KR100428809B1 - A preparation method of exfoliated graphite - Google Patents
A preparation method of exfoliated graphite Download PDFInfo
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- KR100428809B1 KR100428809B1 KR10-2001-0032917A KR20010032917A KR100428809B1 KR 100428809 B1 KR100428809 B1 KR 100428809B1 KR 20010032917 A KR20010032917 A KR 20010032917A KR 100428809 B1 KR100428809 B1 KR 100428809B1
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- graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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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
- B01J20/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
본 발명은 팽창흑연의 제조방법에 관한 것으로서, 더욱 상세하게는 발연황산의 제조공정에 팽창흑연의 제조공정을 접목하여 발연황산의 제조공정에서 생성된 기상의 SO3가스 또는 액상의 발연황산을 산화제로 사용하여 흑연 산화물을 제조하고, 상기 흑연 산화물을 세척한 후, 세척된 흑연에 마이크로파를 조사하거나 또는 전기로를 사용하여 열처리하여 팽창흑연을 제조함으로써, 종래에 비해 발연황산의 가열공정이 없어 경제적이며, 사용된 산의 양을 1/10 ∼ 1/100로 줄일 수 있으며, 사용된 산화제를 다시 발연황산 제조공정으로 투입함으로서 대기오염물질인 SO3가스의 대기배출을 막고 산폐기물 발생도 없어 환경오염을 방지할 수 있으며, 팽창흑연 내 잔류하는 황의 농도를 크게 낮춤으로써 휘발성 유기화합물(VOCs) 흡착제, 가스킷, 패킹 시트, 노즐, 복합재료 등을 제조시 금속의 부식문제를 크게 완화시킬 수 있는 팽창흑연의 제조방법에 관한 것이다.The present invention relates to a method for producing expanded graphite, and more particularly, to oxidizing gaseous SO 3 gas or liquid fuming sulfuric acid produced in the production process of fuming sulfuric acid by incorporating the manufacturing process of expanded graphite into the manufacturing process of fuming sulfuric acid. After preparing the graphite oxide, and washing the graphite oxide, irradiated with microwaves or heat treatment using an electric furnace to produce expanded graphite, there is no heating process of fuming sulfuric acid compared to the prior art is economical In addition, the amount of acid used can be reduced from 1/10 to 1/100, and the used oxidant is added back into the fuming sulfuric acid manufacturing process to prevent the release of SO 3 gas, an air pollutant, and no acid waste. Volatile organic compounds (VOCs) adsorbents, gaskets, packing sheets, furnaces by greatly reducing the concentration of sulfur remaining in the expanded graphite The present invention relates to a method for producing expanded graphite that can greatly alleviate the corrosion problem of metals during the production of bladder, composite materials and the like.
Description
본 발명은 팽창흑연의 제조방법에 관한 것으로서, 더욱 상세하게는 발연황산의 제조공정에 팽창흑연의 제조공정을 접목하여 발연황산의 제조공정에서 생성된 기상의 SO3가스 또는 액상의 발연황산을 산화제로 사용하여 흑연 산화물을 제조하고, 상기 흑연 산화물을 세척한 후, 세척된 흑연에 마이크로파를 조사하거나 또는 전기로를 사용하여 열처리하여 팽창흑연을 제조함으로써, 종래에 비해 발연황산의 가열공정이 없어 경제적이며, 사용된 산의 양을 1/10 ∼ 1/100로 줄일 수 있으며, 사용된 산화제를 다시 발연황산 제조공정으로 투입함으로서 대기오염물질인 SO3가스의 대기배출을 막고 산폐기물 발생도 없어 환경오염을 방지할 수 있으며, 팽창흑연 내 잔류하는 황의 농도를 크게 낮춤으로써 휘발성 유기화합물(VOCs) 흡착제, 가스킷, 패킹 시트, 노즐, 복합재료 등을 제조시 금속의 부식문제를 크게 완화시킬 수 있는 팽창흑연의 제조방법에 관한 것이다.The present invention relates to a method for producing expanded graphite, and more particularly, to oxidizing gaseous SO 3 gas or liquid fuming sulfuric acid produced in the production process of fuming sulfuric acid by incorporating the manufacturing process of expanded graphite into the manufacturing process of fuming sulfuric acid. After preparing the graphite oxide, and washing the graphite oxide, irradiated with microwaves or heat treatment using an electric furnace to produce expanded graphite, there is no heating process of fuming sulfuric acid compared to the prior art is economical In addition, the amount of acid used can be reduced from 1/10 to 1/100, and the used oxidant is added back into the fuming sulfuric acid manufacturing process to prevent the release of SO 3 gas, an air pollutant, and no acid waste. Volatile organic compounds (VOCs) adsorbents, gaskets, packing sheets, furnaces by greatly reducing the concentration of sulfur remaining in the expanded graphite The present invention relates to a method for producing expanded graphite that can greatly alleviate the corrosion problem of metals during the production of bladder, composite materials and the like.
