KR101093524B1 - Preparation method of antibacterial activated carbon - Google Patents

Preparation method of antibacterial activated carbon Download PDF

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KR101093524B1
KR101093524B1 KR1020070038636A KR20070038636A KR101093524B1 KR 101093524 B1 KR101093524 B1 KR 101093524B1 KR 1020070038636 A KR1020070038636 A KR 1020070038636A KR 20070038636 A KR20070038636 A KR 20070038636A KR 101093524 B1 KR101093524 B1 KR 101093524B1
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activated carbon
silver
water
antimicrobial
present
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KR20080094334A (en
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김현택
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(주)삼천리카보텍
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

본 발명은 항균성을 갖는 활성탄의 제조방법에 관한 것으로 활성탄에 은을 포함하는 화합물을 함침하여 은을 담지시키고 산화제를 이용하여 산화시킨 후 활성탄으로부터 산화제를 세척하여 제거하고 이를 수소분위기에서 열처리함에 의하여 은이 첨착된 활성탄을 제조하는 방법에 관한 것이다. 본 발명의 방법에 의하여 제조된 활성탄은 일반적인 은화합물을 담지한 활성탄에 비하여 순수한 은이 활성탄의 표면에 존재하게 되므로 지속적인 항균효과를 가지며 흡착특성이 우수하고 생체에의 위험성이 적은 특징을 가지므로 정수기 등에서의 항균성 흡착제로서 유용하게 사용될 수 있다.The present invention relates to a method for producing activated carbon having antimicrobial properties, by impregnating silver by impregnating a compound containing silver into activated carbon, oxidizing with an oxidizing agent, and then removing the oxidizing agent from the activated carbon by heat treatment in a hydrogen atmosphere. It relates to a method for producing impregnated activated carbon. Activated carbon prepared by the method of the present invention has a continuous antibacterial effect and has excellent adsorption characteristics and has a low risk to the living body since the pure silver is present on the surface of the activated carbon compared to the activated carbon carrying a general silver compound, It can be usefully used as an antimicrobial adsorbent of.

활성탄, 은, 항균, 첨착, 흡착제 Activated Carbon, Silver, Antibacterial, Impregnated, Adsorbent

Description

항균성 활성탄의 제조방법 {PREPARATION METHOD OF ANTIBACTERIAL ACTIVATED CARBON}Preparation method of antimicrobial activated carbon {PREPARATION METHOD OF ANTIBACTERIAL ACTIVATED CARBON}

도 1은 본 발명의 실시예 1, 실시예 2에 의하여 제조된 활성탄과 비교예의 활성탄의 물 통과량에 따른 은 성분의 잔류량 비교 그래프이다.1 is a graph comparing the residual amount of silver components according to the water passage amount of the activated carbon prepared in Examples 1 and 2 of the present invention and the activated carbon of the comparative example.

본 발명은 항균성을 갖는 활성탄의 제조방법에 관한 것으로 보다 상세하게는 활성탄에 은을 포함하는 화합물용액을 가하여 함침함에 의하여 은을 담지시키고 산화제를 이용하여 은산화물로 산화시킨 후 이를 수소분위기에서 열처리함에 의하여 은이 첨착된 활성탄을 제조하는 방법에 관한 것이다. The present invention relates to a method for producing activated carbon having antimicrobial properties, and more particularly, to impregnating silver by adding a compound solution containing silver to activated carbon and oxidizing it to silver oxide using an oxidizing agent, followed by heat treatment in a hydrogen atmosphere. It relates to a method for producing activated carbon impregnated with silver.

