KR20030020004A - Development of adsorption material with curdlan and activated carbon - Google Patents

Development of adsorption material with curdlan and activated carbon Download PDF

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KR20030020004A
KR20030020004A KR1020010052253A KR20010052253A KR20030020004A KR 20030020004 A KR20030020004 A KR 20030020004A KR 1020010052253 A KR1020010052253 A KR 1020010052253A KR 20010052253 A KR20010052253 A KR 20010052253A KR 20030020004 A KR20030020004 A KR 20030020004A
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activated carbon
curdlan
adsorbent
adsorption
development
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KR1020010052253A
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Korean (ko)
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이중헌
김봉영
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이중헌
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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

Abstract

PURPOSE: Provided is an adsorbent with high adsorbability using activated carbon and curdlan. CONSTITUTION: The method comprises the steps of inputting activated carbon and curdlan into water and stirring the same, thereby obtaining activated carbon-curdlan solution; heating the activated carbon-curdlan solution at a temperature of 100 deg.C for obtaining activated carbon-curdlan gel; freezing the activated carbon-curdlan gel at a temperature of -70 deg.C; and freeze drying the frozen activated carbon-curdlan gel.

Description

커들란과 활성탄을 이용한 고성능 흡착제{Development of adsorption material with curdlan and activated carbon}High performance adsorbent using curdlan and activated carbon {Development of adsorption material with curdlan and activated carbon}

활성탄은 오래전부터 악취를 제거하고, 불순물을 흡착하기 때문에 다양한 용도로 사용되어왔다. 특히 숯은 음식물에 넣어 불순물을 흡착하기 때문에 건강에 유익한 것으로 인정받아 왔다. 그러나, 숯을 사용할 경우 단위 질량당 표면적이 적고 숯가루의 경우에는 분산되기 때문에 취급하기 어려운 측면이 많다. 이러한 문제점을 해결하고자 공업적인 방법을 사용하여 숯을 응결화 시켜 이를 이용하여 다양한 분야에 많이 쓰이고 있으나 재료의 대부분이 공업용으로 식품 등의 다양한 용도로 적용하기 힘들었다.Activated carbon has long been used for various purposes because it removes odors and adsorbs impurities. In particular, charcoal has been recognized as beneficial for health because it adsorbs impurities in food. However, when charcoal is used, the surface area per unit mass is small, and in the case of charcoal powder, many aspects are difficult to handle. In order to solve this problem, the coal is condensed by using industrial methods, and it is used in various fields by using it. However, most of the materials were difficult to apply to various uses such as food for industrial purposes.

본 발명에서는 이러한 기존의 흡착제의 문제점을 보완하여 흡착능력이 뛰어나면서 식품용으로 사용이 가능한 고성능 흡착제를 개발하고자 하였다. 본 발명은 미생물 다당류인 커들란에 활성탄을 고정화시키는 방법을 고안하여 고성능 흡착제를 개발하였다. 본 발명에서 악취가스, 독가스, 중금속 등의 유해물질을 흡착하는 우수한 성질을 보유한 고성능 흡착제를 개발하는데 목적이 있다. 특히 본 발명에서 사용한 미생물 다당류는 식품용으로 사용되는 것으로 본 발명에서 개발된 고성능흡착제는 식품정화용으로 사용하는 것이 또한 가능하였다.In the present invention, it was intended to develop a high-performance adsorbent that can be used for food while having excellent adsorption capacity by supplementing the problems of the existing adsorbent. The present invention has devised a method for immobilizing activated carbon in the microorganism polysaccharide curdlan to develop a high performance adsorbent. It is an object of the present invention to develop a high performance adsorbent having excellent properties of adsorbing harmful substances such as odor gas, poison gas, heavy metals. In particular, the microbial polysaccharide used in the present invention is used for food, it was also possible to use the high-performance adsorbent developed in the present invention for food purification.

일반활성탄의 표면은 비극성이며 흡착력이 본질적으로 단순히 반델발스 힘에 의한 물리흡착이기 때문에 악취가스 등의 끓는점이 낮은 성분에 대해서는 충분한 흡착성을 갖지 못한다. 따라서, 활성탄을 화학적으로 처리하거나 화학 약품을 사용 특성을 변형시킴으로써 특이성분에 대해 선택적 흡착을 가진 활성탄 등이 개발되고 있다.Since the surface of general activated carbon is non-polar and the adsorption force is simply physical adsorption by van der Waals forces, it does not have sufficient adsorption to low boiling components such as odor gas. Accordingly, activated carbon and the like having selective adsorption to specific components have been developed by chemically treating activated carbon or modifying chemical use properties.