흑연은 탄소 원자로 구성되는 6각형 구조가 층을 이루는 독특한 층상 결정구조를 가지고 있다. 이러한 흑연을 적절한 산화제로 처리하면 흑연층 사이에 SO3 2-, NO3 -와 같은 화학종이 도입되어 층간 화합물이 만들어진다. 이러한 층간 화합물이 형성된 흑연을 빠르게 가열하거나 마이크로파를 조사하면 층간에 결합된 화학종이 가스화되고 그 압력에 의해 흑연이 수백배 내지 수천배로 팽창된다. 이와 같이 층간에 삽입 가능한 화학종을 흑연의 층상 결정 구조사이에 삽입시킨 후에 이를 열처리 또는 마이크로파로 처리함으로써 흑연을 팽창시킨다. 이렇게 팽창된 흑연은 0.003 내지 0.02 g/cm3의 밀도를 갖는다. 팽창된 흑연의 c축은 일반 흑연의 c축 보다 20 내지 400배 정도 확장되고, 이러한 팽창 흑연은 흡착제, 가스킷, 패킹 시트 등으로 이용된다.Graphite has a unique layered crystal structure in which a hexagonal structure composed of carbon atoms is layered. Treatment of such graphite with a suitable oxidizing agent introduces chemical species such as SO 3 2- and NO 3 − between the graphite layers to form interlayer compounds. Rapid heating or microwave irradiation of the graphite on which such an interlayer compound is formed gasifies the chemical species bound between the layers and expands the graphite hundreds to thousands of times by the pressure. In this way, the intercalable chemical species is intercalated between the layered crystal structures of the graphite and then treated with heat treatment or microwaves to expand the graphite. This expanded graphite has a density of 0.003 to 0.02 g / cm 3 . The c-axis of expanded graphite is expanded by 20 to 400 times than the c-axis of ordinary graphite, and such expanded graphite is used as an adsorbent, a gasket, a packing sheet, and the like.
일반적인 팽창흑연의 제조방법은 천연 및 열분해 흑연을 황산과 질산, 황산과 과망간산칼륨, 황산과 과산화수소, 황산과 과염소산 등의 혼산을 산화제로 산화 처리한 후 물로 세척하고 건조시킨 다음 급격하게 가열하여 팽창흑연을 제조한다. 상기 방법의 예를 들면, 일본특허공개 소 59-35078호에는 50% 황산과 60% 과염소산을 중량비로 100:5로 섞은 혼합산에 침적시킨 흑연을 1000℃에서 열처리하여 팽창흑연을 제조하는 방법이 개시되어 있다. 일본특허공개 소 61-72609호에는 나트륨과 테트라하이드로퓨란을 이용하여 팽창흑연을 제조하는 방법이 개시되어 있고, 이외에도 일본특허공개 소 62-170332호, 소 63-139081호, 평 3-86538호 및 평 4-21509호에는 황산과 과산화수소, 황산과 질산 및 붕산, 진한 황산과 진한 질산 등의 혼산을 산화제로 사용하여 가스킷용 소재, 시멘트와 모르타르의 복합재료, 팽창흑연 시트 등으로 사용될 수 있는 팽창흑연을 제조하는 방법이 개시되어 있다. 또한 일본특허공개 평 7-136501호, 평 8-143856호 및 미국특허 제 5,149,518호에는 황산을 기본으로 한 혼합산을 산화제로 사용하여 팽창흑연 시트, 유사흡착제 및 무기질 섬유복합재료로 사용될 수 있는 팽창흑연을 제조하는 방법이 개시되어 있다. 미국 특허 제5,503,717호는 수용액상에서 전기화학적으로 ZnCl2가 흑연층간에 스며들도록 한 후 이를 열처리하는 방법으로 팽창흑연을 제조하는 방법이 개시되어 있다.The general method for producing expanded graphite is to oxidize mixed acid such as sulfuric acid and nitric acid, sulfuric acid and potassium permanganate, sulfuric acid and hydrogen peroxide, sulfuric acid and perchloric acid with oxidizing agent, wash with water, dry, and then rapidly heat the expanded graphite. To prepare. For example, Japanese Patent Application Laid-Open No. 59-35078 discloses a method of producing expanded graphite by heat-treating graphite deposited at a mixed acid of 50% sulfuric acid and 60% perchloric acid at a weight ratio of 100: 5 by heat treatment at 1000 ° C. Is disclosed. Japanese Patent Application Laid-Open No. 61-72609 discloses a process for producing expanded graphite using sodium and tetrahydrofuran, in addition to Japanese Patent Laid-Open Nos. 62-170332, 63-139081, H3 3-86538, and Pyeong 4-21509 uses expanded acids such as sulfuric acid and hydrogen peroxide, sulfuric acid and nitric acid and boric acid, concentrated sulfuric acid and concentrated nitric acid as oxidizing agents, and expandable graphite which can be used as gasket material, cement and mortar composite material, expanded graphite sheet, etc. A method of preparing is disclosed. In addition, Japanese Patent Application Laid-Open Nos. 7-136501, 8-143856, and U.S. Patent No. 5,149,518 use expansion acids based on sulfuric acid as oxidizing agents to expand expanded graphite sheets, pseudoadsorbents, and inorganic fiber composites. A method of producing graphite is disclosed. U. S. Patent No. 5,503, 717 discloses a process for producing expanded graphite by electrochemically infiltrating ZnCl 2 between graphite layers and then heat treating it.