활성탄은 비표면적이 높아서 정수 및 공기정화등의 용도로 사용되는데 주성분이 탄소로 이루어져 있으므로 생체친화성이 높아서 세균과 같은 미생물이 쉽게 번식하는 특성을 가지고 있다. 따라서 이를 방지하기 위하여 정수기의 필터 등에는 항균성을 가지는 활성탄을 사용하는 것이 보다 바람직하며 일반적으로 은의 항균성을 이용하여 활성탄의 표면에 은을 첨착함으로써 항균성을 부여하는 방법을 사 용하게 된다. 일반적으로 항균성 활성탄은 질산은[AgNO3]과 같은 은화합물을 수용액상으로 활성탄에 첨착하고 세척함에 의하여 제조하게 된다. 대한민국 특허 제 455664호에는 활성탄소섬유를 질산용액으로 전처리한 후 0.5~10%의 질산은 용액에 침지하고 건조시키는 은 표면처리된 활성탄소섬유의 제조방법을 개시하고 있다. 그러나 이와 같이 제조된 활성탄은 정수기의 필터로서 사용시에 활성탄 표면에 첨착된 은화합물이 물에 상대적으로 용이하게 용해되므로 사용초기에 물의 통과에 의하여 용이하게 용출되어 항균효과가 지속적으로 유지되지 못하며 초기에 통과시킨 물에는 지나치게 은의 함량이 높게 되는 단점을 가지고 있었다. 따라서 이러한 점을 보완하기 위하여 대한민국 특허 제523324호에는 활성탄의 표면에 은 을 비롯한 여러가지 전이금속을 나노형태로 전해도금하는 방법에 의하여 항균성 활성탄을 제조하는 방법을 개시하고 있다. 이 방법은 표면에 직접 은 등을 도금하는 방법을 사용하므로 균일하게 도금이 되는 경우 비교적 효과의 지속이 기대되지만 도금시의 전류의 통과 경로에 따라 일부의 활성탄 입자에 편중되어 도금되게 되며 편중된 부분의 경우 비표면적의 손실이 크게 발생하게 되어 흡착력이 크게 저하하며 잔여 부분의 경우에는 도금이 제대로 일어나지 않는 등 활성탄의 제조에 적용하는데 있어서 장치구성이 복잡하며 대량생산에 있어서 해결이 곤란한 문제점을 가지고 있다. 이와 같은 특허로는 대한민국 특허출원 10-2000-0058992, 10-2001-0056031, 10-2000-0058992 등이 출원되었으나 거절사정된 바 있다. 또한 대한민국 특허 제 354956에는 은을 비롯한 여러 금속을 열경화성수지 분말에 혼합하여 섬유화하고 열경화, 탄 화, 활성화하고 기타 생약성분을 담지시키는 방법에 의한 항균성 활성탄소섬유의 제조방법을 개시하고 있으나 이 또한 제조공정이 매우 복잡하며 방사공정 등에서 섬유가 단사에 의한 원활한 제조가 곤란하며 또한 섬유상의 활성탄을 제조하는 방법에 국한되므로 대량생산에 있어서 치명적이며 제조비용이 매우 높게 되는 단점을 가지고 있다.Activated charcoal has high specific surface area and is used for water purification and air purification. Since its main component is carbon, it has high biocompatibility and has the property of easily breeding microorganisms such as bacteria. Therefore, in order to prevent this, it is more preferable to use activated carbon having an antimicrobial property in a filter of a water purifier, etc. In general, a method of imparting antimicrobial properties by attaching silver to the surface of activated carbon using antimicrobial properties of silver is used. In general, the antimicrobial activated carbon is prepared by attaching a silver compound such as silver nitrate [AgNO 3 ] to the activated carbon in an aqueous solution and washing it. Republic of Korea Patent No. 455664 discloses a method for producing a silver surface treated activated carbon fiber, which is pretreated with carbonic acid solution and then immersed in 0.5 to 10% silver nitrate solution and dried. However, the activated carbon prepared in this way is easily dissolved by water when the silver compound adhering to the surface of activated carbon is dissolved in water at the time of use as a filter of water purifier. Passed water had a disadvantage of excessively high content of silver. Therefore, to compensate for this, Korean Patent No. 523324 discloses a method of preparing antimicrobial activated carbon by electroplating various transition metals including silver on the surface of activated carbon in nano form. This method uses a method of plating silver directly on the surface, so if the plating is uniform, relatively effective effect is expected, but it is plated by being biased on some activated carbon particles according to the passage path of current during plating. In this case, the loss of specific surface area is greatly generated, so that the adsorption power is greatly reduced, and in the case of the remaining part, the device composition is complicated in the production of activated carbon, and the problem is difficult to solve in mass production. . Such patents have been filed in the Republic of Korea patent applications 10-2000-0058992, 10-2001-0056031, 10-2000-0058992 and the like, but has been rejected. In addition, Korean Patent No. 354956 discloses a method for producing antimicrobial activated carbon fibers by mixing various metals, including silver, with thermosetting resin powders to fiberize, thermoset, carbonize, activate and support other herbal ingredients. The manufacturing process is very complicated, and in the spinning process, it is difficult to manufacture the fiber smoothly by single yarn, and is limited to the method of manufacturing the fibrous activated carbon, which is fatal in mass production and has a very high manufacturing cost.

