WO2014077559A1 - Method for manufacturing graphite oxide - Google Patents

Method for manufacturing graphite oxide Download PDF

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WO2014077559A1
WO2014077559A1 PCT/KR2013/010222 KR2013010222W WO2014077559A1 WO 2014077559 A1 WO2014077559 A1 WO 2014077559A1 KR 2013010222 W KR2013010222 W KR 2013010222W WO 2014077559 A1 WO2014077559 A1 WO 2014077559A1
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graphite
weight
parts
graphite oxide
slurry
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PCT/KR2013/010222
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French (fr)
Korean (ko)
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홍상진
엄성훈
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주식회사 아이디티인터내셔널
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Publication of WO2014077559A1 publication Critical patent/WO2014077559A1/en

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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
    • C01B32/23—Oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/60—Mixing solids with solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/50—Zeolites wherein inorganic bases or salts occlude channels in the lattice framework, e.g. sodalite, cancrinite, nosean, hauynite

Definitions

  • the present application relates to a method for producing graphite oxide, including removing residual metal ions contained in graphite oxide using a zeolite.
  • Graphene is a recently discovered two-dimensional carbon nanostructure, a hexagonal crystal lattice in the form of a single-plate structure consisting of sp 2 hybrids of carbon atoms.
  • the graphene has the same shape as that in which hexagonal crystal lattice is stacked in a layered structure and the interlayer separation is completely completed in the graphite having a laminated structure.
  • Graphene oxide an intermediate of graphene that is produced during the production of graphene, is added to the graphite powder by adding nitric acid and potassium perchlorate and reacting for several days to produce graphite oxide, the Stadenmaier method, the Brodie method, and The Hummer method is known.
  • Korean Patent No. 1095584 discloses a method for cleaning graphite oxide using an organic solvent.
  • the concentration of the other ions contained in the graphite oxide is difficult to maintain 1,000 ppm or less in the case of K + ions and 100 ppm or more in the case of Mn 2+ ions even after such a series of processes. Additional problems may arise in the formation and synthesis of composites using graphene.
  • This application can provide the manufacturing method of the graphite oxide which can remove the residual metal ion contained in graphite oxide efficiently by using zeolite in the manufacturing process of graphite oxide.
  • a first aspect of the present disclosure includes the steps of oxidizing the graphite in a graphite slurry comprising graphite, an alkali metal salt, and a solvent; Separating graphite oxide from the graphite slurry; And removing the residual metal ions contained in the graphite oxide by mixing and / or stirring the graphite oxide and the zeolite.
  • the present invention during the production of graphite oxide inevitably remove the metal ions and other impurities contained in the graphite oxide without going through a multi-step washing process to produce high quality graphite oxide with high efficiency, Can be provided.
  • the production method of the graphite oxide of the present invention it is economical and efficient to process residual metal ions and other impurities that are difficult to remove by a simple method, and it is possible to minimize impurities when synthesizing a polymer or organic chemical product using graphene.
  • the zeolite used for washing the graphite oxide during the production of the graphite oxide of the present application is economical because it can be recovered and reused.
  • FIG. 1 is a flow chart showing a process for producing graphite oxide according to an embodiment of the present application.
  • the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.
  • a and / or B means “A or B, or A and B.”
  • a first aspect of the present disclosure includes the steps of oxidizing the graphite in a graphite slurry comprising graphite, an alkali metal salt, and a solvent; Separating graphite oxide from the graphite slurry; And removing the residual metal ions contained in the graphite oxide by mixing and / or stirring the graphite oxide and the zeolite.
  • the graphite oxide may include oxidized graphite, but is not limited thereto.
  • the first mixture and the second mixture are mixed to Graphite slurry can be prepared, but is not limited thereto.
  • the graphite slurry is about 0 ° C to about 50 ° C, about 10 ° C to about 50 ° C, about 20 ° C to about 50 ° C, and about 30 ° C to About 50 ° C., about 40 ° C. to about 50 ° C., about 0 ° C. to about 40 ° C., about 0 ° C.
  • the step of oxidizing the graphite in the graphite slurry comprising the graphite, the alkali metal salt, and the solvent may be about 10 hours or less, for example, about 1 minute to about 10 hours, about 5 minutes.
  • the step of oxidizing the graphite in the graphite slurry including the graphite, the alkali metal salt, and the solvent may include a cooling facility to maintain the temperature of the graphite slurry in a predetermined range. It may be to be performed in the heat exchanger is provided, but is not limited thereto.
  • the step of oxidizing the graphite in the graphite slurry containing the graphite, an alkali metal salt, and a solvent and separating the graphite oxide from the graphite slurry is usually in the art It is performed by the method of manufacturing graphite oxide including the Stadenmaier method, the Brodie method, the Hummer method, or an application thereof which can be easily acquired and performed by a person with knowledge of May be, but is not limited thereto.
  • the zeolite in the step of mixing and / or stirring the graphite oxide and the zeolite to remove residual metal ions contained in the graphite oxide, is about 10% by weight or less of the graphite oxide, eg For example, about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 5 wt% to about 10 Wt%, about 7 wt% to about 10 wt%, about 0.1 wt% to about 7 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1
  • the graphite oxide may be included in the ratio of about 1% by weight, about 0.1% by weight to about 0.5% by weight, or about 1% by weight to about 5% by weight, but is not
  • the method of preparing the graphite oxide may further include a vacuum drying step, but is not limited thereto.
  • the reduced pressure drying may be about 0 ° C. to about 200 ° C., about 20 ° C. to about 100 ° C., about 40 ° C. to about 100 ° C., about 50 ° C. to about 100 ° C., about 60 ° C. to about 100 ° C., and about 0 ° C.
  • the reduced pressure drying is about 48 hours or less, for example, about 1 minute to about 48 hours, about 1 hour to about 48 hours, about 5 hours to about 48 hours, about 10 hours to about 48 hours, about 20 hours to about 48 hours, about 30 hours to about 48 hours, about 40 hours to about 48 hours, about 1 hour to about 40 hours, about 1 hour to about 30 hours, about 1 hour to about 20 hours , About 1 hour to about 10 hours, or about 1 hour to about 5 hours, but is not limited thereto.
  • the agitation is about 240 hours or less, for example, about 1 hour to about 240 hours, about 1 hour to about 200 hours, about 1 hour to about 150 hours, about 1 hour to about 100 Hour, about 1 hour to about 50 hours, about 1 hour to about 20 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 240 hours, about 10 hours to about 240 hours, About 20 hours to about 240 hours, about 50 hours to about 240 hours, about 100 hours to about 240 hours, about 150 hours to about 240 hours, or about 200 hours to about 240 hours, but is not limited thereto. It is not.
  • the zeolite is selected from the group consisting of natural zeolite, synthetic zeolite, LSX zeolite (low silica zeolite), ZSM zeolite, zeolite X, zeolite Y, zeolite L, zeolite A, and combinations thereof It may include, but is not limited to.
  • the solvent may include nitric acid, sulfuric acid, hydrochloric acid, or a mixture thereof, but is not limited thereto.
