KR101509181B1 - Manufacturing method of expanded graphite for high efficient oil adsorption - Google Patents

Manufacturing method of expanded graphite for high efficient oil adsorption Download PDF

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KR101509181B1
KR101509181B1 KR20130092045A KR20130092045A KR101509181B1 KR 101509181 B1 KR101509181 B1 KR 101509181B1 KR 20130092045 A KR20130092045 A KR 20130092045A KR 20130092045 A KR20130092045 A KR 20130092045A KR 101509181 B1 KR101509181 B1 KR 101509181B1
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acid
graphite powder
expanded graphite
oil
graphite
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KR20150015950A (en
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박수진
이슬이
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인하대학교 산학협력단
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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Abstract

본 발명은 오일흡착용 팽창흑연의 제조방법에 관한 것으로서, 더욱 상세하게는 건식공정을 통해 제조공정이 간편하고 우수한 팽창률 및 오일흡착능을 갖는 팽창흑연을 제조하는 방법에 관한 것이다.
상기와 같은 본 발명에 따르면, 제조공정이 간단하고 다량의 강산 및 산화제의 세척 및 산폐기물의 배출을 제어하여 친환경적이며 경제성이 우수한 팽창흑연을 제공하는 효과가 있다.
또한, 물과 오일이 공존하는 경우 오일에 대한 선택성이 강하고 빠른 흡수속도를 보이며 오일을 흡수한 후에도 물에 떠 있는 고효율 오일흡착용 팽창흑연을 제공하는 효과가 있다.The present invention relates to a method for producing expanded graphite for oil adsorption, and more particularly, to a method for producing expanded graphite having a simple manufacturing process and excellent expansion ratio and oil adsorbing ability through a dry process.
According to the present invention, the manufacturing process is simple, and washing of a large amount of strong acid and oxidizing agent and discharge of acid waste are controlled, thereby providing expanded graphite that is eco-friendly and excellent in economy.
In addition, when water and oil coexist, it has an effect of providing a high selectivity to oil and exhibiting a fast absorption rate, and also providing expanded graphite for high-efficiency oil adsorption floating in water even after absorption of oil.

Description

오일흡착용 팽창흑연의 제조방법{MANUFACTURING METHOD OF EXPANDED GRAPHITE FOR HIGH EFFICIENT OIL ADSORPTION}TECHNICAL FIELD [0001] The present invention relates to an expanded graphite for oil adsorption,

본 발명은 오일흡착용 팽창흑연의 제조방법에 관한 것으로서, 더욱 상세하게는 건식공정을 통해 제조공정이 간편하고 우수한 팽창률 및 오일흡착능을 갖는 팽창흑연을 제조하는 방법에 관한 것이다.
The present invention relates to a method for producing expanded graphite for oil adsorption, and more particularly, to a method for producing expanded graphite having a simple manufacturing process and excellent expansion ratio and oil adsorbing ability through a dry process.

세계적으로 많은 오일 누수 사건이 발생하고 있으며, 특히, 해상에서 발생하는 오일탱크 사고로 인한 거대한 양의 오일 누수는 해수의 오염뿐만 아니라 해저 및 연안 등으로 확산되어 토양 및 해양 생태계에 심각한 영향을 미치게 된다.Many oil leaks occur in the world, and a huge amount of oil leakage due to an oil tank accident in the sea is spread not only in seawater pollution but also in seabed and coastal areas, and has serious impact on soil and marine ecosystem .