따라서, 본 발명의 목적은 이와 같은 문제점을 해결하기 위하여 안출된 것으로, 종래의 은화합물을 담지한 활성탄에 비하여 순수한 은이 활성탄의 표면에 균일하게 존재하게 되므로 지속적인 항균효과를 가지며 흡착특성이 우수하고 생체에의 위험성이 적은 특징을 가지는 정수기 등에서의 흡착제로서 유용하게 사용될 수 있는 항균성 활성탄의 제조방법을 제공하는 것이다.Therefore, the object of the present invention was devised to solve such a problem, since pure silver is uniformly present on the surface of activated carbon as compared to the activated carbon carrying a conventional silver compound, it has a continuous antibacterial effect and has excellent adsorption characteristics and It is to provide a method for producing antimicrobial activated carbon that can be usefully used as an adsorbent in water purifiers and the like having a low risk of erosion.

본 발명의 방법에 의하면 According to the method of the present invention

(a) 활성탄에 은을 포함하는 화합물 용액을 담지시키는 단계 (b) 상기 은화합물을 은산화물로 산화시키는 단계 (c) 은산화물을 포함하는 활성탄을 물로 세척하는 단계 (d) 이를 수소분위기에서 열처리하는 단계를 포함하는 은이 첨착된 항균성 활성탄을 제조하는 방법이 제공된다. 이하에 본 발명을 상세하게 설명한다. (a) supporting a compound solution containing silver on activated carbon (b) oxidizing the silver compound to silver oxide (c) washing activated carbon containing silver oxide with water (d) heat-treating it in a hydrogen atmosphere Provided is a method of manufacturing an antimicrobial activated carbon impregnated with silver, which comprises the steps of: The present invention will be described in detail below.

본 발명의 첫 번째 단계로서 먼저 통상의 활성탄에 은을 포함하는 화합물 용액을 가하여 은을 담지시킨다. 활성탄은 통상의 활성탄을 모두 이용할 수 있으며 원료로서 야자각, 석탄, 톱밥, 식물 부산물 및 기타 유기물질을 원료로 하여 제조된 흡착재로 이용되는 탄소질의 제품을 포함하며 입상, 조립상, 섬유상 등의 형태에 관계없이 사용할 수 있다. 이와 같은 활성탄에 은을 담지시키기 위하여 은을 포함하는 화합물의 용액중에 활성탄을 함침시킨다. 은을 포함하는 화합물은 가급적 수용성 화합물로서 물에 용해시켜서 수용액상으로 함침시키는 것이 바람직하다. 함침온도는 별도로 제한하지 않으며 은을 포함한 화합물의 용액의 농도는 몰 농도로서 0.1mol/L 이상인 것이 바람직하다. 0.1mol/L 미만인 경우에는 장시간 동안 함침처리를 진행시켜도 최종제품기준으로 은이 0.01중량% 이하의 낮은 담지량을 가지므로 항균성이 낮아지며 또한 항균작용이 너무 단기간 지속되게 되므로 공정의 복잡성에 비하여 효과가 낮아서 바람직하지 않다. 따라서 0.1mol/L 이상 포화농도까지의 용액을 이용하여 함침하는 것이 바람직하다. 은을 포함하는 화합물은 물에 용해가 가능한 것이면 어느것이나 사용할 수 있으며 이와 같은 화합물로써 질산은(AgNO3)을 들 수 있으며 이에 한정되지는 않는다.As a first step of the present invention, silver is first supported by adding a compound solution containing silver to conventional activated carbon. Activated carbon can use all kinds of ordinary activated carbon and includes carbonaceous products which are used as adsorbents manufactured from coconut shell, coal, sawdust, plant by-products and other organic materials as raw materials, and are in the form of granular, granular, fibrous, etc. Can be used regardless. In order to support silver on such activated carbon, activated carbon is impregnated in a solution of a compound containing silver. The compound containing silver is preferably dissolved in water as the water-soluble compound and impregnated into an aqueous solution. The impregnation temperature is not particularly limited and the concentration of the solution of the compound containing silver is preferably 0.1 mol / L or more as molar concentration. In the case of less than 0.1 mol / L, even if the impregnation treatment is carried out for a long time, the silver has a low loading amount of 0.01% by weight or less as a final product standard, and thus the antimicrobial activity is lowered and the antimicrobial activity lasts for too short, so the effect is lower than the complexity of the process. Not. Therefore, it is preferable to impregnate using a solution up to 0.1 mol / L or more saturated concentration. The compound containing silver can be used as long as it can be dissolved in water, and examples of such a compound include silver nitrate (AgNO 3 ), but are not limited thereto.

