abstract

The present invention relates to a porous composite adsorbent, a method for preparing the same, and a filter prepared therefrom.

The porous composite adsorbent includes a porous adsorbent modified by carrying an effective metal and an antimicrobial porous adsorbent supported by silver. The porous adsorbent modified by carrying an effective metal is an oxidative functional group produced by an acid treatment to treat harmful gases. This increased, silver-supported antimicrobial porous adsorbent exhibits the antimicrobial properties of silver and prevents the problem of re-desorption due to the existing weak adsorption force and solves the short exchanger of the adsorbent.

Silver, porous adsorbent, active metal, calcining, antibacterial, hydrogen sulfide, aldehyde, hydrogen chloride, odorous harmful gas, oxidation treatment

Description

Silver impregnated porous antibiosis adsorbent and a process of preparing the same

The present invention relates to a porous composite adsorbent, a method for preparing the same, and a filter prepared therefrom.

The porous composite adsorbent according to the present invention has a weak adsorption force, which is merely physical adsorption, and an adsorption force for removing odorous harmful gases such as aldehyde, hydrogen sulfide, mercaptan, ammonia, hydrogen chloride, etc. There is an advantage that can be solved.

As a porous adsorbent with an antimicrobial function, the toxic gas adsorbent is loaded with a metal phthalocyanine compound and a metal oxide having an oxidative removal effect of malodorous gas on an activated carbon formed into honeycomb, fibrous or other shapes according to Korean Patent Publication No. 10-0144183. There is one related to activated carbon. However, the metal phthalocyanine compound has a heavy metal such as cobalt, copper, nickel, manganese, there is a fear that the heavy metal desorption due to the aging of the material, the manufacturing process is complicated, the productivity is reduced, the deodorizing ability is also poor.

Therefore, the present invention is to prevent the problem that the harmful gas re-desorption due to the weak adsorption of the porous adsorbent, and the porous including the modified porous adsorbent carrying active metal and the antimicrobial porous adsorbent carrying silver in order to extend the short exchanger of the adsorbent. It is an object to provide a composite adsorbent.

In the present invention, the effective metal-supported porous adsorbent is acid-treated with the porous adsorbent in order to introduce an oxidative functional group, and then the porous adsorbent is mixed with the metal precursor solution to react with the modified porous adsorbent carrying the effective metal. Another purpose is to provide a method for preparing a porous composite adsorbent by mixing the silver nano dispersion solution and the acid-treated porous adsorbent and mixing the silver-supported antimicrobial porous adsorbent.

In addition, another object of the present invention to provide a filter using the porous composite adsorbent.

The present invention relates to a porous composite adsorbent, a method for preparing the same, and a filter prepared therefrom.

The porous composite adsorbent according to the present invention includes a porous adsorbent modified by carrying an effective metal and an antimicrobial porous adsorbent supported by silver. The porous adsorbent modified by carrying the effective metal is prepared by mixing and reacting a porous adsorbent or a porous adsorbent having an oxidative functional group with a metal precursor solution by acid treatment thereof, and an antimicrobial porous adsorption supporting silver (Ag). The sieve is characterized in that the silver (Ag) nano dispersion solution is mixed with a porous adsorbent or an acid treated porous adsorbent to support silver on the surface of the porous adsorbent. A porous composite adsorbent is formed by evenly mixing the porous adsorbent modified by supporting the effective metal and the antimicrobial porous adsorbent carrying silver.

The filter using the porous composite adsorbent according to the present invention is prepared by filling a porous composite adsorbent provided by mixing a modified porous adsorbent carrying silver with an effective metal and an antimicrobial porous adsorbent loaded with silver to attach to a filter medium using a binder. can do.

When the present invention is described in detail, the porous composite adsorbent according to the present invention includes a porous adsorbent modified by carrying an effective metal and an antimicrobial porous adsorbent supported by silver. The porous adsorbent includes activated carbon, diatomaceous earth, zeolite, silica gel, starch, bentonite, alumina, and the like, and the specific surface area is 700 m ² / g to 1500 m ² / g and the average pore size is 10 to 30 mm 3. In addition, after the acid treatment and cleaning the porous adsorbent to dry the moisture content to 5% or less to prepare a porous adsorbent is provided with an oxidative functional group. The porous adsorbent does not show sufficient adsorption and adsorption and removal capacity if the specific surface area is less than 700 m ² / g. In addition, if the average pore size is less than 10Å may be blocked by the narrow of the pores, if it exceeds 30Å, the deodorizing ability of the pore is reduced.