  • the nitric acid may include fuming nitric acid
  • the sulfuric acid may include fuming sulfuric acid, but is not limited thereto.
  • the solvent may include, but is not limited to, concentrated nitric acid, concentrated sulfuric acid, or a mixture thereof.
  • the solvent may include, but is not limited to, nitric acid, sulfuric acid, or about 90 wt% or more of nitric acid and sulfuric acid.
  • the solvent may comprise at least about 90 wt%, at least about 91 wt%, at least about 92 wt%, at least about 93 wt%, at least about 94 wt%, about 95 wt% of the nitric acid, sulfuric acid, or nitric acid and sulfuric acid. It may include, but is not limited to, at least about 100 wt%, at least about 96 wt%, at least about 97 wt%, at least about 98 wt%, at least about 99 wt%, or about 100 wt%.
  • the alkali metal salt is selected from the group consisting of potassium chlorate, potassium permanganate, sodium nitrate, lithium hypochlorite, lithium perchlorate, lithium manganate, lithium nitrate, cesium nitrate and combinations thereof It may be included, but is not limited thereto.
  • the alkali metal salt in a powder state may be dissolved in the solvent, but is not limited thereto.
  • the graphite slurry may include, but is not limited to, about 10 parts by weight to about 100 parts by weight of the solvent based on about 1 part by weight of the graphite.
  • the graphite slurry may include about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, about 30 parts by weight to about 100 parts by weight, based on about 1 part by weight of the graphite, About 40 to about 100 parts by weight, about 50 to about 100 parts by weight, about 60 to about 100 parts by weight, about 70 to about 100 parts by weight, about 80 to about 100 parts by weight, About 90 parts by weight to about 100 parts by weight, about 10 parts by weight to about 90 parts by weight, about 10 parts by weight to about 80 parts by weight, about 10 parts by weight to about 70 parts by weight, about 10 parts by weight to about 60 parts by weight, About 10 parts by weight to about 50 parts by weight, about 10 parts by weight to about 40 parts by weight, about 10 parts by weight to about 30 parts by weight
  • the viscosity of the graphite slurry is too high may not be smooth transfer and mixing of the reactants including the graphite slurry during graphite oxide production.
  • the solvent is contained in an amount of about 100 parts by weight based on about 1 part by weight of the graphite, the reaction efficiency for the production of graphite oxide is low and a lot of waste solvent by-products are generated.
  • the graphite slurry may include about 10 parts by weight to about 100 parts by weight of the solvent, based on about 2 parts by weight of the alkali metal salt, but is not limited thereto.
  • the graphite slurry may contain about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, and about 30 parts by weight to about 100 parts by weight of the solvent, based on about 1 part by weight of the alkali metal salt.
  • the graphite slurry may include about 0.2 parts by weight to about 20 parts by weight of the alkali metal salt based on about 1 part by weight of the graphite, but is not limited thereto.
  • the graphite slurry may contain about 0.2 parts by weight to about 20 parts by weight, about 0.5 parts by weight to about 20 parts by weight, and about 1 part by weight to about 20 parts by weight of the alkali metal salt based on about 1 part by weight of the graphite.
  • the graphite may be in powder form, but is not limited thereto.
  • the powder of graphite may include one having a diameter of about 200 ⁇ m or less, but is not limited thereto.
  • the powder of graphite has a diameter of about 1 ⁇ m to about 200 ⁇ m, about 5 ⁇ m to about 200 ⁇ m, about 10 ⁇ m to about 200 ⁇ m, about 50 ⁇ m to about 200 ⁇ m, about 100 ⁇ m to about 200 ⁇ m
  • the particle size is so low that the expansion effect according to the weight density is low, and thus graphene is not easily formed by peeling.
  • the particle size is more than 200 ⁇ m, the particle size is too large to facilitate the conveyance and mixing of the reactants.
  • the step of oxidizing the graphite in the graphite slurry may further include adding a hydrogen peroxide aqueous solution to the graphite slurry, but is not limited thereto.
  • the aqueous hydrogen peroxide solution may terminate the oxidation reaction of graphite by reducing the alkali metal salt included in the graphite slurry to oxidize the graphite, but is not limited thereto.
  • the hydrogen peroxide aqueous solution may contain about 30 wt% or less of hydrogen peroxide, for example, about 1 wt% to about 30 wt%, about 2 wt% to about 30 wt%, about 5 wt% to about 30 wt%, about 7 wt% to about 30 wt%, about 10 wt% to about 30 wt%, about 20 wt% to about 30 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 2 wt%, or about 2 wt% to about 7 wt% It is not limited to this.
  • about 100 parts by weight of the aqueous hydrogen peroxide solution for example, about 10 parts by weight to about 100 parts by weight, about 30 parts by weight to about 100 parts by weight, based on about 1 part by weight of the graphite
  • the aqueous hydrogen peroxide solution is less than about 10 parts by weight with respect to about 1 part by weight of the graphite slurry, the oxidation reaction of the graphite is not completely terminated, and when the aqueous hydrogen peroxide solution is greater than about 100 parts by weight, washing of the prepared graphite oxide And the drying process is expensive.
  • the graphite slurry after adding the aqueous hydrogen peroxide solution to the graphite slurry, about 1 hour or less, for example, about 1 minute to about 1 hour, about 1 minute to about 40 minutes, about 1 minute to about
  • the graphite slurry can be maintained for 20 minutes, about 10 minutes to about 1 hour, or about 30 minutes to about 1 hour, but is not limited thereto.
  • the method for producing graphite oxide the internal temperature can be maintained in a certain temperature range, mixing the graphite powder and sulfuric acid at the beginning of the channel having a start, a reaction part and an outlet Introducing a graphite slurry obtained by the; Injecting and mixing the KMnO 4 sulfuric acid solution obtained by mixing potassium permanganate (KMnO 4 ) powder and sulfuric acid at the beginning of the channel; Maintaining a mixture of the graphite slurry and the KMnO 4 sulfuric acid solution in the channel at a predetermined temperature range; And it may be prepared by the step comprising the step of introducing an aqueous hydrogen peroxide solution near the outlet of the channel, but is not limited thereto.
  • the KMnO 4 sulfuric acid solution may be easily mixed by adding potassium permanganate to the channel in the form of a sulfuric acid solution, and the KMnO 4 sulfuric acid solution may be supplied by a metering pump connected to the reaction part of the channel.
  • the amount of the KMnO 4 sulfuric acid solution supplied may be strictly controlled by a quantitative method or the like.
  • the channel must be tightly controlled, in particular within the appropriate temperature range, to prevent explosion due to local overheating.
  • the channel has an inner diameter of about 50 mm or less, for example, about 1 ⁇ m to about 50 mm, about 10 ⁇ m to about 50 mm, about 50 ⁇ m to about 50 mm, about 100 ⁇ m to About 50 mm, about 500 ⁇ m to about 50 mm, about 1 mm to about 50 mm, about 10 mm to about 50 mm, about 1 ⁇ m to about 10 mm, about 1 ⁇ m to about 1 mm, about 1 ⁇ m to about 500 ⁇ m, about 1 ⁇ m to about 100 ⁇ m, about 1 ⁇ m to about 50 ⁇ m, or about 1 ⁇ m to about 10 ⁇ m or less, but is not limited thereto.