본 발명의 다음 단계로서 이와 같이 함침이 완료된 활성탄은 계속하여 산화제 용액중에서 반응시켜 은산화물을 형성하도록 처리한다. 본 단계의 처리에 앞서서 통상의 방법으로 건조를 행하는 경우에는 본 단계의 공정의 조절이 상대적으로 용이하므로 바람직하나 건조공정이 반드시 필요한 것은 아니므로 공정의 편의성을 증대시키기 위하여 생략하여도 무관하므로 이를 제한하지 않는다. 본 단계에서의 산화제 용액으로는 과산화수소(H2O2), 중크롬산칼륨(K2Cr2O7), 이산화망간(MnO2), 과망간 산칼륨(KMnO4), 과황산칼륨(K2S2O8), 수산화나트륨(NaOH) 등의 화합물을 사용할 수 있다. 이와 같은 산화제와의 반응에 의하여 표면에 담지된 은 화합물은 은산화물로 변화하게 된다. 반응온도는 산화제 용액이 액상으로 존재하는 온도에서 행하면 되므로 이를 별도로 제한하지 않는다. 산화제의 농도는 몰 농도로서 0.1mol/L 이상인 것이 바람직하다. 0.1mol/L 미만인 경우에는 장시간 동안 산화반응을 진행시켜도 반응속도가 너무 낮아 활성탄에 담지된 모든 은화합물 성분을 산화시키기가 곤란하므로 0.1mol/L 이상 포화농도까지의 용액을 이용하여 산화반응을 진행시키는 것이 바람직하다. As a next step of the invention, the impregnated activated carbon is subsequently treated in a oxidant solution to form silver oxide. In the case of drying in a conventional manner prior to the treatment of this step, it is preferable to control the process of this step is relatively easy, but the drying process is not necessarily necessary, so it may be omitted to increase the convenience of the process, so this limitation is limited. I never do that. The oxidant solution in this step is hydrogen peroxide (H 2 O 2 ), potassium dichromate (K 2 Cr 2 O 7 ), manganese dioxide (MnO 2 ), potassium permanganate (KMnO 4 ), potassium persulfate (K 2 S 2 O 8 ), sodium hydroxide (NaOH) and the like can be used. The silver compound supported on the surface by the reaction with such an oxidant is changed to silver oxide. The reaction temperature is not particularly limited because the reaction temperature may be performed at a temperature in which the oxidant solution is present in the liquid phase. The concentration of the oxidant is preferably 0.1 mol / L or more as the molar concentration. In the case of less than 0.1 mol / L, even if the oxidation reaction is carried out for a long time, the reaction rate is so low that it is difficult to oxidize all the silver compound components supported on the activated carbon. It is preferable to make it.

본 발명의 다음 단계로서 앞의 단계까지의 처리에 의하여 은산화물의 피막이 형성된 활성탄을 충분한 양의 물로 세척을 행한다. 이것은 활성탄에 물을 가하여 잔존하는 산화제 용액을 제거하기 위한 것으로 통상의 일반적인 활성탄의 세척방법에 의하여 산화제 용액을 제거하면 되므로 별도로 세척장치나 세척조건을 제한하지 않는다.As a next step of the present invention, activated carbon in which a film of silver oxide is formed by the treatment up to the previous step is washed with a sufficient amount of water. This is to remove the remaining oxidant solution by adding water to the activated carbon, and since the oxidant solution is removed by a general method of cleaning activated carbon, the washing apparatus or the washing conditions are not separately limited.