The porous adsorbent modified by carrying the effective metal may be modified by adding an active metal modifier in the intact state of the porous adsorbent, or may be used by modifying the effective metal after the acid treatment and having an oxidative functional group. More preferably, a porous adsorbent having an oxidative functional group after an acid treatment is used, and the porous adsorbent having an oxidative functional group has a strong supporting force of a modifier, so that there is little damage during post-treatment, and only the adsorption power of harmful gases is increased. In addition, the adsorption duration is also long, resulting in a long exchange cycle.

The acid treatment for forming the porous adsorbent having the oxidative functional group is preferably in the volume ratio of 1: 0.5-5 with the porous adsorbent, so that the acidic solution easily contacts the surface of the porous adsorbent. In order to minimize the number and to provide the oxidative functional group on the porous adsorbent, the volume ratio of 1: 1.5 is more preferable. The acidic solution is at least one aqueous inorganic acid solution selected from hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and maintained at a temperature of 30 ° C. to 110 ° C., and mixed with the porous adsorbent at a rotation speed of 30 to 100 rpm. Although stirring time changes with concentration of the inorganic acid aqueous solution, it is preferable to mix for 1 to 10 hours, More preferably, it is 2 to 5 hours. If it is less than 1 hour, the oxidative functional group may not be sufficiently introduced, and generation of the oxidative functional group is insufficient, and if it exceeds 10 hours, the productivity is bad, so it is appropriately adjusted.

After the acid treatment, the solution is removed and distilled water is added, followed by washing for 10 minutes to 2 hours at the temperature and rotation speed at the time of acid treatment.

The porous adsorbent modified by supporting the effective metal according to the present invention is a porous adsorbent or a porous adsorbent having an oxidative functional group by acid treatment with the metal precursor solution containing the active metal to form an effective metal in the metal precursor solution. It is formed by being modified and supported on the porous adsorbent. The metal precursor solution may include at least one metal component selected from potassium (K), iron (Fe), copper (Cu), vanadium (V), and manganese (Mn), and examples of the metal precursor may include potassium hydroxide. (KOH), potassium iodide (KIO ₃ ), potassium nitrate (KNO ₃ ), iron nitrate (Fe (NO ₃ ) ₃ ), copper nitrate II (Cu (NO ₃ ) ₂ ), vanadium pentoxide (V ₂ O ₅ ) And potassium permanganate (KMnO ₄ ), more preferably at least one selected from these.

Porous adsorbent or acid-treated porous adsorbent according to the present invention and the metal precursor solution containing the effective metal and the effective metal is a volume ratio of 1: 0.5 to 5, more preferably the adsorbent and the metal precursor solution The volume ratio is 1: 1.5. At the time of mixing, the metal precursor solution is an aqueous solution, and the concentration is preferably used in an amount of 1-60% based on anhydrous salt, and more preferably 10-35%. After the mixing, the metal precursor solution containing the adsorbent is maintained at a temperature of 30 ° C. to 110 ° C. and mixed for 3 to 24 hours at a rotation speed of 30 to 100 rpm, and more preferably, the mixing time is 10 to 15 hours. will be. When the mixture was mixed for less than 3 hours at a rotational speed of less than 30 rpm at a low temperature of less than 30 ° C., the contact time between the porous adsorbent equipped with the oxidative functional group and the metal precursor solution was insufficient, and the functionalities of the porous adsorbent and the metal oxide of the metal precursor were insufficient. Coupling rate decreases, and addition reaction of the functional group of the porous adsorbent occurs, and the modification rate decreases.

After the mixing, the solution is discarded, purified water is added to the mixture, stirred and purified, and then dried twice or more in a porous adsorbent in a drier heated to at least 5% to prepare a porous adsorbent carrying an effective metal. The drying temperature is not particularly limited, but is usually dried at 100 ~ 150 ℃. Drying at a temperature below 100 ℃ is not good because it is difficult to remove enough moisture.

The porous metal adsorbent carrying the effective metal according to the present invention may be formed by drying after mixing with the metal precursor solution, and after drying, the porous adsorbent is heated to increase the temperature in the dryer, thereby increasing the bonding strength between the effective metal and the porous adsorbent. In addition, it is possible to increase the ability to remove harmful gases, but firing is preferred because it can increase the ability to remove harmful gases. The firing temperature varies depending on the type of porous adsorbent, but the activated carbon, which is a porous adsorbent according to the present invention, is preferably 150 ° C to 500 ° C. If the temperature is less than 150 ° C., a part in which the calcination is not finished may occur, and at a high temperature exceeding 500 ° C., surface damage of the adsorbent may occur, and the porous pores may be deformed. Although the time of firing also depends on the type and atmosphere of the adsorbent, the atmospheric pressure atmosphere of the present invention is preferably 2 to 10 hours, more preferably 3 to 7 hours. If it is less than 2 hours, it is difficult to hope for completeness of plasticity, and if it is more than 10 hours, deformation of surface pores is feared.