  • the channel may include, but is not limited to, a tubular reactor having one or more of excellent thermal conductivity, corrosion resistance, and acid resistance.
  • the channel should be able to maintain the reaction mixture preferably at 20 ° C. to 35 ° C. to prevent explosion due to local overheating, and for reaction efficiency and safety, the inner diameter is several tens of mm or less, preferably the inner diameter is about 1 ⁇ m to It should be 1 mm.
  • the reaction mixture may move in the channel at a speed of several cm to several m per second, preferably several cm to several tens of cm per second, but is not limited thereto.
  • the graphite slurry, the KMnO 4 sulfuric acid solution, and the aqueous hydrogen peroxide solution may be supplied to the channel by a metering pump, respectively.
  • the graphite slurry and the KMnO 4 sulfuric acid solution may be supplied to the channel at a sufficient pressure and / or speed by the metering pump so that the reaction mixture forms a vortex in the channel.
  • the excess KMnO 4 contained in the graphite slurry is reduced, whereby the reaction mixture in which the reaction is terminated may be discharged to the outlet of the reactor.
  • the reaction mixture in which the reaction discharged to the reactor outlet is terminated may be washed by treating the cationic surfactant solution including the quaternary ammonium salt before drying, but is not limited thereto.
  • the graphite oxide may further include the step of washing with a surfactant solution, but is not limited thereto.
  • the surfactant may include a cationic surfactant including a quaternary ammonium salt, but is not limited thereto.
  • the graphite oxide by removing the zeolite using a sieve may be to include a further step to obtain, but is not limited thereto.
  • the zeolite may further include recovering after removing the zeolite, but is not limited thereto.
  • the recovered zeolite may be used in the step of removing residual metal ions contained in other graphite oxide, but is not limited thereto.
  • the prepared graphite slurry was then mixed with water through a liquid metering pump, and the temperature at the time of mixing was operated at a relatively low temperature of 0 ° C to 35 ° C. Subsequently, hydrogen peroxide was introduced through the metering pump to finally terminate the oxidation reaction.
  • the reaction mixture discharged from the outlet of the hydrogen peroxide mixing tank was then filtered to remove acid and unreacted oxidant, and 10 g of zeolite (Synthetic, A-4, Beads, 8-12 mesh, Wako) was added to 100 g of the resulting graphite oxide cake. Was added and stirred and mixed slowly for 1 to 2 days. Thereafter, the graphite oxide was separated using a sieve to terminate the washing. Graphite oxide was dried under reduced pressure within 48 hours at about 60 ° C. or less after passing through the washing process as described above.
  • zeolite Synthetic, A-4, Beads, 8-12 mesh, Wako
  • the residual metal ion concentration of the prepared graphite oxide was measured and compared by using an inorganic element analysis (ICP) method.
  • ICP inorganic element analysis
  • Table 1 The residual metal ion concentrations of the graphite oxide from which residual metal ions were removed by the conventional filter press method and the centrifugal separation method, and the graphite oxide from which residual metal ions were removed using zeolite are shown in Table 1 below.
  • ICP-AES iCAP-6000 SERIES, Thermo electron
  • Samples were taken using a Teflon vessel of at least 0.1 g with a first dilution of 25 mL and a second dilution of 50 mL.
  • the residual metal ion concentration of the graphite oxide from which residual metal ions were removed using zeolite was significantly lower than that of the graphite oxide from which residual metal ions were removed by a filter press method or a centrifugation method.
  • the graphite oxide prepared by the method of producing graphite oxide of the present application including zeolite treatment is graphite oxide of good quality having a significantly lower residual metal ion concentration than the graphite oxide prepared by the conventional method.

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Abstract

Disclosed is a method for manufacturing graphite oxide including the processing step of removing residual metal ions contained in the graphite oxide by using zeolite.

Description

산화흑연의 제조방법Manufacturing method of graphite oxide
본원은, 제올라이트를 이용하여 산화흑연에 포함된 잔류 금속 이온을 제거하는 것을 포함하는, 산화흑연(graphite oxide)의 제조방법에 관한 것이다.The present application relates to a method for producing graphite oxide, including removing residual metal ions contained in graphite oxide using a zeolite.
그래핀(Graphene)은 최근에 발견된 2 차원의 탄소 나노구조로, 탄소 원자가 sp2 혼성결합으로 이루어진 단일 평판구조의 육각형 결정격자 형태의 물질이다. 상기 그래핀은 육각형 결정격자가 층상 구조로 쌓여 적층 구조를 띤 흑연에서 층간 분리가 완전하게 이루어진 형태와 동일하다.Graphene is a recently discovered two-dimensional carbon nanostructure, a hexagonal crystal lattice in the form of a single-plate structure consisting of sp 2 hybrids of carbon atoms. The graphene has the same shape as that in which hexagonal crystal lattice is stacked in a layered structure and the interlayer separation is completely completed in the graphite having a laminated structure.
그래핀 제조시에 발생하는 그래핀의 중간체인 산화흑연은 흑연 분말에 질산과 과염소산칼륨을 가한 후 수일 동안 반응시켜 산화흑연을 제조하는 스타우덴마이어(Staudenmaier) 법, 브로디(Brodie) 법, 및 허머(Hummer) 법 등이 알려져 있다.Graphene oxide, an intermediate of graphene that is produced during the production of graphene, is added to the graphite powder by adding nitric acid and potassium perchlorate and reacting for several days to produce graphite oxide, the Stadenmaier method, the Brodie method, and The Hummer method is known.
이렇게 제조된 산화흑연은 강한 산성 및 기타 이온을 함유하는 용액에 분산되어 있기 때문에 산화흑연을 분리하기 위해서는 수 차례의 세척 과정을 필연적으로 동반하게 된다. 예를 들어, 대한민국 등록특허 제 1095584 호는 유기용매를 이용한 산화흑연의 세척 방법을 개시하고 있다. 그러나, 이러한 일련의 과정을 거치더라도 산화 흑연에 함유되는 상기 기타 이온의 농도는 종류에 따라 K+ 이온의 경우 1,000 ppm 이하를 유지하기 힘들고 Mn2+이온의 경우는 100 ppm 이상의 농도를 유지하기 때문에 그래핀을 이용한 복합체 형성 및 합성시 부가적인 문제들이 야기될 수 있다.Since the prepared graphite oxide is dispersed in a solution containing strong acid and other ions, it is inevitably accompanied by several washing processes to separate the graphite oxide. For example, Korean Patent No. 1095584 discloses a method for cleaning graphite oxide using an organic solvent. However, the concentration of the other ions contained in the graphite oxide is difficult to maintain 1,000 ppm or less in the case of K + ions and 100 ppm or more in the case of Mn 2+ ions even after such a series of processes. Additional problems may arise in the formation and synthesis of composites using graphene.
본원은, 산화흑연의 제조 과정에 있어서 제올라이트를 사용함으로써 산화흑연에 함유된 잔류 금속 이온을 효율적으로 제거할 수 있는, 산화흑연의 제조방법을 제공할 수 있다.This application can provide the manufacturing method of the graphite oxide which can remove the residual metal ion contained in graphite oxide efficiently by using zeolite in the manufacturing process of graphite oxide.