본 발명의 마지막 단계인 다음 단계로서 은산화물이 표면에 담지된 활성탄은 계속하여 수소분위기에서 열처리함에 의하여 은성분을 활성탄의 세공표면에 노출되도록 하게 된다. 본 단계의 처리에 앞서서 통상의 방법으로 건조를 행하는 경우에는 본 단계의 공정의 조절이 상대적으로 용이하므로 바람직하나 건조공정이 반드시 필요한 것은 아니므로 공정의 편의성을 증대시키기 위하여 생략하여도 무관하므로 이를 제한하지 않는다. 단지 건조를 실시하는 경우 공정의 편의성을 향상시키기 위하 여 먼저 통상의 활성탄 건조방법으로 건조를 행하고 분위기를 불활성 분위기로 전환한 후 본 단계의 열처리 온도까지 승온한 후 수소분위기로 전환하여 본 단계에서의 열처리 공정을 실시할 수 있다. 본 단계는 이전까지의 단계에서 생성된 은산화물을 순수한 은 성분으로 변환시킴에 의하여 최종적으로 제조된 활성탄을 정수용으로 사용시 물과의 접촉에 의하여 은이 지속적으로 용출될 수 있도록 하고자 하는 것이다. 수소 분위기에서의 열처리 온도는 400℃ 내지 1200℃ 범위로 하는 것이 바람직하며 열처리 처리 시간은 2분 내지 5시간 이내로 하는 것이 바람직하다. 만일 수소 분위기의 열처리 온도가 400℃ 미만인 경우 5시간 이상 장시간 열처리하여도 표면의 은산화물의 은으로의 환원반응이 효과적으로 일어나지 않으며, 반면 1200℃ 이상인 경우 2분 미만의 단시간동안 열처리를 수행하여도 활성탄의 미세구조가 결정화가 진행되어 세공의 수축 및 통합에 따른 비표면적의 저하가 일어나게 되므로 바람직하지 않다. 본 단계에 있어서 수소는 반드시 100%를 공급할 필요는 없으며, 질소, 헬륨, 아르곤 등과 같은 불활성 기체와 혼합하여 공급할 수도 있다. 단, 전체 기체 중의 수소의 비율은 부피%로 2% 이상이어야 한다. 수소 기체의 비율이 2% 미만일 경우에는 수소의 분압이 너무 낮으므로 은산화물의 은으로의 환원반응 효율이 떨어져 장시간의 처리에도 반응속도가 지나치게 낮아지기 때문이다. As a next step, which is the last step of the present invention, activated carbon on which silver oxide is supported on the surface is continuously heat treated in a hydrogen atmosphere to expose the silver component to the pore surface of the activated carbon. In the case of drying in a conventional manner prior to the treatment of this step, it is preferable to control the process of this step is relatively easy, but the drying process is not necessarily necessary, so it may be omitted to increase the convenience of the process, so this limitation is limited. I never do that. In the case of only drying, in order to improve the convenience of the process, first, drying is carried out by a general activated carbon drying method, and the atmosphere is converted to an inert atmosphere, and then the temperature is raised to the heat treatment temperature of this step, and then converted into a hydrogen atmosphere. The heat treatment step can be carried out. This step is to convert the silver oxide produced in the previous step to pure silver component so that the silver can be continuously eluted by contact with water when the finally produced activated carbon is used for water purification. The heat treatment temperature in the hydrogen atmosphere is preferably in the range of 400 ° C to 1200 ° C, and the heat treatment time is preferably within 2 minutes to 5 hours. If the heat treatment temperature of the hydrogen atmosphere is less than 400 ℃, even if the heat treatment for a long time for more than 5 hours does not effectively reduce the silver oxide on the surface to silver, whereas if the heat treatment for more than less than 2 minutes for 1200 ℃ or more activated carbon The microstructure of is not preferable because the crystallization proceeds to decrease the specific surface area due to shrinkage and integration of the pores. In this step, hydrogen does not necessarily have to be supplied 100%, and may be supplied by mixing with an inert gas such as nitrogen, helium, argon, or the like. Provided that the proportion of hydrogen in the total gas is at least 2% by volume. This is because when the proportion of hydrogen gas is less than 2%, the partial pressure of hydrogen is so low that the reduction efficiency of silver oxide to silver is reduced, and the reaction rate is too low even for long time treatment.