이에 따라, 오일 누출 사고로 인한 해상 오염을 방지 및 해소하기 위하여 흡착소재를 이용한 오일제거기술이 활발하게 연구 중에 있다. 흡착소재로 폴리프로필렌, 폴리에틸렌 등을 이용한 고분자 흡착소재나 스타이렌, 에틸렌 중합체 등으로 제조되는 형태의 고분자계열이 주로 연구되어 왔지만, 이러한 고분자계열의 소재들은 흡착과정에서 오랜 시간과 많은 비용을 필요로 하며 낮은 오일흡착능을 갖는 단점이 있다. 뿐만 아니라, 물도 함께 흡수하여 오일에 대한 선택적인 흡착성이 떨어지고, 오일을 흡착한 후 흡착소재를 분리할 때에도 많은 비용을 필요로 하는 단점이 있다.Accordingly, in order to prevent and solve marine pollution caused by an oil leakage accident, an oil removing technique using an adsorbent material is actively under research. Polymer adsorption materials using polypropylene and polyethylene as the adsorbent materials and polymers such as styrene and ethylene polymer have been mainly studied. However, these polymer materials require long time and high cost in the adsorption process And has a low oil absorption capacity. In addition, there is a disadvantage in that water is also absorbed together to lower the selective adsorption property to the oil, and a large cost is also required in separating the adsorbed material after adsorbing the oil.

따라서, 최근에는 빠른 오일흡착속도와 고효율 오일흡착능을 지닌 소재 개발에 관심이 집중되고 있다. 흑연분말의 산 처리 및 열처리를 통해 생성된 팽창흑연은 흑연 층상간의 팽창으로 인해 다공성 구조를 지니며 흑연 고유의 표면 소수성을 갖는 특징으로 인해 오일 흡착제로 매우 적합한 것으로 알려져 있다.Therefore, recently, attention has been focused on the development of a material having a high oil adsorption rate and high efficiency oil adsorption capability. Expansion graphite produced through acid treatment and heat treatment of graphite powder is known to be very suitable as an oil adsorbent because of its porous structure due to expansion between graphite layers and its inherent surface hydrophobicity.

관련 선행기술로 대한민국 공개특허 10-2010-0101960(팽창흑연 내부에 자성 분말이 함침된 기름 고속제거제 및 이의 제조방법) 등이 있지만, 종래 강산 및 산화제의 습식처리 방법은 다량의 강산 및 산화제를 투입함에 따라 세척과정에서 다량의 증류수를 필요로 하고 폐산배출로 인해 환경적인 문제를 유발하며 고부식성 액체에 의한 공정상의 부식 문제 등 경제적인 소모가 큰 문제점이 있다.
Korean Patent Laid-Open No. 10-2010-0101960 (a high-speed oil removing agent impregnated with magnetic powder in expanded graphite and a method for producing the same) has been disclosed in related prior art. However, in the conventional wet processing method of strong acid and oxidizing agent, a large amount of strong acid and oxidizing agent A large amount of distilled water is required in the cleaning process, environmental problems are caused due to the discharge of waste acid, and economical consumption such as erosion in process due to high corrosive liquid is problematic.

본 발명의 목적은 제조공정이 간단하고 친환경적이며 경제성이 우수한 고효율 오일흡착용 팽창흑연을 제조하는 방법을 제공함에 있다.
An object of the present invention is to provide a method for producing expanded graphite for high-efficiency oil adsorption which is simple in manufacturing process, is environmentally friendly, and excellent in economy.

상기 목적을 달성하기 위하여, 본 발명은 (1) 흑연분말을 분쇄하는 단계; (2) 상기 (1)단계에서 분쇄된 흑연분말을 강산 및 산화제가 혼합된 혼합용액의 증기로 건식처리하여 층간삽입흑연분말을 제조하는 단계; (3) 상기 (2)단계에서 제조된 층간삽입흑연분말을 열처리하는 단계;를 포함하는 오일흡착용 팽창흑연의 제조방법을 제공한다.In order to achieve the above object, the present invention provides a method for producing a graphite powder, comprising the steps of: (1) pulverizing graphite powder; (2) drying the graphite powder pulverized in the step (1) by steam of a mixed solution of a mixture of a strong acid and an oxidizer to prepare an intercalated graphite powder; (3) heat treating the interlayer-inserted graphite powder produced in the step (2).

상기 (1)단계에서 분쇄공정은 0.5 내지 15 mm의 지르코니아볼을 이용하여 50 내지 600 rpm의 속도로 5 분 내지 24 시간 동안 볼밀처리하는 것을 특징으로 한다.In the step (1), the ball milling is performed using zirconia balls of 0.5 to 15 mm at a speed of 50 to 600 rpm for 5 minutes to 24 hours.