그러나, 본원이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
본원의 제 1 측면은, 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계; 상기 흑연 슬러리로부터 산화흑연을 분리하는 단계; 및 상기 산화흑연과 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계를 포함하는, 산화흑연(graphite oxide)의 제조방법을 제공할 수 있다.A first aspect of the present disclosure includes the steps of oxidizing the graphite in a graphite slurry comprising graphite, an alkali metal salt, and a solvent; Separating graphite oxide from the graphite slurry; And removing the residual metal ions contained in the graphite oxide by mixing and / or stirring the graphite oxide and the zeolite.
본원에 따르면, 산화흑연의 제조 중 필연적으로 산화흑연에 함유되는 금속 이온 및 기타 불순물들을 다단계의 세척 과정을 거치지 않고도 효율적으로 제거함으로써 고품질의 산화흑연을 고효율로 제조할 수 있는, 산화흑연의 제조방법을 제공할 수 있다. 본원의 산화흑연의 제조방법에 의하면, 제거하기 힘든 잔류 금속 이온 및 기타 불순물들을 간단한 방법으로 처리할 수 있어 경제적이고 효율적이며, 그래핀을 이용한 고분자 또는 유기화학제품의 합성시 불순물을 최소화 할 수 있다. 아울러, 본원의 산화흑연의 제조 중에 산화흑연의 세척을 위하여 사용된 제올라이트는 회수하여 재사용할 수 있으므로 경제적이다.According to the present invention, during the production of graphite oxide inevitably remove the metal ions and other impurities contained in the graphite oxide without going through a multi-step washing process to produce high quality graphite oxide with high efficiency, Can be provided. According to the production method of the graphite oxide of the present invention, it is economical and efficient to process residual metal ions and other impurities that are difficult to remove by a simple method, and it is possible to minimize impurities when synthesizing a polymer or organic chemical product using graphene. . In addition, the zeolite used for washing the graphite oxide during the production of the graphite oxide of the present application is economical because it can be recovered and reused.
도 1은 본원의 일 실시예에 따른 산화흑연의 제조 과정을 나타낸 순서도이다.1 is a flow chart showing a process for producing graphite oxide according to an embodiment of the present application.
아래에서는 첨부한 도면을 참조하여 본원이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본원의 실시예를 상세히 설명한다. 그러나 본원은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본원을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.
본원 명세서 전체에서, 어떤 부분이 다른 부분과 "연결"되어 있다고 할 때, 이는 "직접적으로 연결"되어 있는 경우뿐 아니라, 그 중간에 다른 소자를 사이에 두고 "전기적으로 연결"되어 있는 경우도 포함한다. Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.
본원 명세서 전체에서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. 본원 명세서 전체에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본원의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. 본원 명세서 전체에서 사용되는 정도의 용어 "~(하는) 단계" 또는 "~의 단계"는 "~를 위한 단계"를 의미하지 않는다.Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."
본원 명세서 전체에서, 마쿠시 형식의 표현에 포함된 "이들의 조합"의 용어는 마쿠시 형식의 표현에 기재된 구성 요소들로 이루어진 군에서 선택되는 하나 이상의 혼합 또는 조합을 의미하는 것으로서, 상기 구성 요소들로 이루어진 군에서 선택되는 하나 이상을 포함하는 것을 의미한다.Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.
본원 명세서 전체에서, "A 및/또는 B"는 "A 또는 B, 또는 A 및 B"를 의미한다.Throughout this specification, "A and / or B" means "A or B, or A and B."
본원의 제 1 측면은, 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계; 상기 흑연 슬러리로부터 산화흑연을 분리하는 단계; 및 상기 산화흑연과 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계를 포함하는, 산화흑연(graphite oxide)의 제조방법을 제공할 수 있다. 예를 들어, 상기 산화흑연은 산화된 흑연을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.A first aspect of the present disclosure includes the steps of oxidizing the graphite in a graphite slurry comprising graphite, an alkali metal salt, and a solvent; Separating graphite oxide from the graphite slurry; And removing the residual metal ions contained in the graphite oxide by mixing and / or stirring the graphite oxide and the zeolite. For example, the graphite oxide may include oxidized graphite, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연을 상기 용매와 혼합한 제 1 혼합물과, 상기 알칼리 금속염을 상기 용매와 혼합한 제 2 혼합물을 준비한 후, 상기 제 1 혼합물과 상기 제 2 혼합물을 혼합하여 상기 흑연 슬러리를 제조할 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 제 1 혼합물과 상기 제 2 혼합물을 혼합한 후, 상기 흑연 슬러리는 약 0℃ 내지 약 50℃, 약 10℃ 내지 약 50℃, 약 20℃ 내지 약 50℃, 약 30℃ 내지 약 50℃, 약 40℃ 내지 약 50℃, 약 0℃ 내지 약 40℃, 약 0℃ 내지 약 30℃, 약 0℃ 내지 약 20℃, 약 0℃ 내지 약 10℃, 또는 약 20℃ 내지 약 35℃의 온도에서 유지될 수 있으나, 이에 제한되는 것은 아니다. 상기 흑연 슬러리가 약 0℃ 미만에서 유지되는 경우, 산화흑연 제조의 반응 효율이 낮고, 약 50℃ 초과의 온도에서 유지되는 경우 폭발 위험성이 있으므로, 상기 흑연 슬러리는 국지적인 과열에 의한 폭발을 방지하기 위하여 상기 온도 범위 내에서 조절될 수 있으나, 이에 제한되지 않을 수 있다. According to the exemplary embodiment of the present application, after preparing a first mixture of the graphite and the solvent and a second mixture of the alkali metal salt and the solvent, the first mixture and the second mixture are mixed to Graphite slurry can be prepared, but is not limited thereto. For example, after mixing the first mixture and the second mixture, the graphite slurry is about 0 ° C to about 50 ° C, about 10 ° C to about 50 ° C, about 20 ° C to about 50 ° C, and about 30 ° C to About 50 ° C., about 40 ° C. to about 50 ° C., about 0 ° C. to about 40 ° C., about 0 ° C. to about 30 ° C., about 0 ° C. to about 20 ° C., about 0 ° C. to about 10 ° C., or about 20 ° C. to about It may be maintained at a temperature of 35 ℃, but is not limited thereto. When the graphite slurry is kept below about 0 ° C., the reaction efficiency of graphite oxide production is low and there is a risk of explosion when it is maintained at a temperature above about 50 ° C., so that the graphite slurry is prevented from explosion due to local overheating. In order to be adjusted within the temperature range, but may not be limited thereto.