종래 조립상 활성탄소는 형상이 균일하여 유속분포가 일정하고 통기저항도 작아 동력비가 절약된다는 장점을 보유하고 있지만, 그 흡착특성이 일반활성탄소에 의한 물리적 흡착(Physical Adsorption)으로서, 흡착제 표면과 흡착질간에 전자의 공유를 갖지 않기 때문에 흡착질은 흡착제의 표면 가까이에 일시적으로 붙잡힌 상태에 놓여 있게 되는 것이다. 따라서 이렇게 약하게 흡착된 분자는 용액의 농도변화나 그다지 크지 않은 온도와 압력의 변화에 의해 쉽게 탈착되며 이로서 흡착용량이 낮고, 흡착 선택성과 효율이 낮은 단점이 있었다.Conventional granular activated carbon has the advantage of uniform shape, low velocity distribution and low air flow resistance, which saves energy cost. However, its adsorption characteristics are physical adsorption by general activated carbon, Since it does not have electron sharing, the adsorbate is placed in a state of being temporarily trapped near the surface of the adsorbent. Therefore, the weakly adsorbed molecules are easily desorbed due to the change of solution concentration or the change of temperature and pressure which are not so large, and thus have the disadvantage of low adsorption capacity and low adsorption selectivity and efficiency.

위의 이유 등으로 장치 규모가 대형화되고 설비비 및 흡착제 구입비가 증대되는 문제가 생기게 되었다. 또한, 분뇨처리장의 배기가스 탈취, 하수처리장 및 쓰레기 소각장 등에서 발생하는 산성가스, 염기성 가스, 중성가스 등을 흡착제거 하는데 그 선택성과 효율면에서도 문제점이 있었다. 그러므로, 현재 사용되고 있는 조립상 활성탄소에 특정한 금속염을 첨착시켜 문제점을 보완한 조립상 첨착 활성탄소에 관한 연구가 필요하게 된 것이다. 조립상 첨착 활성탄소란 미세공(Micropore, IUPAC 규정에 의해 크기가 20Å이하를 의미하며 이것이 70%이상 존재.) 이 잘 발달되어 물리적 흡착력이 뛰어나고 경도가 99.9% 이상으로 단단한 조립상 활성탄소에 특정한 금속염을 첨착(Impregnation)시킨 것으로 촉매적 기능 즉 화학적 활성을 높인 조립상 활성탄소를 말한다.Due to the above reasons, there is a problem that the size of the device is enlarged and the cost of equipment and adsorbent purchase is increased. In addition, the adsorption and removal of acidic gases, basic gases, neutral gases, etc. generated in the exhaust gas deodorization, sewage treatment plants and waste incinerators of the manure treatment plant had problems in terms of selectivity and efficiency. Therefore, there is a need for a study on the impregnated impregnated activated carbon supplementing the problem by the addition of a specific metal salt to the coarse activated carbon currently used. Activated carbon impregnated in granulation means that micropores (size less than 20Å by micropore, IUPAC regulations, which exists more than 70%) are well developed, so that they have high physical adsorption power and hardness of 99.9%. (Impregnation) refers to granulated activated carbon with enhanced catalytic function, ie chemical activity.

활성탄의 조립상의 상업화에도 불구하고 가정용 및 식품용도의 불순물 흡착 및 악취제거를 위한 흡착제의 발달은 많이 이루어지지 않고 있다. 본 발명에서는 이러한 문제를 해결하고자 식품용도로 개발되어 있는 미생물 다당류에 활성탄을 흡착시켜 공극률을 증가시키면서 식품용도로 사용이 가능한 고성능 흡착제를 개발하고자 하였다.Despite the commercialization of activated carbon, the development of adsorbents for adsorbing impurities and removing odors for household and food use has not been achieved. In order to solve this problem, the present invention has been made to develop a high-performance adsorbent that can be used for food while increasing the porosity by adsorbing activated carbon to microbial polysaccharides developed for food use.