상기 (2)단계에서 강산은 발연황산(Oleum, SO3 gas), 황산(H2SO4), 질산(HNO3) 및 염산(HCl)을 포함하는 군에서 선택되는 1 이상이며, 산화제는 과산화수소(H2O2), 과산화이황산암모늄((NH4)2S2O8), 과염소산(HClO4), 하이포염소산(HClO), 과망간산(HMnO4), 크롬산(H2CrO4), 이산화납(PbO2), 이산화망간(MnO2), 산화구리(CuO) 및 삼염화철(FeCl3)을 포함하는 군에서 선택되는 1 이상인 것을 특징으로 한다.In step (2), the strong acid is at least one selected from the group consisting of fuming sulfuric acid (Oleum, SO 3 gas), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ) and hydrochloric acid (HCl) (H 2 O 2 ), ammonium peroxodisulfate ((NH 4 ) 2 S 2 O 8 ), perchloric acid (HClO 4 ), hypochlorous acid (HClO), permanganic acid (HMnO 4 ), chromic acid (H 2 CrO 4 ) (PbO 2 ), manganese dioxide (MnO 2 ), copper oxide (CuO) and iron trichloride (FeCl 3 ).

상기 (3)단계에서 열처리공정은 500 내지 1200 ℃에서 10 초 내지 10 분간 열처리하는 것을 특징으로 한다.In the step (3), the heat treatment is performed at 500 to 1200 ° C for 10 seconds to 10 minutes.

또한, 본 발명은 상기와 같은 방법으로 제조된 오일흡착용 팽창흑연을 제공한다.
The present invention also provides expanded graphite for oil adsorption produced by the above method.

상기와 같은 본 발명에 따르면, 강산 및 산화제의 혼합용액을 증기로 건식처리하고 상대적으로 낮은 온도에서 열처리함으로써, 제조공정이 간단하고 다량의 강산 및 산화제의 세척 및 산폐기물의 배출을 제어하여 친환경적이며 경제성이 우수한 팽창흑연을 제공하는 효과가 있다. According to the present invention, the manufacturing process is simple and the washing of a large amount of strong acid and oxidizing agent and the discharge of acid waste are controlled by dry treatment of a mixed solution of strong acid and oxidizing agent with steam and heat treatment at a relatively low temperature, There is an effect of providing expandable graphite excellent in economy.

또한, 물과 오일이 공존하는 경우 오일에 대한 선택성이 강하고 빠른 흡수속도를 보이며 오일을 흡수한 후에도 물에 떠 있는 고효율 오일흡착용 팽창흑연을 제공하는 효과가 있다.
In addition, when water and oil coexist, it has an effect of providing a high selectivity to oil and exhibiting a fast absorption rate, and also providing expanded graphite for high-efficiency oil adsorption floating in water even after absorption of oil.

도 1은 본 발명에 따른 팽창흑연의 SEM 사진.
도 2는 본 발명에 따른 팽창흑연의 오일흡착능 그래프.1 is a SEM photograph of expanded graphite according to the present invention.
2 is a graph showing the oil adsorption capacity of expanded graphite according to the present invention.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 (1) 흑연분말을 분쇄하는 단계; (2) 상기 (1)단계에서 분쇄된 흑연분말을 강산 및 산화제가 혼합된 혼합용액의 증기로 건식처리하여 층간삽입흑연분말을 제조하는 단계; 및 (3) 상기 (2)단계에서 제조된 층간삽입흑연분말을 열처리하는 단계;를 포함하는 오일흡착용 팽창흑연의 제조방법을 제공한다.(1) pulverizing graphite powder; (2) drying the graphite powder pulverized in the step (1) by steam of a mixed solution of a mixture of a strong acid and an oxidizer to produce an intercalated graphite powder; And (3) heat treating the intercalated graphite powder prepared in the step (2).