이와 같이 제조된 활성탄은 종래의 은화합물을 담지한 활성탄에 비하여 순수한 은이 활성탄의 표면에 균일하게 존재하게 되므로 지속적인 항균효과를 가지며 흡착특성이 우수하고 생체에의 위험성이 적은 특징을 가지게 된다.Since the activated carbon prepared as described above has pure silver present uniformly on the surface of activated carbon as compared to the activated carbon carrying a conventional silver compound, it has a continuous antibacterial effect, has excellent adsorption characteristics, and has a low risk to a living body.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기 의 실시예는 본 발명을 쉽게 이해하기 위하여 제공되는 것일 뿐, 본 발명이 하기의 실시예에 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to easily understand the present invention, the present invention is not limited to the following examples.

<실시예 1> &Lt; Example 1 >

야자각을 원료로 하여 제조된 비표면적 1150m2/g인 상용의 활성탄을 7mol/L 농도의 질산은(AgNO3) 수용액을 80℃로 유지시키고 24시간 동안 교반하면서 침적하여 질산은을 담지시켰다. 이 활성탄을 상온에서 무게비로 5% mol/L 농도의 과망간산칼륨(KMnO4) 수용액에서 8시간 반응시켰다. 반응이 완료된 활성탄을 과량의 물로 세척하고 건조한 후 계속하여 부피기준 50%의 수소와 50%의 질소로 이루어진 혼합가스 분위기에서 600℃로 1시간 동안 열처리를 실시하였다. 이와 같이 제조된 활성탄의 은의 함량은 정량분석결과 0.72중량%를 나타내었으며 비표면적은 1020m2/g을 나타내었다. 이 활성탄을 카트리지 형태의 칼럼에 45g 장입하고 50ml/분의 유속으로 물을 계속하여 통과시켰다. 일정량의 물을 통과시킨 후에는 물을 정지시키고 활성탄의 일부를 시료로 채취하여 활성탄 중의 은함량을 정량분석하였다. 활성탄 시료를 채취한 후에는 시료채취에 의하여 감소된 장입량 만큼의 비율로 물의 통과량을 감소시켜서 장입무게당 유속을 동일하게 유지하였다. 그결과 활성탄 1g당 10L의 물을 통과시킨 후의 잔량은 0.12중량%를 나타내었으며 물의 통과량에 따른 활성탄중에 잔류하고 있는 은의 함량을 도 1에 나타내었다. 도1로부터 지속적으로 은이 용출되는 것을 확인할 수 있었다.A commercial activated carbon having a specific surface area of 1150 m 2 / g prepared using palm shell as a raw material was deposited while maintaining a 7 mol / L silver nitrate (AgNO 3 ) aqueous solution at 80 ° C. with stirring for 24 hours to support silver nitrate. The activated carbon was reacted in aqueous solution of potassium permanganate (KMnO 4 ) at a weight ratio of 5% mol / L at room temperature for 8 hours. After the reaction was completed, the activated carbon was washed with excess water, dried, and then heat-treated at 600 ° C. for 1 hour in a mixed gas atmosphere composed of 50% hydrogen and 50% nitrogen by volume. The content of silver in the activated carbon thus obtained was 0.72 wt% and the specific surface area was 1020 m 2 / g. 45 g of this activated carbon was charged into a cartridge type column and water was continuously passed through at a flow rate of 50 ml / min. After passing a certain amount of water, the water was stopped and a portion of the activated carbon was taken as a sample to quantify the silver content in the activated carbon. After collecting the activated carbon sample, the flow rate of water was maintained at the same rate by reducing the passage of water at a rate equivalent to the amount of charge reduced by sampling. As a result, the residual amount after passing 10L of water per 1g of activated carbon was 0.12% by weight, and the content of silver remaining in the activated carbon according to the amount of water passed is shown in FIG. 1. From Figure 1 it was confirmed that the silver is continuously eluted.