Silver-supported antibacterial porous adsorbent

a) a solution in which a polymer compound is mixed is continuously added to an alcohol solution containing silver (Ag) compound and mixed, and silver is reduced by addition of an organic acid to prepare a silver nano dispersion solution (Ag nano solution);

b) adding purified water to the silver nano dispersion solution of a), followed by mixing by adding a porous adsorbent and / or an acid treated porous adsorbent, drying and firing;

Characterized in that it comprises a.

The alcohol aqueous solution containing the silver compound according to the present invention is a mixture of a silver compound and alcohol and / or distilled water, and the silver compound is silver peroxide (Ag ₂ O), silver sulfide (Ag ₂ S), silver nitrate (AgNO ₃ ), silver sulfate (Ag ₂ SO ₄ ) and silver acetate (Ag (CH ₃ COO)) are preferred, more preferably silver nitrate (AgNO ₃ ). Although the alcohol containing the said silver compound is not restrict | limited, Preferably dihydric aliphatic saturated alcohol is more preferable, In particular, ethylene glycol, propylene glycol, polyethyleneglycol, etc. are mentioned, Alcohol, such as isopropyl alcohol, can also be used. The alcohol controls the amount of silver (Ag) compound and the amount of alcohol so that the silver (Ag) content is 0.1-10 wt% when the silver compound is added. Although the mixing of the solution containing the silver compound is not particularly limited, it is preferably maintained at 60 ° C to 100 ° C and mixed at a rotational speed of 30 to 100 rpm for 10 minutes to 1 hour.

The polymer compound according to the present invention is not limited so long as it is a mixture of at least one selected from polyvinyl alcohol or an oxide derived from polyvinyl alcohol and a water-soluble polymer. The water-soluble polymer used in the present invention is not limited as long as it is commonly known in the art. The polymer compound of the present invention includes, for example, a mixed polymer compound of polyvinylbutylal (PVB; Polyvinylbutylal) and polyvinylpyrrolidone (PVP; Polyvinyl pyrolidone), and the mixture of the polymer compound is polyvinyl alcohol or poly It is preferable to use a mixture of at least one selected from oxides derived from vinyl alcohol and a water-soluble polymer. The mixing ratio is not particularly limited, but preferably, at least one polymer selected from polyvinyl alcohol or an oxide thereof may be a mixture of 1 to 99% by weight and 99 to 1% by weight of a water-soluble polymer. It is preferable to use aliphatic alcohol as the solution which melt | dissolves the said high molecular compound, For example, polyethyleneglycol, isopropyl alcohol, etc. are mentioned. The alcohol and the polymer compound are mixed and dissolved at a rotational speed of 30 to 100 rpm for 1 hour to 2 hours while maintaining a temperature of 60 ° C. to 100 ° C. When the temperature is less than 50 ° C., dissolution is insufficient, and a polymer compound may precipitate, and when dissolved at a temperature higher than 100 ° C., the chain of the polymer may be damaged and the physical properties may be deformed.

After the alcohol solution containing the silver compound (Ag) according to the present invention, more preferably the alcohol solution is slowly added to the mixed solution of the polymer compound and stirred at the same stirring speed, temperature and time as the mixing conditions of the polymer compound, the organic acid By adding to reduce to prepare a silver nano dispersion solution which can control the silver content.

Next, the organic acid component of this invention is demonstrated. The organic acid of the present invention is not particularly limited, but it is preferable to use one organic acid selected from ascorbic acid, sulfonic acid, carboxylic acid, formic acid and citric acid, and ascorbic acid is more preferable due to the ease of process, and the amount of organic acid used is The silver is reduced by mixing silver with a weight ratio of 1: 1.5. It is preferable to keep the temperature and speed at the same time as the mixing of the polymer compound because no side reaction is generated, and the stirring is preferably performed for 5 minutes to 1 hour.

The silver nano dispersion solution (Ag nano solution) according to the present invention is mixed with water, and then the porous adsorbent and / or the acid-treated porous adsorbent are added to prepare an antimicrobial porous adsorbent on which silver is supported. Although the mixing ratio of the silver nano dispersion solution and the porous adsorbent can be appropriately selected and used as necessary, the use ratio is not limited, but the porous adsorbent and / or acid are usually added to an aqueous solution in which water is added to the silver nano dispersion solution. The use of the treated porous adsorbents in a solid phase: liquid volume ratio of 1: 0.5 to 5 can be economically and completely supported. The dispersion of the silver nano dispersion solution containing the porous adsorbent is not particularly limited, but is preferably maintained at a temperature of 30 ° C. to 100 ° C. and mixed for 1 to 4 hours at a rotation speed of 30 to 100 rpm. Dispersion is not easy at low temperatures below 30 ° C, so that silver is not completely supported on the porous adsorbent, and at a high temperature above 100 ° C, addition reactions may occur, thereby resorbing and depositing the silver.