상술한 황산을 기본으로 하는 혼합산을 산화제로 사용하여 팽창흑연을 제조하는 경우는 흑연입자를 다량(흑연의 1.5배 이상)의 진한 혼합산 원액 내에서 장시간에 걸쳐 직접 함침시켜 팽창흑연을 제조함으로써 산의 소모량이 대단히 많고 또 다량의 폐산이 발생할 뿐 아니라 이러한 폐산은 단일산이 아닌 여러가지 산 혼합물 또는 산화제로 이루어진 혼합용액이므로 폐산처리가 어려운 문제로 남기 때문에 이러한 팽창흑연 제조방법은 상업화되기 어렵다. 또한 상기 팽창흑연의 제조과정 중에 막대한 SO3및 SO2가스가 발생하여 이들이 환경오염의 원인이 되고, 팽창흑연에 잔류하는 황은 팽창흑연이 패킹, 가스킷 시트 등으로 사용될 경우에 이에 접촉하는 금속을 부식시키는 원인이 되기도 한다.In the case of producing expanded graphite using the above-described mixed acid based sulfuric acid as an oxidizing agent, the expanded graphite is produced by directly impregnating graphite particles in a large amount (more than 1.5 times of graphite) in a concentrated mixed acid stock solution for a long time. The acid consumption is very high and a large amount of waste acid is generated, and since such waste acid is not a single acid but a mixed solution composed of various acid mixtures or oxidizing agents, it is difficult to commercialize such expanded graphite production because waste acid treatment remains difficult. In addition, huge SO 3 and SO 2 gases are generated during the manufacturing process of the expanded graphite, which causes environmental pollution, and sulfur remaining in the expanded graphite corrodes the metal in contact with the expanded graphite when it is used as a packing or a gasket sheet. It can also cause you to.
알칼리 금속과 하이드로퓨란을 이용한 팽창흑연의 제조방법과 ZnCl2을 이용한 전기화학적인 팽창흑연의 제조방법은 상기한 문제점은 없으나, 알카리 금속의 가격이 비싸고 2000 내지 5000 A/㎡의 전류밀도를 갖는 전류를 사용해야 하는 등소요되는 에너지 비용이 크므로 팽창흑연의 제조단가가 상승되는 문제가 있다.The production method of expanded graphite using alkali metal and hydrofuran and the production method of electrochemical expanded graphite using ZnCl 2 do not have the above-mentioned problems, but the price of alkali metal is high and the current density has a current density of 2000 to 5000 A / m 2. There is a problem that the manufacturing cost of the expanded graphite is increased because the required energy cost is large.
이러한 문제점을 개선하기 위하여 본 발명자들이 발명한 대한민국 특허 제254483호에서는 발연황산 혹은 무수황산을 가열하여 발생시킨 SO3가스와 흑연을 건식접촉시켜 팽창흑연을 제조하는 방법을 개발한 바 있다. 상기 방법은 사용되는 발연황산 혹은 무수황산 등의 산의 양을 최소화 할 수 있으며, 황산의 재생 연속 사용에 의한 제조단가를 감소시키면서 폐산의 양을 최소화하여 환경오염 문제를 줄여주고, 팽창흑연 내의 잔류 황의 농도를 크게 감소시키나, 가열공정과 열처리 공정에 있어 사용되는 에너지를 절감시킬 필요가 있다.In order to improve this problem, Korean Patent No. 254483, which was invented by the present inventors, has developed a method of manufacturing expanded graphite by dry contacting SO 3 gas and graphite generated by heating fuming sulfuric acid or sulfuric anhydride. The method can minimize the amount of acid, such as fuming sulfuric acid or sulfuric anhydride used, and minimize the amount of waste acid while reducing the production cost by the continuous use of sulfuric acid to reduce the environmental pollution problem, the residual in the expanded graphite It is necessary to greatly reduce the concentration of sulfur, but to reduce the energy used in the heating process and the heat treatment process.
이에, 본 발명은 종래의 상기와 같은 문제점을 개선하기 위하여 연구 노력한 결과, 발연황산의 제조공정에 팽창흑연의 제조공정을 접목시키며, 산화된 흑연의 팽창시 강한 파장의 마이크로파를 조사하거나 또는 열처리를 실시하는 단일 공정을 적용시켜 본 발명을 완성하였다.Thus, the present invention, as a result of research efforts to improve the problems as described above, as a result of incorporating the manufacturing process of expanded graphite to the manufacturing process of fuming sulfuric acid, irradiating a microwave or heat treatment of a strong wavelength during the expansion of oxidized graphite The present invention was completed by applying a single process to be carried out.