상기 (1)단계에서 분쇄공정은 0.5 내지 15 mm의 지르코니아볼을 이용하여 50 내지 600 rpm의 속도로 5 분 내지 24 시간 동안 볼밀처리하는 것이 바람직하며, 2 내지 10 mm의 지르코니아볼을 이용하여 100 내지 500 rpm의 속도로 10 분 내지 24 시간 동안 볼밀처리하는 것이 최적의 효과를 나타낸다.In the step (1), the ball milling is preferably performed using a zirconia ball having a diameter of 0.5 to 15 mm at a speed of 50 to 600 rpm for 5 to 24 hours, and a ball milling with a zirconia ball having a diameter of 2 to 10 mm To 500 rpm for 10 minutes to 24 hours.

상기 (2)단계에서 강산은 발연황산(Oleum, SO3 gas), 황산(H2SO4), 질산(HNO3) 및 염산(HCl)을 포함하는 군에서 선택되는 1 이상이며, 산화제는 과산화수소(H2O2), 과산화이황산암모늄((NH4)2S2O8), 과염소산(HClO4), 하이포염소산(HClO), 과망간산(HMnO4), 크롬산(H2CrO4), 이산화납(PbO2), 이산화망간(MnO2), 산화구리(CuO) 및 삼염화철(FeCl3)을 포함하는 군에서 선택되는 1 이상인 것이 바람직하다.In step (2), the strong acid is at least one selected from the group consisting of fuming sulfuric acid (Oleum, SO 3 gas), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ) and hydrochloric acid (HCl) (H 2 O 2 ), ammonium peroxodisulfate ((NH 4 ) 2 S 2 O 8 ), perchloric acid (HClO 4 ), hypochlorous acid (HClO), permanganic acid (HMnO 4 ), chromic acid (H 2 CrO 4 ) (PbO 2 ), manganese dioxide (MnO 2 ), copper oxide (CuO) and iron trichloride (FeCl 3 ).

이때, 강산 및 산화제가 담긴 반응조 내부온도는 heating mantle을 이용하여 120 내지 200 ℃를 유지하는 것이 바람직하며, 1 내지 24 시간 동안 강산 및 산화제의 혼합용액으로 증기처리하는 것이 바람직하다.At this time, the internal temperature of the reaction vessel containing the strong acid and the oxidizing agent is preferably maintained at 120 to 200 ° C. by using a heating mantle, and it is preferable to steam treatment with a mixed solution of strong acid and oxidizing agent for 1 to 24 hours.

상기 (3)단계에서 열처리공정은 500 내지 1200 ℃에서 10 초 내지 10 분간 열처리하는 것이 바람직하며, 500 내지 1100 ℃에서 30 초 내지 5 분간 열처리하는 것이 최적의 효과를 나타낸다. In the step (3), the heat treatment is preferably performed at 500 to 1200 ° C for 10 seconds to 10 minutes, and the heat treatment is preferably performed at 500 to 1100 ° C for 30 seconds to 5 minutes.

흑연 층간에 삽입된 산화제, 유기휘발성 물질(분자종)이 고온의 열에너지에 의해 빠르게 기화되어 빠져나옴으로써 흑연의 층간 간격을 팽창시키며 흑연 특유의 층간 구조물을 생성하여 팽창흑연이 제조된다.The oxidizer and organic volatiles (molecular species) inserted between the graphite layers are rapidly vaporized and escaped by the high temperature thermal energy, thereby expanding the interlayer spacing of the graphite and producing the intergranular structure peculiar to the graphite to produce the expanded graphite.

온도가 500 ℃보다 낮을 경우 흑연 층간에 삽입된 분자종의 원활한 이탈이 불가하여 충분한 팽창이 이루어지지 않거나 분자종의 완전한 제거가 어렵고, 1200 ℃보다 높은 경우에는 흑연 구조 자체의 붕괴가 나타나면서 온전한 팽창이 이루어지지 않는 문제가 있다. 또한, 열처리 시간이 30 초보다 적을 경우 분자종의 이탈이 충분히 이루어지지 않아 충분한 팽창이 일어나지 않으며, 5 분보다 많은 경우에는 흑연 자체의 빠른 산화가 이루어지기 때문에 팽창흑연의 수득률이 낮아지는 문제가 있다. If the temperature is lower than 500 ° C, it is impossible to smoothly separate the molecular species inserted between the graphite layers. Thus, it is impossible to sufficiently expand or completely remove the molecular species. When the temperature is higher than 1200 ° C, the graphite structure itself collapses, There is a problem that this is not achieved. Further, when the heat treatment time is less than 30 seconds, the molecular species are not sufficiently removed and sufficient expansion does not occur. When the heat treatment time is more than 5 minutes, the graphite itself is rapidly oxidized and the yield of expanded graphite is lowered .