After the dispersion, the liquid phase is discharged and dried and calcined the remaining porous adsorbent. Although there is a difference in drying time depending on the amount of porous adsorbent, the activated carbon according to the present invention dries water in the porous adsorbent to 5% or less in a dryer maintained at 110 ° C to 130 ° C for at least 1 hour. Typically 1 hour to 2 hours are required.

Hereinafter, the firing conditions of the present invention will be described. The firing is not particularly limited in terms of conditions, but it is preferable to keep the temperature in the dryer at 200 ° C to 500 ° C for 2 to 5 hours. If it is too low, plasticity is incomplete, and there exists a possibility that the pore of the surface of a porous adsorption body may deform | transform at high temperature exceeding 500 degreeC.

In the case of a dryer to be dried and calcined, a conventional furnace can be selected without limitation, but a rotary furnace that is easy in the manufacturing process of the porous composite adsorbent according to the present invention is preferable.

The porous antimicrobial composite adsorbent according to the present invention is formed by mixing the porous metal adsorbed on the effective metal and the antimicrobial porous adsorbent loaded with silver as described above. There is no particular limitation on the mixing ratio when mixing, but preferably, the ratio between the porous metal adsorbed on the effective metal and the antimicrobial porous adsorbent on which silver is supported is 1 to 99 parts by weight to 99 to 1 parts by weight, and the volume ratio varies depending on the use. can do. Preferably, the volume ratio of the porous adsorbent modified by supporting the effective metal and the antimicrobial porous adsorbent supported by silver is about 2: 1. Although there is no restriction on the mixing method, physical mixing method using a screw mixer is preferable in consideration of the breaking strength and uniform mixing of the porous adsorbent.

It is also possible to prepare a porous composite adsorbent filter filled with a porous composite adsorbent provided by mixing the porous metal adsorbent modified with supporting effective metal according to the present invention and an antimicrobial porous adsorbent loaded with silver. The filter may be attached to the filter medium using a binder. The size and manufacturing method of the filter can be different depending on the intended use, and can also be produced by the existing filter manufacturing method.

Example 1

1) Preparation of Activated Carbon Containing Iron (Fe)

Coconut shell granular activated carbon having a specific surface area of 1100 m ² / g and an average pore diameter of 15 kPa was added to distilled water, stirred for 45 minutes at a rotation speed of 50 rpm at a temperature of 70 ° C., and activated carbon in a rotary kiln maintained at 130 ° C. Dry until the moisture content is below 5%.

5 g of the activated carbon is added with an aqueous solution containing an excess of 20% by weight of Fe (NO ₃ ) ₃ .9H ₂ O as a modifier of anhydrous salt and stirred at a rotational speed of 50 rpm at a temperature of 70 ° C. for 14 hours. The solution was discharged, distilled water was added, and the mixture was washed by stirring for 45 minutes at a rotational speed of 50 rpm at a temperature of 70 ° C. Washing three times while changing the distilled water, and dried for 1 hour so that the moisture in the activated carbon is less than 5% in a rotary furnace maintained at a temperature of 130 ℃ to prepare a porous adsorbent loaded with iron.

2) Preparation of Activated Carbon Supported by Silver (Ag)

16 g of silver nitrate (AgNO ₃ ) and 20 g of isopropyl alcohol (Isopropyl alcohol) are mixed, and distilled water is added to the silver nitrate solution to prepare an aqueous solution of isopropyl alcohol containing 1 mol of silver nitrate. The aqueous solution was uniformly dispersed with silver nitrate in the solution while stirring at a rotational speed of 50 rpm at a temperature of 80 ° C. for 45 minutes, and 5 g of aqueous solution containing 15% of polyvinyl butylal (PVB, Polyvinyl Butylal, JUNSEI) and poly After mixing 5 g of an aqueous solution containing 15% of vinyl pyrilidone (PVP, Polyvinyl pyrolidone, JUNSEI), 5 g of polyethylene glycol (PEG, Polyethyleneglycol, JUNSEI, MW = 12,000) is added, and dissolved at 70 rpm for 70 minutes. Slowly add to the solution containing the polymer compound formed by stirring at 85 ℃ for 45 minutes at a rotational speed of 50rpm. 3 g of polyethylene glycol (PEG, Polyethyleneglycol, JUNSEI, MW = 12,000) mixed with 7.5 g of ascorbic acid was added to the stirring solution to reduce the silver nano dispersion solution containing Ag (Ag nano solution). Was prepared. DI water was added to the silver nano dispersion solution in an amount of 1: 1 by volume to prepare a silver nano dispersion solution.