따라서, 본 발명은 발연황산 제조공정에 사용하는 SO3가스 또는 발연황산 제조공정을 통해 제조된 액체 발연황산을 산화제로 사용하여 흑연 산화물을 제조하고, 상기 흑연 산화물을 세척한 뒤 마이크로파를 조사하거나 또는 전기로를 사용하여 열처리하여 팽창흑연을 제조함으로써, 종래에 비해 사용된 산의 양을 최소로 줄일 수 있으며, 사용된 산화제를 다시 발연황산 제조공정으로 투입함으로서 대기오염물질인 SO3가스의 대기배출을 막고, 산폐기물 발생도 없어 환경오염을 방지할 수 있으며, 팽창흑연 내 잔류하는 황의 농도를 크게 낮추며, 발연황산의 가열공정이 없어 사용되는 에너지 비용을 절감시킬 수 있을 뿐만 아니라, 상기 산화된 흑연을 팽창시 강한 파장의 마이크로파를 조사하거나 열처리를 단독 실시함으로써 팽창 흑연의 제조공정을 단축하며, 에너지가 획기적으로 절감된 개선된 팽창흑연의 제조방법을 제공하는데 그 목적이 있다.Accordingly, the present invention is to prepare a graphite oxide using the SO 3 gas or liquid fuming sulfuric acid prepared through the fuming sulfuric acid manufacturing process as an oxidant, washing the graphite oxide and irradiating microwaves or By manufacturing heat-expanded graphite by heat treatment using an electric furnace, the amount of acid used can be reduced to a minimum compared to the conventional one, and by introducing the used oxidant back into the fuming sulfuric acid manufacturing process, air emissions of SO 3 gas, which are air pollutants, can be reduced. It prevents the environmental pollution by preventing the generation of acid wastes, greatly reduces the concentration of sulfur remaining in the expanded graphite, and reduces the energy cost used because there is no heating process of fuming sulfuric acid, as well as the oxidized graphite Process of manufacturing expanded graphite by irradiating microwave of strong wavelength or by performing heat treatment alone when expanding Speed and energy to provide a method for producing an improved dramatically reduce expanded graphite it is an object.
본 발명은 발연황산의 제조공정 중에서 생성된 것으로 농도가 2 ∼ 100%인 기상의 SO3가스 또는 발연황산에 직접 침지하여 흑연을 산화시키는 1 단계; 상기 산화된 흑연을 가성소다액 또는 물유리로 세척하는 2 단계; 상기 세척된 흑연에 30 ∼ 30000 MHz의 마이크로파를 1분 ∼ 1시간 동안 조사하거나 또는 400 ∼ 1200 ℃의 온도범위에서 30초 ∼ 30 분 동안 수행되는 열처리를 하나의 단계만 실시하여 팽창시키는 3 단계; 및 상기 1 단계의 흑연을 산화시키고 잔류한 기상의 SO3가스 또는 액상의 발연황산을 저농도 황산에 흡수시켜 황산으로 회수하여 재투입하는 4 단계로 이루어지는 팽창흑연의 제조방법을 그 특징으로 한다.The present invention is produced during the production of fuming sulfuric acid, the first step of oxidizing the graphite by immersing directly in the gaseous SO 3 gas or fuming sulfuric acid having a concentration of 2 to 100%; Washing the oxidized graphite with caustic soda solution or water glass; Irradiating the washed graphite with a microwave of 30 to 30000 MHz for 1 minute to 1 hour or expanding the heat treated by performing one step for 30 seconds to 30 minutes in a temperature range of 400 to 1200 ° C .; And oxidizing the graphite of step 1, absorbing the remaining gaseous SO 3 gas or liquid fuming sulfuric acid in low concentration sulfuric acid, recovering it as sulfuric acid, and re-injecting the expanded graphite.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 발연황산의 제조공정에 팽창흑연의 제조공정을 접목시켜 인상흑연 입자를 황을 산화시켜 만들어지는 SO3가스와 접촉시키거나 발연황산 내에 직접 침지시켜 흑연층 내에 SO3 2-를 도입시켜 층간 화합물을 만들고, 이렇게 제조된 층간 화합물을 마이크로파 또는 열 처리하여 팽창시켜 팽창흑연을 제조하는 방법에 관한 것이다.The present invention incorporates the manufacturing process of expanded graphite into the manufacturing process of fuming sulfuric acid to contact the impression graphite particles with SO 3 gas produced by oxidizing sulfur or to directly immerse in fuming sulfuric acid to introduce SO 3 2- into the graphite layer. The present invention relates to a method for producing expanded graphite by expanding the prepared interlayer compound by microwave or heat treatment.
본 발명은 발연황산 제조공정에 사용하는 SO3가스 또는 발연황산 제조공정을 통해 제조된 액체 발연황산을 산화제로 사용하여 흑연 산화물을 제조하는 1 단계를포함한다.The present invention includes one step of preparing graphite oxide using SO 3 gas or liquid fuming sulfuric acid prepared through the fuming sulfuric acid manufacturing process as an oxidant.