상기 열처리 과정은 개폐식 머플 퍼니스를 이용하는 것이 바람직하며, 산소와 공기의 유입이 원활한 퍼니스가 바람직하다.It is preferable to use an openable and closable muffle furnace in the heat treatment process, and a furnace in which oxygen and air flow smoothly is preferable.

상기 제조된 팽창흑연은 진공 오븐에서 120 내지 200 ℃에서 24 시간 이상 충분히 건조하여 잔존하는 미반응 유기물을 완전히 제거하는 것이 바람직하다.Preferably, the expanded graphite is sufficiently dried in a vacuum oven at 120 to 200 ° C for at least 24 hours to completely remove remaining unreacted organic materials.

또한, 본 발명은 상기와 같은 방법으로 제조된 오일흡착용 팽창흑연을 제공한다.The present invention also provides expanded graphite for oil adsorption produced by the above method.

상기 오일흡착용 팽창흑연은 부피팽창률이 150 내지 350 mL/g이고, 오일흡착능이 20 내지 55 g/g이다.
The expanded graphite for oil adsorption has a volume expansion rate of 150 to 350 mL / g and an oil adsorption capacity of 20 to 55 g / g.

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

실시예 1.Example 1.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3 (g), 25%) 및 100 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 100℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 700℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of ground graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 100 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 100 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 700 ° C, heat treated for 1 minute, taken out rapidly, and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 2.Example 2.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3 (g), 25%) 및 50 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 100℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 800℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of crushed graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 50 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 100 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 800 ° C and heat treated for 1 minute, then rapidly taken out and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 3.Example 3.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3 (g), 25%) 및 30 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 100℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 900℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of ground graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 30 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 100 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 900 ° C. and heat treated for 1 minute, then rapidly taken out and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 4.Example 4.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3 (g), 25%) 및 100 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 100℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 1000℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of ground graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 100 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 100 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by sufficiently reacting with the oxidizing agent was placed in a muffle furnace prepared at 1000 ° C and heat treated for 1 minute, then taken out rapidly and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 5.Example 5.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3(g), 25%) 및 150 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 100℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 1100℃로 준비된 머플퍼니스에 넣고 30 초간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of ground graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 150 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 100 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 1100 ° C, heat treated for 30 seconds, taken out rapidly, and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 6.Example 6.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 진한황산(H2SO4, 98%) 및 100 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 150℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 700℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Then, 5 g of the crushed graphite powder was filled in a top of a round flask reactor containing a mixed solution of 300 mL of concentrated sulfuric acid (H 2 SO 4 , 98%) and 100 mL of hydrogen peroxide (H 2 O 2 , 30% After that, it was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 150 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 700 ° C, heat treated for 1 minute, taken out rapidly, and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 7.Example 7.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 진한황산(H2SO4, 98%) 및 30 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 150℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 900℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Then, 5 g of the crushed graphite powder was filled in a top of a round flask reactor containing a mixed solution of 300 mL of concentrated sulfuric acid (H 2 SO 4 , 98%) and 30 mL of hydrogen peroxide (H 2 O 2 , 30% After that, it was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 150 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 900 ° C. and heat treated for 1 minute, then rapidly taken out and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

실시예 8.Example 8.