The 5% HCl solution and activated carbon were mixed in a volume ratio of 1.5: 1 in the silver nano dispersion solution in advance, stirred at a rate of 60 rpm at a temperature of 70 ° C. for 2 hours, acid treatment, and then the solution was discharged, and the purified water was washed three times. After drying, the activated carbon having an oxidative functional group was added at a volume ratio of 1.5: 1 and stirred at a rotational speed of 50 rpm at a temperature of 80 ° C. for 2 hours. After stirring, the liquid phase was discharged and the remaining solid phase was dried in a rotary kiln maintained at a temperature of 130 ° C. for 1 hour and calcined at 400 ° C. for 3 hours in an atmospheric pressure atmosphere.

Activated carbon containing iron and activated carbon containing silver (Ag) particles as the effective metal were mixed in a screw type mixer in a weight ratio of 2: 1 to prepare a porous composite adsorbent.

Experimental Example 1 Performance Evaluation of Porous Antimicrobial Composite Adsorbents-Evaluation Method and Result of Adsorption Force

A convection oven is used to fill the filter with 5 g of the porous antibacterial adsorbent in the filter by using a filter attached to a lower portion of a cylindrical glass tube having a diameter of 15 mm and a length of 300 mm as a column. After installation, the inside of the convection oven is maintained at a temperature of 30 ℃, ammonia (NH ₃ 10 v / v%, N ₂ Balance ), Hydrogen sulfide ((H ₂ S 10v / v%, N ₂ Balance), acetaldehyde (CH ₃ CHO 1 v / v%, N ₂ Balance ) Was diluted with nitrogen (N ₂ ) gas (99.999% purity) to carry out adsorption experiment. The harmful gas flow rate was 40ml / min, the dilution gas flow rate was 160ml / min and accurately adjusted through a mass flow controller (MFC) connected to the control system, and the pressure of each inlet gas was maintained at 1kgf / cm2. The adsorption capacity is collected from the sampling port every 5 minutes through the adsorbent and measured by the Gastec detection tube gas concentration meter to determine the concentration of harmful gas in the exhaust gas and then to exceed 10% of the inlet gas concentration. Noxious gas removal rate up to 90%) is determined as breakthrough. The adsorption capacity is calculated from the flow rate of halogen gas passing through the column to the breakthrough point and the weight of the adsorbent used. The formula for calculating the adsorption capacity is as follows.

Adsorption Capacity (%) = Hazardous Gas Flow Rate (ml / min) × Breakthrough Time (min) × (1 L / 1000 cm 3) × (1 Mole / 22.414 L) × (g Molecular Weight of Molecular Gas / mol) × (Hazardous Gas Concentration) % / 100) × (1 / g of used adsorbent g) × 100

The experimental results and the adsorption capacity calculation results showed that the very good adsorption effect and adsorption breakthrough time are long as shown in Table 1 below.

Experimental Example 2 Performance Evaluation of Porous Antimicrobial Composite Adsorbents-Method and Results of Antimicrobial Activity of Porous Composite Adsorbents

E. coli is inoculated into sterilized LB (Luria Bertani) medium and incubated at 37 ° C. for 24 hours in a bacterial incubator. After preparing 50 ml vial using distilled water to contain 8000 ppm of activated carbon, the cultured E. Coli culture was aliquoted to an OD value of 0.1, and a vial for blank test was prepared together. Aliquot E. Coli cultures as above. Incubate at a temperature of 37 ℃ for 24 hours at a rotational speed of 150rpm in a rotary bacterial incubator to enable the contact between activated carbon and E. coli (E. Coli). After 24 hours, 0.05 ml of the supernatant was taken and smeared in a previously sterilized LB (Luria Bertani) medium and incubated at 37 ° C. in a bacterial incubator for 24 hours, and the number of colonies shown was determined to determine bacterial resistance of activated carbon. The antimicrobial activity of the above measurement result was found to have a very good antimicrobial activity as shown in Table 2.

Example 2

The experiment was the same as in Example 1 except for using the acid-treated porous activated carbon containing iron (Fe) as follows.

Coconut granular activated carbon having a specific surface area of 1100 m ² / g and an average pore size of 15 kPa is added to an aqueous solution having a concentration of 5% HCl. The activated carbon and aqueous HCl solution were stirred for 4 hours at a rotational speed of 50 rpm at a temperature of 80 ° C. in a reactor with a volume ratio of 1: 1.5 in a solid phase: liquid phase, and the solution was discharged, followed by addition of distilled water at 50 rpm at 80 ° C. After stirring for 45 minutes at a rotational speed of the washing, and washed three times while changing the distilled water and dried until the moisture content of the activated carbon is less than 5% in a rotary kiln maintained at a temperature of 130 ℃.