본원의 일 구현예에 따르면, 상기 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계는 약 10 시간 이하, 예를 들어, 약 1 분 내지 약 10 시간, 약 5 분 내지 약 10 시간, 약 10 분 내지 약 10 시간, 약 30 분 내지 약 10 시간, 약 1 시간 내지 약 10 시간, 약 2 시간 내지 약 10 시간, 약 5 시간 내지 약 10 시간, 약 1 분 내지 약 5 시간, 약 1 분 내지 약 2 시간, 약 1 분 내지 약 1 시간, 약 1 분 내지 약 30 분, 약 1 분 내지 약 20 분, 약 1 분 내지 약 10 분, 또는 약 5 분 내지 약 2 시간 동안 수행되는 것일 수 있으나, 이에 제한되는 것은 아니다. According to an embodiment of the present disclosure, the step of oxidizing the graphite in the graphite slurry comprising the graphite, the alkali metal salt, and the solvent may be about 10 hours or less, for example, about 1 minute to about 10 hours, about 5 minutes. To about 10 hours, about 10 minutes to about 10 hours, about 30 minutes to about 10 hours, about 1 hour to about 10 hours, about 2 hours to about 10 hours, about 5 hours to about 10 hours, about 1 minute to about 5 hours, about 1 minute to about 2 hours, about 1 minute to about 1 hour, about 1 minute to about 30 minutes, about 1 minute to about 20 minutes, about 1 minute to about 10 minutes, or about 5 minutes to about 2 It may be performed for a time, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계를 포함하는 단계는, 상기 흑연 슬러리가 일정 범위의 온도를 유지할 수 있도록, 냉각설비가 구비되어 있는 열 교환기 내에서 수행되는 것일 수 있으나, 이에 제한되는 것은 아니다.According to the exemplary embodiment of the present disclosure, the step of oxidizing the graphite in the graphite slurry including the graphite, the alkali metal salt, and the solvent may include a cooling facility to maintain the temperature of the graphite slurry in a predetermined range. It may be to be performed in the heat exchanger is provided, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계 및 상기 흑연 슬러리로부터 산화흑연을 분리하는 단계는, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 습득하여 수행할 수 있는 스타우덴마이어(Staudenmaier) 법, 브로디(Brodie) 법, 허머(Hummer) 법, 또는 그 응용법을 포함하는 산화흑연의 제조방법에 의하여 수행되는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present invention, the step of oxidizing the graphite in the graphite slurry containing the graphite, an alkali metal salt, and a solvent and separating the graphite oxide from the graphite slurry, is usually in the art It is performed by the method of manufacturing graphite oxide including the Stadenmaier method, the Brodie method, the Hummer method, or an application thereof which can be easily acquired and performed by a person with knowledge of May be, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 산화흑연과 상기 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계에서, 상기 제올라이트는 상기 산화흑연의 약 10 중량% 이하, 예를 들어, 약 0.1 중량% 내지 약 10 중량%, 약 0.5 중량% 내지 약 10 중량%, 약 1 중량% 내지 약 10 중량%, 약 3 중량% 내지 약 10 중량%, 약 5 중량% 내지 약 10 중량%, 약 7 중량% 내지 약 10 중량%, 약 0.1 중량% 내지 약 7 중량%, 약 0.1 중량% 내지 약 5 중량%, 약 0.1 중량% 내지 약 3 중량%, 약 0.1 중량% 내지 약 1 중량%, 약 0.1 중량% 내지 약 0.5 중량%, 또는 약 1 중량% 내지 약 5 중량%의 비율로 상기 산화흑연에 포함될 수 있으나, 이에 제한되는 것은 아니다. According to one embodiment of the present application, in the step of mixing and / or stirring the graphite oxide and the zeolite to remove residual metal ions contained in the graphite oxide, the zeolite is about 10% by weight or less of the graphite oxide, eg For example, about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 5 wt% to about 10 Wt%, about 7 wt% to about 10 wt%, about 0.1 wt% to about 7 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1 The graphite oxide may be included in the ratio of about 1% by weight, about 0.1% by weight to about 0.5% by weight, or about 1% by weight to about 5% by weight, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 산화흑연의 제조방법은 감압건조 단계를 추가로 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 감압건조는 약 0℃ 내지 약 200℃, 약 20℃ 내지 약 100℃, 약 40℃ 내지 약 100℃, 약 50℃ 내지 약 100℃, 약 60℃ 내지 약 100℃, 약 0℃ 내지 약 90℃, 약 0℃ 내지 약 80℃, 약 0℃ 내지 약 50℃, 약 0℃ 내지 약 60℃, 약 0℃ 내지 약 50℃, 약 0℃ 내지 약 40℃, 또는 약 50℃ 내지 약 60℃의 온도에서 수행될 수 있으나, 이에 제한되는 것은 아니다.According to the exemplary embodiment of the present application, the method of preparing the graphite oxide may further include a vacuum drying step, but is not limited thereto. For example, the reduced pressure drying may be about 0 ° C. to about 200 ° C., about 20 ° C. to about 100 ° C., about 40 ° C. to about 100 ° C., about 50 ° C. to about 100 ° C., about 60 ° C. to about 100 ° C., and about 0 ° C. ° C to about 90 ° C, about 0 ° C to about 80 ° C, about 0 ° C to about 50 ° C, about 0 ° C to about 60 ° C, about 0 ° C to about 50 ° C, about 0 ° C to about 40 ° C, or about 50 ° C To about 60 ° C., but is not limited thereto.
본원의 일 구현예에 따르면, 상기 감압건조는 약 48 시간 이하, 예를 들어, 약 1 분 내지 약 48 시간, 약 1 시간 내지 약 48 시간, 약 5 시간 내지 약 48 시간, 약 10 시간 내지 약 48 시간, 약 20 시간 내지 약 48 시간, 약 30 시간 내지 약 48 시간, 약 40 시간 내지 약 48 시간, 약 1 시간 내지 약 40 시간, 약 1 시간 내지 약 30 시간, 약 1 시간 내지 약 20 시간, 약 1 시간 내지 약 10 시간, 또는 약 1 시간 내지 약 5 시간 동안 수행되는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present disclosure, the reduced pressure drying is about 48 hours or less, for example, about 1 minute to about 48 hours, about 1 hour to about 48 hours, about 5 hours to about 48 hours, about 10 hours to about 48 hours, about 20 hours to about 48 hours, about 30 hours to about 48 hours, about 40 hours to about 48 hours, about 1 hour to about 40 hours, about 1 hour to about 30 hours, about 1 hour to about 20 hours , About 1 hour to about 10 hours, or about 1 hour to about 5 hours, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 교반은 약 240 시간 이하, 예를 들어, 약 1 시간 내지 약 240 시간, 약 1 시간 내지 약 200 시간, 약 1 시간 내지 약 150 시간, 약 1 시간 내지 약 100 시간, 약 1 시간 내지 약 50 시간, 약 1 시간 내지 약 20 시간, 약 1 시간 내지 약 10 시간, 약 1 시간 내지 약 5 시간, 약 5 시간 내지 약 240 시간, 약 10 시간 내지 약 240 시간, 약 20 시간 내지 약 240 시간, 약 50 시간 내지 약 240 시간, 약 100 시간 내지 약 240 시간, 약 150 시간 내지 약 240 시간, 또는 약 200 시간 내지 약 240 시간 동안 수행되는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present disclosure, the agitation is about 240 hours or less, for example, about 1 hour to about 240 hours, about 1 hour to about 200 hours, about 1 hour to about 150 hours, about 1 hour to about 100 Hour, about 1 hour to about 50 hours, about 1 hour to about 20 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 240 hours, about 10 hours to about 240 hours, About 20 hours to about 240 hours, about 50 hours to about 240 hours, about 100 hours to about 240 hours, about 150 hours to about 240 hours, or about 200 hours to about 240 hours, but is not limited thereto. It is not.