5 g의 흑연분말을 볼밀장치(Planetary ball mill)을 이용하여 건식조건으로 크기 5 mm의 지르코니아볼을 사용하여 300 rpm의 속도로 12 시간동안 처리하여 분쇄흑연분말을 준비하였다. 그 다음, 5 g의 분쇄흑연분말은 300 mL의 발연황산(Oleum, SO3 (g), 25%) 및 100 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 150℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 900℃로 준비된 머플퍼니스에 넣고 1 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was treated with a planetary ball mill under a dry condition at a speed of 300 rpm for 12 hours using a zirconia ball having a size of 5 mm to prepare crushed graphite powder. Next, 5 g of ground graphite powder was mixed with 300 mL of fuming sulfuric acid (Oleum, SO 3 (g), 25%) and a mixed solution of 100 mL of hydrogen peroxide (H 2 O 2 , 30% And the mixture was allowed to stand for 24 hours. At this time, the temperature of the reaction vessel was maintained at 150 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 900 ° C. and heat treated for 1 minute, then rapidly taken out and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

비교예 1.Comparative Example 1

5 g의 흑연분말을 분쇄과정없이 300 mL의 염산(HCl, 36%) 및 100 mL의 과산화수소(H2O2, 30%)의 혼합용액이 담긴 둥근플라스크 반응조의 상부에 채운 후, 24 시간 방치하였다. 이때, 반응조의 온도는 150℃로 유지하여 반응기 내부가 산화제의 증기로 포화되도록 유지하였다. 산화제와 충분히 반응하여 제조된 층간삽입흑연분말은 450℃로 준비된 머플퍼니스에 넣고 12 분간 열처리한 후, 재빠르게 꺼내어 상온에서 냉각시켰다. 상기와 같이 제조된 팽창흑연은 잔존하는 미반응 유기물을 완전히 제거하기 위하여 150℃의 진공오븐에서 24시간 이상 완전 진공 건조하여 제조하였다.
5 g of graphite powder was charged to the top of a round flask reactor containing a mixed solution of 300 mL of hydrochloric acid (HCl, 36%) and 100 mL of hydrogen peroxide (H 2 O 2 , 30%) without pulverization, Respectively. At this time, the temperature of the reaction vessel was maintained at 150 ° C., and the inside of the reactor was kept saturated with the vapor of the oxidizing agent. The intercalated graphite powder prepared by reacting sufficiently with the oxidizing agent was placed in a muffle furnace prepared at 450 ° C and heat treated for 12 minutes, then rapidly taken out and cooled at room temperature. The expanded graphite thus prepared was completely vacuum dried for 24 hours or more in a vacuum oven at 150 ° C to completely remove the remaining unreacted organic matter.

측정예 1. 팽창흑연의 모폴로지 관찰Measurement example 1. Observation of morphology of expanded graphite

주사전자현미경(Hitachi S-4300, Hitachi, Japan)을 통해 제조된 팽창흑연의 표면을 관찰하였다.
The surface of the expanded graphite produced through a scanning electron microscope (Hitachi S-4300, Hitachi, Japan) was observed.

측정예 2. 팽창흑연의 팽창율 측정Measurement example 2. Measurement of expansion coefficient of expanded graphite

팽창흑연의 팽창율은 겉보기 밀도를 이용하여 측정하였으며, 겉보기 밀도는 매스실린더에 팽창흑연을 채우고 초음파로 30 초 동안 일정한 진동을 준 후 부피를 측정하여 계산하였으며, 팽창율은 팽창흑연의 밀도를 원료흑연의 밀도로 나누고 역수를 취하여 구하였다.
The expansion ratio of expanded graphite was measured by using apparent density. The apparent density was calculated by filling the mass cylinder with expanded graphite, measuring the volume after ultrasonic vibration for 30 seconds, and measuring the density. The expansion ratio was calculated by dividing the density of expanded graphite Density and reciprocal were obtained.