미생물 유래 다당류인 커들란은 고온에서 젤을 형성하여 낮은 온도에서도 이러한 형태를 유지한다. 그러나, 자연상태에서 건조시키는 경우 수분의 증발로 인한 성상의 변화가 일어나 수축하게 되어 성상을 유지하기가 힘들다. 그러나, 겔화된 커들란을 냉동 건조시킬 경우 부피는 동일하면서 수분 증발로 인하여 내부에 수많은 공극이 생겨 단위 질량 당 표면적을 증가 시켜준다. 이러한 기술적인 발견을 토대로 커들란에 활성탄을 고정화 시킴으로써 표면적이 증가된 고성능 흡착제의 개발이 필요하였다. 또한, 커들란의 사용으로 인한 부피 증가로 인하여 단위부피 당 질량감소 등의 많은 효과를 유발할 수 있으며 커들란 자체가 식품용으로 개발되어 있기 때문에 식품용의 고성능 흡착제로서 활용이 가능하다.Curdlan, a microbial-derived polysaccharide, forms a gel at high temperatures and maintains this form even at low temperatures. However, in the case of drying in the natural state, the change of properties due to evaporation of moisture occurs, it is difficult to maintain the properties. However, freeze-drying the gelled curdlan has the same volume, but due to the evaporation of water, a large number of pores are formed inside, increasing the surface area per unit mass. Based on these technical findings, the development of high-performance adsorbents with increased surface area was required by immobilizing activated carbon in curdlan. In addition, due to the increase in volume due to the use of curdlan can cause a lot of effects such as mass reduction per unit volume, and because the curdlan itself is developed for food it can be utilized as a high performance adsorbent for food.

본 발명의 특징은 커들란이 공극률을 증가시킴과 동시에 활성탄 분말의 결속력을 유지 시켜준다. 또한 본 발명에서 고안된 흡착제의 제조방법인 활성탄과 커들란을 섞은 상태에서 냉동 건조시키는 방법은 커들란과 결합한 활성탄과의 성상을 유지시키며 표면적을 증가시킴으로써 흡착능력이 우수한 고성능 흡착제를 제조하는 것이 가능하다.A feature of the present invention is that the curdlan increases the porosity and at the same time maintains the binding force of the activated carbon powder. In addition, the method of manufacturing the adsorbent of the present invention, which is a method of freeze drying in the state of mixing activated carbon and curdlan, can maintain a property of activated carbon combined with curdlan and increase the surface area to prepare a high-performance adsorbent having excellent adsorption capacity. .

고성능 흡착제 제조공정High Performance Adsorbent Manufacturing Process

흡착제로서는 활성탄 뿐만아니라, 규조토 ·제올라이트 ·실리카겔 ·녹말 ·벤토나이트 ·알루미나 등이 있다. 그런데 대다수의 흡착제는 반영구적일 뿐만 아니라 무기물이므로 2차적인 문제점을 야기시킬 수 있다. 그러나 커들란을 이용한 활성탄의 담체는 생분해성이므로 분해시 발생될 문제점을 해소 할 수 있다는 점에서 담체의 개발이 필요하다.As the adsorbent, not only activated carbon, but also diatomaceous earth, zeolite, silica gel, starch, bentonite, alumina and the like can be given. However, most of the adsorbents are not only semi-permanent but also inorganic and can cause secondary problems. However, since the carrier of activated carbon using curdlan is biodegradable, it is necessary to develop a carrier in that it can solve the problems caused during decomposition.

① Curdlan과 활성탄의 비를 다르게 하여 증류수(30㎖)가 들어있는 50㎖튜브에 넣는다.① Put Curdlan and activated carbon in different 50ml tube containing distilled water (30ml).

② 항온조에 넣어 100℃로 끓인 뒤 초저온조(-70℃)에서 넣고 동결시킨다.② Put it in a thermostat and boil it at 100 ℃ and put it in an ultra low temperature tank (-70 ℃) and freeze it.

③ 동결된 커들란을 동결건조시킨다.③ Freeze-dried frozen curdlan.

④ 건조되어진 담체를 이용 VOC 흡착특성을 조사한다.④ Investigate the adsorption characteristics of VOC using dried carrier.

실험결과Experiment result

실험에서 얻어진 결과물을 증류수에 넣어 혼합하여 흡착제를 만든 결과 커들란의 양이 활성탄에 비해 높을 경우 흡착제의 강도가 증가함을 알 수 있다. 먼저 커들란만을 증류수에 녹여 100℃로 가열하여 동결시킨 후 동결건조 시킨것과 커들란과 활성탄을 섞은 뒤 염기를 넣고 산을 넣은 뒤 가열하여 젤을 만든 뒤 동결건조시킨 것을 SEM을 이용하여 공극률 및 형태를 관찰하였다. 커들란과 활성탄에 증류수만을 넣은 경우 첨가한 비에 따라 커다란 차이가 났다. 커들란이 활성탄에 비해 적을 경우 입자의 형태가 잘 나오지 않았으나, 염기성 아미노산를 첨가하여 녹인 후 유기산으로 중화 처리한 경우 만들어진 입자의 강도가 증가하였다.As a result of making the adsorbent by mixing the resultant obtained in the experiment into distilled water, it can be seen that the strength of the adsorbent increases when the amount of curdlan is higher than that of activated carbon. First, only curdlan is dissolved in distilled water and heated to 100 ° C to freeze and then freeze-dried, mixed with curdlan and activated charcoal, base is added, acid is added, heated to make gel, and lyophilized using SEM. Was observed. When only distilled water was added to curdlan and activated carbon, there was a big difference according to the added ratio. When the curdlan was less than the activated carbon, the shape of the particles did not come out well, but when the basic amino acid was dissolved and neutralized with organic acid, the strength of the particles increased.