본원의 일 구현예에 따르면, 상기 제올라이트는 천연 제올라이트, 합성 제올라이트, LSX 제올라이트 (low silica zeolite), ZSM 제올라이트, 제올라이트 X, 제올라이트 Y, 제올라이트 L, 제올라이트 A, 및 이들의 조합들로 이루어지는 군으로부터 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the invention, the zeolite is selected from the group consisting of natural zeolite, synthetic zeolite, LSX zeolite (low silica zeolite), ZSM zeolite, zeolite X, zeolite Y, zeolite L, zeolite A, and combinations thereof It may include, but is not limited to.
본원의 일 구현예에 따르면, 상기 용매는, 질산, 황산, 염산, 또는 이들의 혼합물을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 질산은 발연질산을 포함하는 것일 수 있으며, 상기 황산은 발연황산을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 용매는 진한질산, 진한황산, 또는 이들의 혼합물을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 용매는, 상기 질산, 황산, 또는 질산 및 황산을 약 90 중량% 이상 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 용매는, 상기 질산, 황산, 또는 질산 및 황산을 약 90 중량% 이상, 약 91 중량% 이상, 약 92 중량% 이상, 약 93 중량% 이상, 약 94 중량% 이상, 약 95 중량% 이상, 약 96 중량% 이상, 약 97 중량% 이상, 약 98 중량% 이상, 약 99 중량% 이상, 또는 약 100 중량% 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the solvent may include nitric acid, sulfuric acid, hydrochloric acid, or a mixture thereof, but is not limited thereto. For example, the nitric acid may include fuming nitric acid, and the sulfuric acid may include fuming sulfuric acid, but is not limited thereto. For example, the solvent may include, but is not limited to, concentrated nitric acid, concentrated sulfuric acid, or a mixture thereof. For example, the solvent may include, but is not limited to, nitric acid, sulfuric acid, or about 90 wt% or more of nitric acid and sulfuric acid. For example, the solvent may comprise at least about 90 wt%, at least about 91 wt%, at least about 92 wt%, at least about 93 wt%, at least about 94 wt%, about 95 wt% of the nitric acid, sulfuric acid, or nitric acid and sulfuric acid. It may include, but is not limited to, at least about 100 wt%, at least about 96 wt%, at least about 97 wt%, at least about 98 wt%, at least about 99 wt%, or about 100 wt%.
본원의 일 구현예에 따르면, 상기 알칼리 금속염은, 염소산칼륨, 과망간산칼륨, 질산나트륨, 차아염소산리튬, 과염소산리튬, 망간산리튬, 질산리튬, 질산세슘 및 이들의 조합들로 이루어지는 군으로부터 선택되는 것을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 분말 상태의 상기 알칼리 금속염을 상기 용매에 용해시키는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the alkali metal salt is selected from the group consisting of potassium chlorate, potassium permanganate, sodium nitrate, lithium hypochlorite, lithium perchlorate, lithium manganate, lithium nitrate, cesium nitrate and combinations thereof It may be included, but is not limited thereto. For example, the alkali metal salt in a powder state may be dissolved in the solvent, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연 슬러리는, 상기 흑연 약 1 중량부에 대하여 상기 용매를 약 10 중량부 내지 약 100 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 흑연 슬러리는, 상기 흑연 약 1 중량부에 대하여 상기 용매를 약 10 중량부 내지 약 100 중량부, 약 20 중량부 내지 약 100 중량부, 약 30 중량부 내지 약 100 중량부, 약 40 중량부 내지 약 100 중량부, 약 50 중량부 내지 약 100 중량부, 약 60 중량부 내지 약 100 중량부, 약 70 중량부 내지 약 100 중량부, 약 80 중량부 내지 약 100 중량부, 약 90 중량부 내지 약 100 중량부, 약 10 중량부 내지 약 90 중량부, 약 10 중량부 내지 약 80 중량부, 약 10 중량부 내지 약 70 중량부, 약 10 중량부 내지 약 60 중량부, 약 10 중량부 내지 약 50 중량부, 약 10 중량부 내지 약 40 중량부, 약 10 중량부 내지 약 30 중량부, 약 10 중량부 내지 약 20 중량부, 또는 약 30 중량부 내지 약 50 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the graphite slurry may include, but is not limited to, about 10 parts by weight to about 100 parts by weight of the solvent based on about 1 part by weight of the graphite. For example, the graphite slurry may include about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, about 30 parts by weight to about 100 parts by weight, based on about 1 part by weight of the graphite, About 40 to about 100 parts by weight, about 50 to about 100 parts by weight, about 60 to about 100 parts by weight, about 70 to about 100 parts by weight, about 80 to about 100 parts by weight, About 90 parts by weight to about 100 parts by weight, about 10 parts by weight to about 90 parts by weight, about 10 parts by weight to about 80 parts by weight, about 10 parts by weight to about 70 parts by weight, about 10 parts by weight to about 60 parts by weight, About 10 parts by weight to about 50 parts by weight, about 10 parts by weight to about 40 parts by weight, about 10 parts by weight to about 30 parts by weight, about 10 parts by weight to about 20 parts by weight, or about 30 parts by weight to about 50 parts by weight It may be included, but is not limited thereto.
상기 흑연 약 1 중량부에 대하여 상기 용매가 약 10 중량부 미만 포함되는 경우, 상기 흑연 슬러리의 점도가 너무 높아져 산화흑연 제조 중 상기 흑연 슬러리를 포함하는 반응물의 이송과 혼합이 원활하지 않을 수 있다. 또한, 상기 흑연 약 1 중량부에 대하여 상기 용매가 약 100 중량부 초과 포함되는 경우, 산화흑연 제조를 위한 반응 효율성이 낮고 폐 용매 부산물이 많이 발생하게 된다.When the solvent is included in less than about 10 parts by weight with respect to about 1 part by weight of the graphite, the viscosity of the graphite slurry is too high may not be smooth transfer and mixing of the reactants including the graphite slurry during graphite oxide production. In addition, when the solvent is contained in an amount of about 100 parts by weight based on about 1 part by weight of the graphite, the reaction efficiency for the production of graphite oxide is low and a lot of waste solvent by-products are generated.