측정예 3. 팽창흑연의 오일흡착능 측정Measurement example 3. Measurement of oil adsorption capacity of expanded graphite

팽창흑연의 오일흡착능은 직접 흡착제를 첨가하여 실험하는 방법을 사용하였으며, 비커에 증류수와 오일(n-dodecane)을 첨가하고 팽창흑연을 일정시간 동안 방치하였다. 미흡착된 오일의 제거 및 잔류 수분을 증발시키기 위하여 오일이 흡착된 팽창흑연을 90 ℃의 진공오븐에서 건조하였으며, 건조된 팽창흑연의 무게를 재어 흡착된 오일의 양을 측정하였다.The oil adsorption capacity of expanded graphite was measured by adding an adsorbent directly to the beaker. Distilled water and oil (n-dodecane) were added to the beaker and the expanded graphite was allowed to stand for a certain period of time. In order to remove unadsorbed oil and evaporate residual water, the expanded graphite adsorbed on oil was dried in a 90 ° C vacuum oven, and the amount of adsorbed oil was measured by weighting the dried expanded graphite.

Figure 112013070298600-pat00001
Figure 112013070298600-pat00001

상기 Q는 팽창흑연의 오일흡착량, m0는 팽창흑연의 무게 및 m은 오일을 흡착한 팽창흑연의 무게를 뜻한다.
Q is the amount of oil adsorbed on the expanded graphite, m0 is the weight of the expanded graphite, and m is the weight of the expanded graphite adsorbing the oil.

Figure 112013070298600-pat00002
Figure 112013070298600-pat00002

Figure 112013070298600-pat00003

Figure 112013070298600-pat00003

이상, 본 발명내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시태양일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의해 정의된다고 할 것이다.
Having described specific portions of the present invention in detail, it will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (5)

(1) 흑연분말을 0.5 내지 15 mm의 지르코니아볼을 이용하여 50 내지 600 rpm의 속도로 5 분 내지 24 시간 동안 볼밀처리하여 분쇄하는 단계;
(2) 상기 (1)단계에서 분쇄된 흑연분말을 강산 및 산화제가 혼합된 혼합용액의 반응으로 발생한 증기로 건식처리하여 층간삽입흑연분말을 제조하는 단계;
(3) 상기 (2)단계에서 제조된 층간삽입흑연분말을 열처리하는 단계;를 포함하는 오일흡착용 팽창흑연의 제조방법.(1) milling the graphite powder by ball milling at a speed of 50 to 600 rpm for 5 minutes to 24 hours using zirconia balls of 0.5 to 15 mm;
(2) drying the graphite powder pulverized in the step (1) by steam generated by a reaction of a mixed solution of a strong acid and an oxidizing agent to produce an intercalated graphite powder;
(3) heat-treating the interlayer-intercalated graphite powder produced in the step (2). 삭제delete 제 1항에 있어서,
상기 (2)단계에서 강산은 발연황산(Oleum, SO3 gas), 황산(H2SO4), 질산(HNO3) 및 염산(HCl)을 포함하는 군에서 선택되는 1 이상이며, 산화제는 과산화수소(H2O2), 과산화이황산암모늄((NH4)2S2O8), 과염소산(HClO4), 하이포염소산(HClO), 과망간산(HMnO4), 크롬산(H2CrO4), 이산화납(PbO2), 이산화망간(MnO2), 산화구리(CuO) 및 삼염화철(FeCl3)을 포함하는 군에서 선택되는 1 이상인 것을 특징으로 하는 오일흡착용 팽창흑연의 제조방법.
The method according to claim 1,
In step (2), the strong acid is at least one selected from the group consisting of fuming sulfuric acid (Oleum, SO 3 gas), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ) and hydrochloric acid (HCl) (H 2 O 2 ), ammonium peroxodisulfate ((NH 4 ) 2 S 2 O 8 ), perchloric acid (HClO 4 ), hypochlorous acid (HClO), permanganic acid (HMnO 4 ), chromic acid (H 2 CrO 4 ) (PbO 2 ), manganese dioxide (MnO 2 ), copper oxide (CuO) and iron trichloride (FeCl 3 ).
제 1항에 있어서,
상기 (3)단계에서 열처리공정은 500 내지 1200 ℃에서 10 초 내지 10 분간 열처리하는 것을 특징으로 하는 오일흡착용 팽창흑연의 제조방법.
The method according to claim 1,
Wherein the heat treatment step in the step (3) is a heat treatment at 500 to 1200 占 폚 for 10 seconds to 10 minutes.
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