중금속 흡착실험Heavy Metal Adsorption Experiment

위 발명결과에서 제조된 고성능 흡착제(Sample 3)의 중금속 흡착 능을 조사하기 위하여 Cd(Ⅱ), Cu(Ⅱ), Pb(Ⅱ), Zn(Ⅱ) 등의 중금속을 사용하였다. 흡착실험은 100 ppm씩인 중금속 이온의 혼합용액에 1 g의 흡착제를 첨가하여 5시간동안 회분식 진탕기에서 흡착시킨 후 원심분리하여 상등액을 Atomic Absorption Spectrometer(PERKIN ELMER3100)로 중금속의 잔류농도를 측정하여 흡착량을 구하였다. 실험결과 각 중금속의 흡착용량을 비교하면 흡착제 1 g에 각 중금속의 흡착량이 Cd, Cu, Pb, Zn 각각 64.5 mg, 73.2 mg, 61.2 mg, 58.8 mg으로 나타나 다른 수지형 중금속 흡착제보다 흡착능력이 우수한 것으로 실험결과 나타났다.Heavy metals such as Cd (II), Cu (II), Pb (II), and Zn (II) were used to investigate the heavy metal adsorption capacity of the high performance adsorbent (Sample 3) prepared in the above invention results. Adsorption experiment was performed by adding 1 g of adsorbent to a mixed solution of heavy metal ions in 100 ppm increments and adsorbing them in a batch shaker for 5 hours. The amount was calculated. Experimental results showed that the adsorption capacity of each heavy metal was 64.5 mg, 73.2 mg, 61.2 mg, and 58.8 mg of Cd, Cu, Pb, and Zn, respectively. Experimental results showed that.

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Claims (3)

커들란 및 활성탄의 복합체로 만든 일반 및 식품용 고성능 흡착제High performance adsorbent for general and food made from complex of curdlan and activated carbon 커들란 활성탄 혼합물을 가열하여 젤로 만든 후 냉동 건조시켜 강도 및 형태를 유지시키며 고성능 흡착제를 제조하는 공정Process to prepare a high-performance adsorbent by heating the curdlan activated carbon mixture into a gel and freeze-drying to maintain strength and shape 청구항 2에서 고성능 흡착제 제조 시 염기성 아미노산 및 유기산을 첨가하여 강도를 증가시켜 제조하는 방법Method of preparing a high performance adsorbent in claim 2 by adding a basic amino acid and an organic acid to increase the strength
KR1020010052253A 2001-08-28 2001-08-28 Development of adsorption material with curdlan and activated carbon KR20030020004A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030043161A (en) * 2001-11-27 2003-06-02 주식회사 더멋진 바이오텍 Oil-absorbent using curdlan

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5542210A (en) * 1978-09-12 1980-03-25 Koichi Ogawa Special activated carbon
JPS6371158A (en) * 1986-09-16 1988-03-31 Kazuo Hara Production of foamable hydrophobic gel of devil's-tongue and foamable hydrophobic gelatinous substance
JPH06157807A (en) * 1992-11-19 1994-06-07 Mitsui Toatsu Chem Inc Production of porous polymeric material
KR20000029491A (en) * 1996-07-22 2000-05-25 아오야기 주로 Novel adsorbent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5542210A (en) * 1978-09-12 1980-03-25 Koichi Ogawa Special activated carbon
JPS6371158A (en) * 1986-09-16 1988-03-31 Kazuo Hara Production of foamable hydrophobic gel of devil's-tongue and foamable hydrophobic gelatinous substance
JPH06157807A (en) * 1992-11-19 1994-06-07 Mitsui Toatsu Chem Inc Production of porous polymeric material
KR20000029491A (en) * 1996-07-22 2000-05-25 아오야기 주로 Novel adsorbent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030043161A (en) * 2001-11-27 2003-06-02 주식회사 더멋진 바이오텍 Oil-absorbent using curdlan

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