<비교예> Comparative Example

상용의 일반 은첨착활성탄을 이용하여 은의 함량을 분석한 결과 0.44중량%를 나타내었으며 비표면적은 980m2/g을 나타내었다. 이 활성탄을 실시예1에서와 동일한 카트리지 형태의 칼럼에 동일한 조건과 방법으로 물을 통과시키면서 활성탄의 일부를 시료로 채취하여 활성탄 중의 은함량을 정량분석하였다. 그 결과 활성탄 1g당 10L의 물을 통과시킨 후의 잔량은 0.005중량%를 나타내었으며 물의 통과량에 따른 활성탄중에 잔류하고 있는 은의 함량을 실시예 1의 결과와 함께 도 1의 상용활성탄 항목에 나타내었으며 물을 통과시킨 초기에 대부분의 은성분이 용출되어 제거된 것을 확인할 수 있었다.As a result of analyzing silver content using commercially available silver impregnated activated carbon, the specific surface area was 0.44% by weight and 980m 2 / g. The activated carbon was sampled while a portion of the activated carbon was sampled while passing water through the same cartridge type column as in Example 1 under the same conditions and methods. As a result, the residual amount after passing 10L of water per 1g of activated carbon was 0.005% by weight. The amount of silver remaining in the activated carbon according to the amount of water passing through is shown in the commercially available activated carbon of FIG. It was confirmed that most of the silver component was eluted and removed at the beginning of the passage.

<실시예2> Example 2

야자각을 원료로 하여 제조된 비표면적 1150m2/g인 상용의 활성탄을 3mol/L 농도의 질산은(AgNO3) 수용액을 80℃로 유지시키고 24시간 동안 교반하면서 침적하여 질산은을 담지시켰다. 이 활성탄을 상온에서 무게비로 3% mol/L 농도의 이산화망간(MnO2) 수용액에서 8시간 반응시켰다. 반응이 완료된 활성탄을 과량의 물로 세척하고 건조한 후 계속하여 부피기준 50%의 수소와 50%의 질소로 이루어진 혼합가스 분위기에서 600℃로 1시간 동안 열처리를 실시하였다. 이와 같이 제조된 활성탄의 은의 함량은 정량분석결과 0.22중량%를 나타내었으며 비표면적은 1070m2/g을 나타내었다. 이 활성탄을 실시예1과 동일한 방법으로 물을 통과시키면서 활성탄중에 잔류하는 은의 함량을 측정하였다. 그 결과 물의 통과량에 따른 활성탄중에 잔류하고 있는 은의 함량을 도 1에 나타내었다. 도 1로부터 7.5L/g 정도의 물을 통과할 때까지 지속적으로 은이 용출되는 것을 확인할 수 있었다. A commercial activated carbon having a specific surface area of 1150 m 2 / g prepared using coconut shell was deposited on an aqueous solution of 3 mol / L concentration of silver nitrate (AgNO 3 ) at 80 ° C., and stirred for 24 hours to support silver nitrate. The activated carbon was reacted for 8 hours in an aqueous solution of manganese dioxide (MnO 2 ) at a weight ratio of 3% mol / L at room temperature. After the reaction was completed, the activated carbon was washed with excess water, dried, and then heat-treated at 600 ° C. for 1 hour in a mixed gas atmosphere composed of 50% hydrogen and 50% nitrogen by volume. The content of silver in the activated carbon thus produced was 0.22% by weight, and the specific surface area was 1070m 2 / g. The content of silver remaining in the activated carbon was measured while passing the water through the activated carbon in the same manner as in Example 1. As a result, the amount of silver remaining in the activated carbon according to the amount of water passage is shown in FIG. From Figure 1 it was confirmed that the silver is continuously eluted until passing through the water of about 7.5L / g.

상기한 바와 같이 본 발명의 방법으로 제조된 실시예 1 및 2의 활성탄은 비교예 1의 활성탄보다 물을 통과시킴에 따른 은의 잔류함량의 지속성이 크게 향상되었으며 이에 따라 항균성능이 지속되게 되는 것을 알 수 있었다. 또한 비표면적이 크게 감소하지 않으므로 흡착성능이 유지되는 것을 알 수 있었으며 산화 및 환원반응을 거치게 되면서 유독성을 갖는 질산은이 완전히 제거되게 되므로 생체에의 위험성이 크게 향상되게 되는 것은 별도의 실시실험을 행하지 않아도 관련분야의 당업자에게는 용이하게 인지될 수 있을 것이다.As described above, the activated carbons of Examples 1 and 2 prepared by the method of the present invention have significantly improved the persistence of the residual content of silver as water passes through the activated carbon of Comparative Example 1, and thus the antimicrobial performance is sustained. Could. In addition, the specific surface area did not decrease significantly, so it was found that the adsorption performance was maintained. As the toxic silver nitrate was completely removed during the oxidation and reduction reaction, the risk to the living body was greatly improved without additional experiments. It will be readily appreciated by those skilled in the art.