5 g of the activated carbon is added with an aqueous solution containing an excess amount of Fe (NO ₃ ) ₃ .9H ₂ O as a modifier at a concentration of 20% by weight based on anhydrous salt and stirred at a rotational speed of 50 rpm at a temperature of 80 ° C. for 14 hours. The solution is discharged, distilled water is added, and the mixture is washed by stirring for 45 minutes at a rotational speed of 50 rpm at a temperature of 80 ° C. Washing three times while changing the distilled water, and dried for 1 hour so that the moisture in the activated carbon is less than 5% in a rotary furnace maintained at a temperature of 130 ℃ to prepare an acid-treated porous adsorbent loaded with iron.

The iron-supported acid-treated porous activated carbon was prepared by mixing the silver-supported antimicrobial porous adsorbent prepared in Example 1 with a screw-type mixer in a weight ratio of 2: 1 to prepare a porous composite adsorbent.

The adsorption force measurement method and the antimicrobial force measurement method according to Example 1 were carried out, and the adsorption force measurement results are shown in Table 1, and the antimicrobial force measurement results are shown in Table 2, respectively. As a result, it was confirmed that the acid-treated porous adsorbent had better adsorption power and longer breakthrough time than Example 1. The antimicrobial activity of the above measurement result was found to have a very good antimicrobial activity as shown in Table 2.

Example 3

The activated carbon of Example 2 was tested in the same manner as in Example 2 except that it was acid-treated and ferrous in the same manner, dried under the same conditions, and calcined at 250 ° C. in an atmospheric pressure atmosphere for 4 hours.

As a result, the adsorption force measurement method and the antimicrobial force measurement method according to Example 1 were carried out using the composite adsorbent prepared in the same weight ratio as in Example 2, and the adsorption force measurement results are shown in Table 1, and the antimicrobial force measurement results are shown in Table 2, respectively. As a result, the adsorption capacity and breakthrough point showed the best results, and it was found that the adsorption capacity and breakthrough point were very excellent in acid treatment and firing treatment. The antimicrobial activity of the above measurement result was found to have a very good antimicrobial activity as shown in Table 2.

Example 4

Except for adopting the excess aqueous solution containing Cu (NO ₃ ) ₂ 3H ₂ O in 20% by weight based on anhydrous salt in order to support copper as an active metal component in Example 3 It was carried out.

The composite adsorbent was subjected to the adsorption force measuring method according to Experimental Example 1 and the antimicrobial force measuring method according to Experimental Example 2, and the adsorption force measurement results are shown in Table 1, and the antimicrobial force measurement results are shown in Table 2, respectively. The antimicrobial activity measurement result was found to have a very good antimicrobial activity as shown in Table 2.

Comparative Example 1

Coconut granular activated carbon with specific surface area of 1100m ² / g and average pore size of 15 흡착 was subjected to the adsorption force measurement method and the antibacterial activity measurement method according to Experimental Example 1 and Experimental Example 2, and the results of the adsorption force measurement are shown in Table 1, 2 is shown respectively. As a result, the adsorption capacity and breakthrough point were very poor.

Comparative Example 2

Coconut granular activated carbon having a specific surface area of 1100 m ² / g and an average pore diameter of 15 kPa was added to distilled water, stirred for 45 minutes at a rotational speed of 50 rpm at a temperature of 80 ° C., and activated carbon in a rotary furnace maintained at a temperature of 130 ° C. Dry until the moisture content is below 5%.

The activated carbon was added to an excess aqueous solution containing 20% of potassium hydroxide (KOH) as a modifier and stirred at a rotational speed of 50 rpm at a temperature of 80 ° C. for 14 hours. The solution is discharged, distilled water is added, and the mixture is washed by stirring for 45 minutes at a rotational speed of 50 rpm at a temperature of 80 ° C. Washing three times while changing the distilled water, and dried for 1 hour to evaporate water in the activated carbon to less than 5% in a rotary furnace maintained at a temperature of 130 ℃ to prepare activated carbon modified with potassium hydroxide (KOH).

The activated carbon modified with potassium hydroxide (KOH) was subjected to the adsorption force measuring method and the antimicrobial force measuring method according to Experimental Example 1 and Experimental Example 2, and the results of the adsorption force measurement are shown in Table 1, and the antimicrobial force measurement results are shown in Table 2, respectively. The adsorption capacity and breakthrough point were increased compared to the unmodified adsorbent as in Comparative Example 1, but showed a worse result than the adsorbent according to the example.

Comparative Example 3

Coconut granular activated carbon having a specific surface area of 1100 m ² / g and an average pore diameter of 15 kPa was added to distilled water, stirred for 45 minutes at a rotation speed of 50 rpm at a temperature of 80 ° C., and activated carbon in a rotary furnace maintained at a temperature of 130 ° C. Dry until the moisture content is below 5%.