본 발명의 흑연 산화물을 제조하는 1 단계에서 산화제로 사용되는 SO3가스는 발연황산 제조공정에서 황을 산화시켜 얻은 것으로, SO3가스를 발연황산에 접촉시키기 전의 배관에 천연흑연을 넣은 반응기를 연결하여 흑연 반응기 내에서 흑연과 접촉하여 흑연을 산화시키고 미반응 SO3가스는 발연황산의 제조 공정에 보내어 묽은 황산에 흡수시켜 발연황산의 제조공정에 재사용함으로써 기상의 대기 오염물질의 발생을 원칙적으로 저감시키고 종래의 가열공정을 없앰으로써 비용을 절감시키는 장점이 있다. 상기 SO3가스는 발연황산의 제조공정의 특성에 따라 2 ∼ 100% SO3가스로 발생하며, 2 ∼ 50% SO3가스일 경우에는 1 시간 이상, 51 ∼ 100%일 경우에는 10 분 이상 접촉시켜 흑연을 산화시킨다.The SO 3 gas used as an oxidant in the first step of producing the graphite oxide of the present invention is obtained by oxidizing sulfur in the fuming sulfuric acid manufacturing process, and connecting a reactor in which natural graphite is put into a pipe before the SO 3 gas is contacted with the fuming sulfuric acid. Contact with graphite in the graphite reactor to oxidize the graphite, and send unreacted SO 3 gas to the manufacturing process of fuming sulfuric acid, absorb it in dilute sulfuric acid, and reuse it in the manufacturing process of fuming sulfuric acid to reduce the generation of air pollutants in the gas phase in principle. The cost is reduced by eliminating the conventional heating process. The SO 3 gas is generated as 2 to 100% SO 3 gas according to the characteristics of the manufacturing process of fuming sulfuric acid, and in the case of 2 to 50% SO 3 gas, for 1 hour or more, for 51 to 100%, for 10 minutes or more To oxidize the graphite.
그리고, 본 발명의 흑연 산화물을 제조하는 다른 방법으로는 산화제로 액상 발연황산을 사용하는 방법이다. 사용되는 액상 발연황산은 발연황산 제조공정을 통해 제조된 것으로 천연흑연을 넣은 반응기를 발연황산 제조공정의 말단에 연결하여 발연황산 제조공정을 통해 제조된 발연황산을 흑연 반응기에 넣어 직접 침지시켜 반응시키는 것으로 5분 이상 침지시켜 흑연을 산화시킨다. 산화된 흑연은 글래스 필터(glass filter) 등으로 여과하고 여액인 발연황산은 SO3가스를 주입하여 발연황산을 다시 제조하게 되므로, 액상 폐기물의 발생이 전혀 없고 종래에 비해 발연황산의 양과 반응시간을 단축시킬수 있으며 가열공정이 필요없어 경제적인 장점이 있다.Another method for producing the graphite oxide of the present invention is to use liquid fuming sulfuric acid as the oxidizing agent. The liquid fuming sulfuric acid used is manufactured through the fuming sulfuric acid manufacturing process. The reactor containing natural graphite is connected to the end of the fuming sulfuric acid manufacturing process, and the fuming sulfuric acid produced through the fuming sulfuric acid manufacturing process is directly immersed in the graphite reactor to react. 5 minutes or more to oxidize the graphite. The oxidized graphite is filtered through a glass filter, and the fumed sulfuric acid, the filtrate, is injected into SO 3 gas to produce fumed sulfuric acid again. Therefore, there is no generation of liquid waste, and the amount and reaction time of fumed sulfuric acid are reduced. It can be shortened and there is no economical process because no heating process is required.
따라서, 본 발명에 따른 흑연을 산화시키는 1 단계는 기상의 SO3가스를 이용하는 방법 또는 액상의 발연황산에 침지시키는 방법을 사용할 수 있으며, 두 방법 모두 가열공정이 없고 폐산의 발생이 없는 경제적이고 환경 친화적인 방법이다.Therefore, the first step of oxidizing the graphite according to the present invention may use a method using a gaseous SO 3 gas or a method of immersing it in a liquid fuming sulfuric acid, both methods do not have a heating process and there is no generation of waste acid and economical It's a friendly way.
본 발명은 상기 산화제를 사용하여 산화된 흑연을 제조한 다음, 산화된 흑연을 물, 가성소다액 또는 물유리(Na2SiO3·xH2O) 등의 세척액에 분산시켜 흑연 표면에 붙어있는 미반응 SO3를 제거하는 2 단계를 포함한다. 상기 세척 단계는 흑연입자 표면 또는 층내 삽입된 일부의 SO3를 제거한 후 흑연입자를 여과함으로써 SO3및 H20가 층간 결정 구조내에 함입된 흑연층간화합물을 얻는다. 상기한 세척액 중 물에 분산시 생성된 황산액은 황산 제조공정 또는 발연황산 제조공정에 재사용할 수 있으며, 가성소다액에 분산시에는 망초(Na2SO4)가 생성되어 폐기물의 발생이 없다. 그리고, 물유리에 분산은 열 처리시 물유리가 접착제로 작용하여 팽창흑연 입자들을 뭉치도록 하여 팽창흑연 덩어리를 만드는 특징을 가지므로 기름 흡착제 또는 휘발성 유기화합물 흡착제 등의 특수한 목적을 위해 활용할 수 있다.According to the present invention, an oxidized graphite is prepared using the oxidizing agent, and then the oxidized graphite is dispersed in a washing solution such as water, caustic soda solution or water glass (Na 2 SiO 3 · xH 2 O), and the unreacted adhering to the graphite surface Two steps to remove SO 3 . The washing step removes a part of SO 3 inserted into the surface of the graphite particles or in the layer and then filters the graphite particles to obtain a graphite intercalation compound in which SO 3 and H 2 O are embedded in the interlayer crystal structure. Sulfuric acid produced during the dispersion in water in the washing solution can be reused in the sulfuric acid manufacturing process or fuming sulfuric acid manufacturing process, when dispersed in caustic soda solution is produced without the generation of waste (Na 2 SO 4 ). In addition, the dispersion in the water glass has a characteristic of making the expanded graphite agglomerates by agglomerated the expanded graphite particles by acting as an adhesive during the heat treatment, it can be used for special purposes such as oil adsorbent or volatile organic compound adsorbent.