본 발명에 의한 방법에 의하여 순수한 은이 활성탄의 표면에 존재하여 향상된 지속적인 항균효과와 높은 흡착특성을 가지며 생체에의 위험성이 적은 특징을 갖는 항균성 활성탄의 제조가 가능하며 이와 같은 특징을 이용하여 정수기 등에서의 흡착제로 사용이 가능하다.By the method according to the present invention, pure silver is present on the surface of activated carbon, and thus, it is possible to prepare antimicrobial activated carbon having improved persistent antimicrobial effect, high adsorption characteristics, and low risk to the living body. It can be used as an adsorbent.

Claims (3)

(a) 활성탄에 0.1mol/L 이상의 농도를 가지며 물에 용해가능한 은화합물을 담지시키는 단계;(a) supporting a silver compound having a concentration of at least 0.1 mol / L in activated carbon and soluble in water; (b) 담지된 은화합물을 0.1mol/L 이상의 농도의 산화제와 반응시켜 은산화물로 산화키는 단계;(b) reacting the supported silver compound with an oxidant at a concentration of at least 0.1 mol / L to oxidize it to silver oxide; (c) 은산화물이 포함된 활성탄을 물로 세척하는 단계;(c) washing activated carbon containing silver oxide with water; (d) 세척된 활성탄을 부피기준 2% 이상의 농도의 수소분위기, 400℃ 내지 1200℃의 온도에서 2분 내지 5시간 동안 열처리하는 단계;를 포함하는 것을 특징으로 하는 은이 첨착된 항균성 활성탄의 제조방법.(d) heat-treating the washed activated carbon at a concentration of 2% or more by volume in a hydrogen atmosphere, at a temperature of 400 ° C. to 1200 ° C. for 2 minutes to 5 hours. . 제 1항에 있어서,The method of claim 1, 상기 은화합물은 질산은(AgNO3)인 것을 특징으로 하는 은이 첨착된 항균성 활성탄의 제조방법.The silver compound is silver nitrate (AgNO 3 ) characterized in that the production method of the antimicrobial activated carbon impregnated with silver. 제 1항에 있어서,The method of claim 1, 상기 산화제는 과산화수소(H2O2), 중크롬산칼륨(K2Cr2O7), 이산화망간(MnO2), 과망간산칼륨(KMnO4), 과황산칼륨(K2S2O8), 수산화나트륨(NaOH) 중에서 선택되는 1종인 것을 특징으로 하는 은이 첨착된 항균성 활성탄의 제조방법.The oxidizing agent is hydrogen peroxide (H 2 O 2 ), potassium dichromate (K 2 Cr 2 O 7 ), manganese dioxide (MnO 2 ), potassium permanganate (KMnO 4 ), potassium persulfate (K 2 S 2 O 8 ), sodium hydroxide ( NaOH) The production method of the antimicrobial activated carbon impregnated with silver, characterized in that one kind selected from.
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JPS5719083A (en) 1980-07-07 1982-02-01 Yukio Okura Production of silver-impregnated active carbon
JPH1085759A (en) 1996-09-13 1998-04-07 Ichiro Arai Preparation of purifying agent for sterilization
JPH10137524A (en) 1996-11-18 1998-05-26 Sakai Chem Ind Co Ltd Anti-bacterial activated carbon and its production

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5719083A (en) 1980-07-07 1982-02-01 Yukio Okura Production of silver-impregnated active carbon
JPH1085759A (en) 1996-09-13 1998-04-07 Ichiro Arai Preparation of purifying agent for sterilization
JPH10137524A (en) 1996-11-18 1998-05-26 Sakai Chem Ind Co Ltd Anti-bacterial activated carbon and its production

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