The activated carbon was added to an aqueous solution containing Fe (NO ₃ ) _{3 ·} 9H ₂ O as a modifier at a concentration of 20% by weight based on anhydrous salt, stirred at a rotational speed of 50 rpm at a temperature of 20 ° C. for 1 hour, and the solution was discharged. Distilled water is added, and it wash | cleans by stirring for 45 minutes at the rotation speed of 50 rpm at the temperature of 20 degreeC. Washed three times while changing the distilled water, and dried for 1 hour to evaporate all the moisture in the activated carbon in a rotary furnace maintained at a temperature of 130 ℃ to prepare an activated carbon modified with Fe (NO ₃ ) ₃ .

The activated carbon modified with Fe (NO ₃ ) ₃ was subjected to the adsorption force measuring method and the antimicrobial force measuring method according to Experimental Example 1 and Experimental Example 2, and the results of the adsorption force measurement are shown in Table 1, and the antimicrobial force measurement results are shown in Table 2, respectively. In the same manner, thirteen physical properties were shown.

As shown in Table 1, it can be seen that the adsorption capacity is better when the modifier and the auxiliary modifier according to the present invention are used. More preferably, the mixture of activated carbon calcined and supported with an active metal modifier at 80 ° C. after acid treatment and activated carbon carrying silver (Ag) with silver nitrate (AgNO ₃ ) as an auxiliary modifier is mixed. Although excellent properties were shown, the cause of such physical properties caused by the mixing of the two kinds of porous adsorbents of the present invention is unknown, but it showed a surprising effect with a very large adsorption capacity and breakthrough point.

As shown in Table 2, the antimicrobial activity of the activated carbon can be seen that the embodiment according to the present invention to add a modifier and a secondary modifier is more excellent. In particular, in the case of Example 3 and Example 4 which was added after the acid treatment and the modifier was calcined, the E. coli viability was extremely rare.

As described above, the porous composite adsorbent according to the present invention is prepared by mixing a porous metal adsorbent modified with an effective metal and an antimicrobial porous adsorbent loaded with silver to optimize the proper concentration, treatment time, and temperature of the solution during modification and support. After reforming, it was calcined in a specific atmosphere and temperature to increase adhesion between adsorbent surface and modifier, and formed metal oxide suitable for removal of harmful gas, and by using silver nano dispersion solution, do not excessively block pores of adsorbent, It has the effect of reducing the waste of the modifier while maintaining the high porosity of the adsorbent to the surface support.

Claims (32)