본 발명은 상기 세척된 흑연을 제조한 다음 마이크로파를 조사하거나 열처리하여 팽창흑연을 제조하는 3 단계를 포함한다.The present invention includes three steps of preparing expanded graphite by preparing the washed graphite and then irradiating or heat-treating microwaves.
상기 마이크로파를 조사하여 팽창흑연을 제조하는 방법은 세척된 흑연을 마이크로파로 1분 이상, 바람직하게는 3 ∼ 10분간 조사하여 급격히 팽창시킴으로써 팽창흑연을 제조한다. 이때, 조사된 마이크로파의 파장은 약 30 ∼ 30000 MHz이고, 출력은 100 ∼ 1000 W인 것이 바람직하다.In the method of producing expanded graphite by irradiation with microwaves, expanded graphite is prepared by rapidly expanding the washed graphite by microwave for 1 minute or more, preferably 3 to 10 minutes. At this time, it is preferable that the wavelength of the irradiated microwave is about 30-30000 MHz, and the output is 100-1000W.
상기 열처리하여 팽창흑연을 제조하는 방법은 세척된 흑연을 400 내지 1,200℃, 바람직하게는 600℃ 이상의 온도에서 열처리하여 팽창흑연을 제조한다. 열처리시간은 30초 ∼ 10분, 바람직하게는 1분 ∼ 10분이 좋다.마지막으로, 본 발명은 상기 1 단계의 흑연을 산화시키고 잔류한 기상의 SO3가스 또는 액상의 발연황산을 저농도 황산에 흡수시켜 황산으로 회수하여 재투입하는 4 단계로 이루어진다.In the method for producing expanded graphite by heat treatment, the expanded graphite is heat-treated at 400 to 1,200 ° C., preferably at a temperature of 600 ° C. or more to produce expanded graphite. The heat treatment time is 30 seconds to 10 minutes, preferably 1 minute to 10 minutes. Finally, the present invention oxidizes the graphite of the first step and absorbs the remaining gaseous SO 3 gas or liquid fuming sulfuric acid in low concentration sulfuric acid. It is made up of four steps to recover the sulfuric acid.
이와같은 본 발명에 따른 팽창흑연의 제조방법은 가열공정이 없고 산화제로 단일산을 사용함으로써 혼산을 사용하는 종래방법에 비해 1/10 ∼ 1/100로 소량 사용 할 뿐만 아니라 미반응 SO3가스를 발연황산 제조공정에 재투입함으로서 대기오염물질의 발생 및 폐혼산의 발생을 원천적으로 없앰으로서 경제적이고 환경친화적인 방법으로, 제조된 팽창흑연은 0.003 내지 0.02ｇ/㎤의 밀도를 갖고 1ｇ당 10 내지 100ｇ의 유류를 흡착하는 특성을 가질 뿐만 아니라 VOCs를 효율적으로 흡착하는 특성을 갖는다. 따라서, 상기 본 발명에 따른 팽창흑연의 제조방법을 통해 제조된 팽창흑연은 유류 흡착제, 휘발성 유기물 흡착제, 내열 시트 등에 유용하게 사용될 수 있으며, 본 발명은 이들을 포함한다.Such a method for producing expanded graphite according to the present invention has no heating step and uses a small amount of 1/10 to 1/100 as compared to the conventional method using mixed acid by using a single acid as an oxidant, as well as using unreacted SO 3 gas. By re-inserting into the fuming sulfuric acid manufacturing process, by eliminating the generation of air pollutants and the generation of waste mixed acid in an economical and environmentally friendly way, the expanded graphite produced has a density of 0.003 to 0.02 g / cm 3 and 10 to 1 g per Not only does it have the property of adsorbing 100 g of oil, it also has the property of efficiently adsorbing VOCs. Therefore, the expanded graphite prepared by the method for producing expanded graphite according to the present invention may be usefully used in oil adsorbents, volatile organic adsorbents, heat resistant sheets, and the like, and the present invention includes them.