본원의 일 구현예에 따르면, 상기 흑연 슬러리는, 상기 알칼리 금속염 약 2 중량부에 대하여, 상기 용매를 약 10 중량부 내지 약 100 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 흑연 슬러리는, 상기 알칼리 금속염 약 1 중량부에 대하여, 상기 용매를 약 10 중량부 내지 약 100 중량부, 약 20 중량부 내지 약 100 중량부, 약 30 중량부 내지 약 100 중량부, 약 40 중량부 내지 약 100 중량부, 약 50 중량부 내지 약 100 중량부, 약 60 중량부 내지 약 100 중량부, 약 70 중량부 내지 약 100 중량부, 약 80 중량부 내지 약 100 중량부, 약 90 중량부 내지 약 100 중량부, 약 10 중량부 내지 약 90 중량부, 약 10 중량부 내지 약 80 중량부, 약 10 중량부 내지 약 70 중량부, 약 10 중량부 내지 약 60 중량부, 약 10 중량부 내지 약 50 중량부, 약 10 중량부 내지 약 40 중량부, 약 10 중량부 내지 약 30 중량부, 약 10 중량부 내지 약 20 중량부, 또는 약 30 중량부 내지 약 50 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to the exemplary embodiment of the present application, the graphite slurry may include about 10 parts by weight to about 100 parts by weight of the solvent, based on about 2 parts by weight of the alkali metal salt, but is not limited thereto. For example, the graphite slurry may contain about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, and about 30 parts by weight to about 100 parts by weight of the solvent, based on about 1 part by weight of the alkali metal salt. About 40 parts by weight to about 100 parts by weight, about 50 parts by weight to about 100 parts by weight, about 60 parts by weight to about 100 parts by weight, about 70 parts by weight to about 100 parts by weight, about 80 parts by weight to about 100 parts by weight About 90 parts by weight to about 100 parts by weight, about 10 parts by weight to about 90 parts by weight, about 10 parts by weight to about 80 parts by weight, about 10 parts by weight to about 70 parts by weight, about 10 parts by weight to about 60 parts by weight About 10 parts by weight to about 50 parts by weight, about 10 parts by weight to about 40 parts by weight, about 10 parts by weight to about 30 parts by weight, about 10 parts by weight to about 20 parts by weight, or about 30 parts by weight to about 50 parts by weight. It may be included in parts by weight, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연 슬러리는, 상기 흑연 약 1 중량부에 대하여 상기 알칼리 금속염을 약 0.2 중량부 내지 약 20 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 흑연 슬러리는, 상기 흑연 약 1 중량부에 대하여 상기 알칼리 금속염을 약 0.2 중량부 내지 약 20 중량부, 약 0.5 중량부 내지 약 20 중량부, 약 1 중량부 내지 약 20 중량부, 약 5 중량부 내지 약 20 중량부, 약 10 중량부 내지 약 20 중량부, 약 0.2 중량부 내지 약 10 중량부, 약 0.2 중량부 내지 약 5 중량부, 약 0.2 중량부 내지 약 1 중량부, 또는 약 0.2 중량부 내지 약 0.5 중량부 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to the exemplary embodiment of the present application, the graphite slurry may include about 0.2 parts by weight to about 20 parts by weight of the alkali metal salt based on about 1 part by weight of the graphite, but is not limited thereto. For example, the graphite slurry may contain about 0.2 parts by weight to about 20 parts by weight, about 0.5 parts by weight to about 20 parts by weight, and about 1 part by weight to about 20 parts by weight of the alkali metal salt based on about 1 part by weight of the graphite. About 5 parts by weight to about 20 parts by weight, about 10 parts by weight to about 20 parts by weight, about 0.2 parts by weight to about 10 parts by weight, about 0.2 parts by weight to about 5 parts by weight, about 0.2 parts by weight to about 1 parts by weight Or about 0.2 parts by weight to about 0.5 parts by weight, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연은 분말 형태인 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the graphite may be in powder form, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연의 분말은 직경이 약 200 ㎛ 이하인 것을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 흑연의 분말은 직경이 약 1 ㎛ 내지 약 200 ㎛, 약 5 ㎛ 내지 약 200 ㎛, 약 10 ㎛ 내지 약 200 ㎛, 약 50 ㎛ 내지 약 200 ㎛, 약 100 ㎛ 내지 약 200 ㎛, 약 150 ㎛ 내지 약 200 ㎛, 약 1 ㎛ 내지 약 150 ㎛, 약 1 ㎛ 내지 약 100 ㎛, 약 1 ㎛ 내지 약 50 ㎛, 약 1 ㎛ 내지 약 10 ㎛, 약 1 ㎛ 내지 약 5 ㎛, 또는 약 5 ㎛ 내지 약 50 ㎛인 것을 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to the exemplary embodiment of the present application, the powder of graphite may include one having a diameter of about 200 μm or less, but is not limited thereto. For example, the powder of graphite has a diameter of about 1 μm to about 200 μm, about 5 μm to about 200 μm, about 10 μm to about 200 μm, about 50 μm to about 200 μm, about 100 μm to about 200 μm About 150 μm to about 200 μm, about 1 μm to about 150 μm, about 1 μm to about 100 μm, about 1 μm to about 50 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, or It may include, but is not limited to about 5 ㎛ to about 50 ㎛.
상기 분말 형태의 흑연은, 그 입도가 1 ㎛ 미만인 경우, 입도가 너무 낮아 중량 밀도에 따른 팽창 효과가 낮으므로 박리에 의한 그래핀 형성이 용이하지 않다. 또한 그 입도가 200 ㎛ 초과인 경우, 입도가 너무 커 반응물의 이송과 혼합이 용이하지 않다. When the graphite in powder form has a particle size of less than 1 μm, the particle size is so low that the expansion effect according to the weight density is low, and thus graphene is not easily formed by peeling. In addition, when the particle size is more than 200 μm, the particle size is too large to facilitate the conveyance and mixing of the reactants.
본원의 일 구현예에 따르면, 상기 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계 후에, 상기 흑연 슬러리에 과산화수소 수용액을 첨가하는 단계를 추가로 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 상기 과산화수소 수용액은 상기 흑연 슬러리에 포함되어 상기 흑연을 산화시키는 상기 알칼리 금속염을 환원시킴으로써 흑연의 산화반응을 종결시킬 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, after the step of oxidizing the graphite in the graphite slurry, it may further include adding a hydrogen peroxide aqueous solution to the graphite slurry, but is not limited thereto. The aqueous hydrogen peroxide solution may terminate the oxidation reaction of graphite by reducing the alkali metal salt included in the graphite slurry to oxidize the graphite, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 과산화수소 수용액은 과산화수소를 약 30 중량% 이하, 예를 들어, 약 1 중량% 내지 약 30 중량%, 약 2 중량% 내지 약 30 중량%, 약 5 중량% 내지 약 30 중량%, 약 7 중량% 내지 약 30 중량%, 약 10 중량% 내지 약 30 중량%, 약 20 중량% 내지 약 30 중량%, 약 1 중량% 내지 약 20 중량%, 약 1 중량% 내지 약 10 중량%, 약 1 중량% 내지 약 7 중량%, 약 1 중량% 내지 약 5 중량%, 약 1 중량% 내지 약 2 중량%, 또는 약 2 중량% 내지 약 7 중량% 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. According to one embodiment of the present disclosure, the hydrogen peroxide aqueous solution may contain about 30 wt% or less of hydrogen peroxide, for example, about 1 wt% to about 30 wt%, about 2 wt% to about 30 wt%, about 5 wt% to about 30 wt%, about 7 wt% to about 30 wt%, about 10 wt% to about 30 wt%, about 20 wt% to about 30 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 2 wt%, or about 2 wt% to about 7 wt% It is not limited to this.