A porous composite adsorbent comprising a porous adsorbent modified by carrying at least one metal selected from potassium, iron, copper, vanadium and manganese, and an antimicrobial porous adsorbent supported by silver. The method of claim 1, The porous adsorbent is at least one selected from activated carbon, diatomaceous earth, zeolite, silica gel, starch and bentonite. The method of claim 2, The porous adsorbent has a specific surface area of 700 m ² / g ~ 1500 m ² / g, the average pore diameter is 10 ~ 30Å porous composite adsorbent. The method of claim 1, The modified porous adsorbent is a porous composite adsorbent formed by mixing and reacting a porous adsorbent having a porous adsorbent or an oxidative functional group and a metal precursor solution. The method of claim 4, wherein The porous adsorbent provided with the oxidative functional group is a porous composite adsorbent prepared by drying the acid after treating the porous adsorbent. The method of claim 1, The antimicrobial porous adsorbent loaded with silver (Ag) is a porous adsorbent, after adding purified water to a silver nano dispersion solution prepared by adding an alcoholic solution containing an silver (Ag) compound and an organic acid to a solution containing a polymer compound. Porous composite adsorbent prepared by adding acid treated porous adsorbent or mixtures thereof. The method of claim 1, The porous composite adsorbent is a porous composite adsorbent, characterized in that formed by mixing a modified porous adsorbent and an antimicrobial porous adsorbent. a) mixing a metal precursor solution on a porous adsorbent having a porous adsorbent or an oxidative functional group to support a metal component, and then drying and firing to prepare a modified porous adsorbent; b) mixing the silver nano dispersion solution with a porous adsorbent, an acid-treated porous adsorbent or a mixture thereof to support silver components, and then drying and calcining to prepare an antimicrobial porous adsorbent supported silver; c) mixing the modified porous adsorbent and the silver-supported antimicrobial porous adsorbent with a mixer to form a porous composite adsorbent; Porous composite adsorbent manufacturing method comprising a. The method of claim 8, The porous adsorbent having the oxidative functional group of step a) is a porous composite adsorbent manufacturing method in which the oxidative functional group is provided on the porous adsorbent through acid treatment of mixing the porous adsorbent and the acidic solution in a volume ratio of 1: 0.5 to 5. The method of claim 9, The acid solution is a porous composite adsorbent manufacturing method of at least one inorganic acid aqueous solution selected from hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid. The method of claim 10, The acid treatment is maintained at a temperature of 30 ℃ to 110 ℃, and mixed for 1 hour to 10 hours at a rotational speed of 30 to 100rpm to prepare a porous composite adsorbent in which the oxidative functional group is provided in the porous adsorbent. delete The method of claim 8, The metal precursor solution is a porous composite adsorbent manufacturing method containing at least one metal component selected from potassium (K), iron (Fe), copper (Cu), vanadium (V) and manganese (Mn). The method of claim 13, The metal precursors are potassium hydroxide (KOH), potassium iodide (KIO ₃ ), potassium nitrate (KNO ₃ ), iron nitrate (Fe (NO ₃ ) ₃ ), copper nitrate II (Cu (NO ₃ ) ₂ ), vanadium pentoxide (V ₂ O ₅ ) and potassium permanganate (KMnO ₄ ) is at least one selected from porous composite adsorbent manufacturing method. The method according to claim 13 or 14, The metal precursor solution is a porous composite adsorbent manufacturing method is mixed in a volume ratio 1: 0.5-5 with respect to the porous adsorbent having a porous adsorbent or an oxidative functional group. The method of claim 15, Mixing of the porous adsorbent having a porous adsorbent or an oxidative functional group and the metal precursor solution is a method for producing a porous composite adsorbent for 3 to 24 hours at a rotational speed of 30 to 100rpm at a temperature of 30 ℃ to 110 ℃. The method of claim 8, The firing of step a) is a porous composite adsorbent manufacturing method in which a modified porous adsorbent is formed by maintaining a temperature of 150 ℃ to 500 ℃ for 2 to 10 hours in the air. The method of claim 8, Step b) i) preparing a silver nano-dispersion solution by continuously adding an alcohol aqueous solution containing silver (Ag) compound to the solution mixed with the polymer compound, and then adding silver to reduce the silver by adding an organic acid; ii) adding purified water to the silver nano dispersion solution, followed by mixing by adding a porous adsorbent, an acid-treated porous adsorbent or a mixture thereof, and then drying and calcining; Porous composite adsorbent manufacturing method comprising a. The method of claim 18, Alcohol used in step i) is an aliphatic saturated alcohol porous composite adsorbent manufacturing method. The method of claim 18, The solution mixture of the polymer compound of step i) is a porous composite adsorbent manufacturing method containing at least one selected from polyvinyl alcohol and oxides derived from polyvinyl alcohol and water-soluble polymer. The method of claim 20, The mixed solution of the polymer compound is a porous composite adsorbent manufacturing method prepared by dissolving the polymer compound in aliphatic alcohol at a rotational speed of 30 to 100rpm for 1 to 2 hours while maintaining a temperature of 60 ℃ to 100 ℃. The method of claim 18, The alcohol aqueous solution containing the silver compound is mixed with purified water after the addition of the silver compound to the alcohol and maintained at 60 ℃ to 100 ℃, a porous composite adsorbent manufacturing method for producing at a rotational speed of 30 to 100rpm for 10 minutes to 1 hour . The method of claim 22, The silver compound is porous, which is one compound selected from silver peroxide (Ag ₂ O), silver sulfide (Ag ₂ S), silver nitrate (AgNO ₃ ), silver sulfate (Ag ₂ SO ₄ ), or silver acetate (Ag (CH ₃ COO)). Composite adsorption method. delete The method of claim 18, The organic acid of step i) is a porous composite adsorbent manufacturing method selected from ascorbic acid, sulfonic acid, carboxylic acid, formic acid or citric acid. The method of claim 25, The organic acid is added to the mixed solution of the alcohol aqueous solution containing silver (Ag) compound and the polymer compound mixed to maintain a temperature of 60 ℃ to 100 ℃ and mixed for 5 minutes to 1 hour at a rotation speed of 30 to 100 rpm Method for producing a porous composite adsorbent to reduce the silver to produce a silver nano dispersion solution. The method of claim 18, In the mixing of step ii), a porous composite adsorbent is prepared by adding a porous adsorbent, an acid-treated porous adsorbent, or a mixture thereof to a solid solution: liquid volume ratio of 1: 0.5 to 5 in an aqueous solution in which purified water is added to the silver nano dispersion solution. Way. The method of claim 27, Mixing of step ii) is a method for producing a porous composite adsorbent to maintain the temperature of 30 ℃ to 100 ℃, carried out for 1 to 4 hours at a rotational speed of 30 to 100rpm. The method of claim 28, The firing of step ii) is a porous composite adsorbent manufacturing method carried out for 2 to 5 hours while maintaining a temperature of 200 ℃ to 500 ℃. delete A porous composite adsorbent filter prepared by filling the porous composite adsorbent according to any one of claims 1 to 7. The method of claim 31, wherein The porous composite adsorbent filter is attached to the filter medium of the filter using a binder.