또한, 본 발명은 상기 본 발명에 따른 팽창흑연의 제조방법 1 단계에 의해 얻은 흑연을 산화시킨 층간 흑연을 포함한다.In addition, the present invention includes an interlayer graphite obtained by oxidizing the graphite obtained by step 1 of the method for producing expanded graphite according to the present invention.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
실시예 1Example 1
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서 SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 7%의 SO3가스를 3시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 물을 이용하여 세척, 여과함으로서 천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 5분간 2450MHz의 파장 및 700W의 출력으로 마이크로파를 조사하여 급격하게 팽창시켰다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of a 7% SO 3 The gas was passed through for 3 hours to oxidize the interlayers of natural graphite with SO 3 . The oxidized natural graphite was washed with water and filtered to remove excess SO 3 condensed on the surface of the natural graphite, and rapidly expanded by irradiating microwaves at a wavelength of 2450 MHz and an output of 700 W for 5 minutes. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 2Example 2
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서 SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 100%의 SO3가스를 1시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 물을 이용하여 세척, 여과함으로서천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 5분간 2450MHz의 파장 및 700W의 출력으로 마이크로파를 조사하여 급격하게 팽창시켰다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of 100% SO 3 Gas was passed for 1 hour to oxidize the interlayer of natural graphite to SO 3 . The oxidized natural graphite was washed with water and filtered to remove SO 3 condensed in excess on the surface of the natural graphite, and rapidly expanded by irradiating microwaves at a wavelength of 2450 MHz and an output of 700 W for 5 minutes. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 3Example 3
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정의 말단에 천연흑연 1kg이 들어있는 반응기를 설치하여 이 반응기에 상기 제조된 액체 발연황산 1kg을 넣어 교반한 후 상온에서 3시간 방치하여 천연흑연의 층간을 SO3로 산화시켰다. 이를 물로 세척하고 여과한 5분간 2450MHz의 파장 및 700W의 출력에서 마이크로파를 조사하여 급격하게 팽창시켰다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.A reactor containing 1 kg of natural graphite was installed at the end of the process for producing fuming sulfuric acid using SO 3 gas generated by oxidizing sulfur, and the mixture was stirred at room temperature for 3 hours after adding 1 kg of the liquid fuming sulfuric acid prepared above. The interlayer of natural graphite was oxidized to SO 3 . It was washed with water and filtered for 5 minutes at a wavelength of 2450 MHz and a power of 700 W to expand rapidly. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 4Example 4
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서 SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 7%의 SO3가스를 3시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 물을 이용하여 세척, 여과함으로서 천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 이를 반응로내에서 900℃에서 1분간 급격하게 열처리하였다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of a 7% SO 3 The gas was passed through for 3 hours to oxidize the interlayers of natural graphite with SO 3 . The oxidized natural graphite was washed with water and filtered to remove SO 3 condensed excessively on the surface of the natural graphite, which was then rapidly heat treated at 900 ° C. for 1 minute. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 5Example 5
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서 SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 100%의 SO3가스를 1시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 물을 이용하여 세척, 여과함으로서 천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 이를 반응로내에서 900℃에서 1분간 급격하게 열처리하였다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of 100% SO 3 Gas was passed for 1 hour to oxidize the interlayer of natural graphite to SO 3 . The oxidized natural graphite was washed with water and filtered to remove SO 3 condensed excessively on the surface of the natural graphite, which was then rapidly heat treated at 900 ° C. for 1 minute. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 6Example 6
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정의 말단에 천연흑연 1kg이 들어있는 반응기를 설치하여 이 반응기에 상기 제조된 액체 발연황산 1kg을 넣어 교반한 후 상온에서 3시간 방치하여 천연흑연의 층간을 SO3로 산화시켰다. 이를 물로 세척하고 여과한 흑연을 반응로내에서 900℃에서 1분간 급격하게 열처리하였다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.A reactor containing 1 kg of natural graphite was installed at the end of the process for producing fuming sulfuric acid using SO 3 gas generated by oxidizing sulfur, and the mixture was stirred at room temperature for 3 hours after adding 1 kg of the liquid fuming sulfuric acid prepared above. The interlayer of natural graphite was oxidized to SO 3 . This was washed with water and the filtered graphite was heat treated rapidly at 900 ° C. for 1 minute in a reactor. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 7Example 7
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서 SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 100%의 SO3가스를 1시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 0.1M NaOH 수용액을 이용하여 세척, 여과함으로서 천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 이를 반응로내에서 900℃에서 1분간 급격하게 열처리하였다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of 100% SO 3 Gas was passed for 1 hour to oxidize the interlayer of natural graphite to SO 3 . The oxidized natural graphite was washed with 0.1 M NaOH aqueous solution and filtered to remove SO 3 that was excessively condensed on the surface of the natural graphite, which was rapidly heat treated at 900 ° C. for 1 minute in a reactor. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
실시예 8Example 8
유황을 산화시켜 발생한 SO3가스를 사용하여 발연황산을 제조하는 공정에서SO3가스를 황산에 투입하여 발연황산을 제조하기 직전에 천연흑연 5kg이 들어있는 반응기를 설치하여 반응기에 100%의 SO3가스를 1시간동안 통과시켜 천연흑연의 층간을 SO3로 산화시켰다. 산화된 천연흑연을 1% 물유리 수용액을 이용하여 세척, 여과함으로서 천연흑연의 표면에 과량으로 응축된 SO3를 제거하였고 이를 반응로내에서 900℃에서 1분간 급격하게 열처리하였다. 이렇게 제조한 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.In the reactor by installing a reactor that contains a natural graphite 5kg just prior to the production of fuming sulfuric acid charged into the SO 3 gas in sulfuric acid in the process of producing the fuming sulfuric acid with the SO 3 gas generated by oxidizing the sulfur of 100% SO 3 Gas was passed for 1 hour to oxidize the interlayer of natural graphite to SO 3 . The oxidized natural graphite was washed with 1% water glass aqueous solution and filtered to remove SO 3 that was excessively condensed on the surface of the natural graphite, which was then rapidly heat treated at 900 ° C. for 1 minute. The density of the expanded graphite thus prepared, the amount of residual sulfur, and the amount of bunker C oil adsorbed per g were measured by piconometer, and the results are shown in Table 1 below.
비교예 1 ∼ 2Comparative Examples 1-2
종래의 통상적인 방법인 혼산(황산과 질산)을 이용하여 팽창흑연을 제조하였으며, 제조된 팽창흑연의 밀도와 잔류황의 량, g당 벙커C유 흡착량을 피코노메터로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.Expanded graphite was prepared by using a conventional method of mixed acid (sulfuric acid and nitric acid), and the density of the expanded graphite, the amount of residual sulfur, and the adsorption amount of bunker C oil per gram were measured by piconometer. It is shown in Table 1 below.
상기 표 1에 나타난 바와 같이, 본 발명의 실시예 1 ∼ 8은 비교예 1 ∼ 2에 비해 잔류황의 량이 약 1/4 ∼ 1/10 정도로 감소하였고, 팽창흑연 1g 당 60 ∼ 70 g의 벙커C유를 흡착하므로 우수한 흡착성을 가짐을 확인할 수 있었다.As shown in Table 1, Examples 1 to 8 of the present invention reduced the amount of residual sulfur by about 1/4 to 1/10 compared to Comparative Examples 1 to 2, 60 to 70 g of bunker C per 1 g of expanded graphite As it adsorbed oil, it could be confirmed that it had excellent adsorptivity.
상술한 바와 같이, 본 발명에 따른 팽창흑연의 제조방법은 발연황산의 제조공정에 팽창흑연의 제조공정을 접목시켜 산화제로 발연황산의 제조공정에서 생성된 기상의 SO3가스 또는 액상의 발연황산을 사용함으로써 산의 양을 기존 방법에 비해1/10 ∼ 1/100로 줄일 수 있을 뿐만 아니라, 산폐기물이 거의 배출되지 않으며, 팽창흑연내에 잔류하는 황의 함량을 1/4 ∼ 1/10로 줄일 수 있으며, 가열공정이 없어 경제적인 장점이 있다. 따라서, 본 발명의 방법에 따른 팽창흑연은 유류흡착제, 가스킷, 패킹 시트 등과 같은 팽창흑연의 응용과 관련된 산업분야의 유용하게 사용할 수 있다.As described above, the method for producing expanded graphite according to the present invention combines the production process of expanded graphite with the production process of fuming sulfuric acid to produce gaseous SO 3 gas or liquid fuming sulfuric acid produced in the production process of fuming sulfuric acid as an oxidizing agent. By using this, the amount of acid can be reduced to 1/10 to 1/100 compared to the existing method, and almost no acid waste is emitted, and the content of sulfur remaining in the expanded graphite can be reduced to 1/4 to 1/10. There is no heating process, and there is an economic advantage. Therefore, the expanded graphite according to the method of the present invention can be usefully used in the industrial field related to the application of expanded graphite such as oil adsorbents, gaskets, packing sheets, and the like.
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| JP2001306283A JP3761438B2 (en) | 2001-06-12 | 2001-10-02 | Method for producing expanded graphite |
| DE10150220A DE10150220A1 (en) | 2001-06-12 | 2001-10-12 | Production of expanded graphite, useful as adsorbent for oils and volatile organic compounds, comprises contacting graphite with sulfur trioxide produced by oxidizing sulfur |
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| GB0720429D0 (en) | 2007-10-18 | 2007-11-28 | Electroclean Technology Ltd | Treatment of contaminated gases |
| CN101450797B (en) * | 2007-11-29 | 2013-05-08 | 索尼株式会社 | Method for processing carbon nanotube, carbon nanotube and carbon nanotube element |
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| CN104495803A (en) * | 2014-11-27 | 2015-04-08 | 林前锋 | Purification method of natural microcrystalline graphite |
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| CN105460924A (en) * | 2015-12-25 | 2016-04-06 | 中国人民解放军后勤工程学院 | Preparation method of sulfur-free nano graphite |
| JP2020041044A (en) * | 2018-09-10 | 2020-03-19 | 積水化学工業株式会社 | Fire-resistant resin composition and molding |
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| JPH06144814A (en) * | 1992-10-30 | 1994-05-24 | Nippon Kokuen Kogyo Kk | Production of acid-treated graphite |
| JPH10330108A (en) * | 1997-05-30 | 1998-12-15 | Nippon Kasei Chem Co Ltd | Thermally expandable graphite |
| KR19990065389A (en) * | 1998-01-13 | 1999-08-05 | 최상원 | Expanded Graphite Manufacturing Method |
| JP2001048514A (en) * | 1999-07-29 | 2001-02-20 | Korea Inst Of Mach & Materials | Production of expanded graphite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06144814A (en) * | 1992-10-30 | 1994-05-24 | Nippon Kokuen Kogyo Kk | Production of acid-treated graphite |
| JPH10330108A (en) * | 1997-05-30 | 1998-12-15 | Nippon Kasei Chem Co Ltd | Thermally expandable graphite |
| KR19990065389A (en) * | 1998-01-13 | 1999-08-05 | 최상원 | Expanded Graphite Manufacturing Method |
| JP2001048514A (en) * | 1999-07-29 | 2001-02-20 | Korea Inst Of Mach & Materials | Production of expanded graphite |
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