본원의 일 구현예에 따르면, 상기 흑연 약 1 중량부에 대하여, 상기 과산화수소 수용액을 약 100 중량부 이하, 예를 들어, 약 10 중량부 내지 약 100 중량부, 약 30 중량부 내지 약 100 중량부, 약 50 중량부 내지 약 100 중량부, 약 70 중량부 내지 약 100 중량부, 약 10 중량부 내지 약 70 중량부, 약 10 중량부 내지 약 50 중량부, 약 10 중량부 내지 약 30 중량부, 또는 약 30 중량부 내지 약 50 중량부 첨가하는 것일 수 있으나, 이에 제한되는 것은 아니다. 상기 흑연 슬러리 약 1 중량부에 대하여, 상기 과산화수소 수용액이 약 10 중량부 미만인 경우, 상기 흑연의 산화반응이 완전히 종결되지 않으며, 상기 과산화수소 수용액이 약 100 중량부 초과인 경우, 제조되는 산화흑연의 세척 및 건조 과정에 비용이 많이 들게 된다.According to one embodiment of the present application, about 100 parts by weight of the aqueous hydrogen peroxide solution, for example, about 10 parts by weight to about 100 parts by weight, about 30 parts by weight to about 100 parts by weight, based on about 1 part by weight of the graphite About 50 parts by weight to about 100 parts by weight, about 70 parts by weight to about 100 parts by weight, about 10 parts by weight to about 70 parts by weight, about 10 parts by weight to about 50 parts by weight, about 10 parts by weight to about 30 parts by weight , Or about 30 parts by weight to about 50 parts by weight, but is not limited thereto. When the aqueous hydrogen peroxide solution is less than about 10 parts by weight with respect to about 1 part by weight of the graphite slurry, the oxidation reaction of the graphite is not completely terminated, and when the aqueous hydrogen peroxide solution is greater than about 100 parts by weight, washing of the prepared graphite oxide And the drying process is expensive.
본원의 일 구현예에 있어서, 상기 흑연 슬러리에 상기 과산화수소 수용액을 첨가한 후, 약 1 시간 이하, 예를 들어, 약 1 분 내지 약 1 시간, 약 1 분 내지 약 40 분, 약 1 분 내지 약 20 분, 약 10 분 내지 약 1 시간, 또는 약 30 분 내지 약 1 시간 동안 상기 흑연 슬러리를 유지할 수 있으나, 이에 제한되는 것은 아니다.In one embodiment of the present application, after adding the aqueous hydrogen peroxide solution to the graphite slurry, about 1 hour or less, for example, about 1 minute to about 1 hour, about 1 minute to about 40 minutes, about 1 minute to about The graphite slurry can be maintained for 20 minutes, about 10 minutes to about 1 hour, or about 30 minutes to about 1 hour, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 산화흑연의 제조방법은, 내부의 온도가 일정 온도 범위에서 유지될 수 있고, 시작부, 반응부와 출구를 가지는 채널의 상기 시작부에 흑연 분말과 황산을 혼합하여 수득된 흑연 슬러리를 유입하는 단계; 상기 채널의 상기 시작부에 과망간산칼륨(KMnO4) 분말과 황산을 혼합하여 수득된 상기 KMnO4 황산 용액을 투입하여 혼합하는 단계; 상기 채널 내에서 상기 흑연 슬러리 및 상기 KMnO4 황산 용액의 혼합물을 일정 온도 범위에서 유지시키는 단계; 및 상기 채널의 출구 가까이에서 과산화수소 수용액을 투입하는 단계를 포함하는 단계에 의하여 제조되는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the method for producing graphite oxide, the internal temperature can be maintained in a certain temperature range, mixing the graphite powder and sulfuric acid at the beginning of the channel having a start, a reaction part and an outlet Introducing a graphite slurry obtained by the; Injecting and mixing the KMnO 4 sulfuric acid solution obtained by mixing potassium permanganate (KMnO 4 ) powder and sulfuric acid at the beginning of the channel; Maintaining a mixture of the graphite slurry and the KMnO 4 sulfuric acid solution in the channel at a predetermined temperature range; And it may be prepared by the step comprising the step of introducing an aqueous hydrogen peroxide solution near the outlet of the channel, but is not limited thereto.
예를 들어, 상기 KMnO4 황산 용액은 상기 채널에 과망간산칼륨을 황산 용액의 형태로 용이하게 첨가하여 혼합할 수 있으며, 상기 KMnO4 황산 용액은 상기 채널의 반응부에 연결된 정량펌프에 의하여 공급될 수 있으나, 이에 제한되는 것은 아니다. 상기 공급된 KMnO4 황산 용액의 양은 정량 방식 등에 의하여 엄격하게 조절될 수 있다.For example, the KMnO 4 sulfuric acid solution may be easily mixed by adding potassium permanganate to the channel in the form of a sulfuric acid solution, and the KMnO 4 sulfuric acid solution may be supplied by a metering pump connected to the reaction part of the channel. However, it is not limited thereto. The amount of the KMnO 4 sulfuric acid solution supplied may be strictly controlled by a quantitative method or the like.
상기 채널은 국지적인 과열에 의한 폭발을 방지하기 위하여, 특히 상기 채널의 상기 반응부는 적절한 온도 범위 내에서 엄격하게 조절되어야 한다.The channel must be tightly controlled, in particular within the appropriate temperature range, to prevent explosion due to local overheating.
본원의 일 구현예에 따르면, 상기 채널은 내경이 약 50 mm 이하, 예를 들어, 약 1 ㎛ 내지 약 50 mm, 약 10 ㎛ 내지 약 50 mm, 약 50 ㎛ 내지 약 50 mm, 약 100 ㎛ 내지 약 50 mm, 약 500 ㎛ 내지 약 50 mm, 약 1 mm 내지 약 50 mm, 약 10 mm 내지 약 50 mm, 약 1 ㎛ 내지 약 10 mm, 약 1 ㎛ 내지 약 1 mm, 약 1 ㎛ 내지 약 500 ㎛, 약 1 ㎛ 내지 약 100 ㎛, 약 1 ㎛ 내지 약 50 ㎛, 또는 약 1 ㎛ 내지 약 10 ㎛ 이하인 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 채널은 열전도성, 내식성, 및 내산성 중 하나 이상의 특성이 우수한 튜브형의 반응기를 포함할 수 있으나, 이에 제한되는 것은 아니다. 상기 채널은 국지과열에 의한 폭발 방지를 위하여 반응 혼합물을 바람직하게는 20℃ 내지 35℃로 유지할 수 있어야 하고, 반응 효율성 및 안전성을 위하여, 내경이 수십 ㎜ 이하, 바람직하게는 내경이 약 1 ㎛ 내지 1 ㎜ 여야 한다. 반응 혼합물은 상기 채널 내에서 초당 수 cm 내지 수 m, 바람직하게는 초당 수 cm 내지 수십 cm의 속도로 이동할 수 있으나, 이에 제한되는 것은 아니다.According to an embodiment of the present disclosure, the channel has an inner diameter of about 50 mm or less, for example, about 1 μm to about 50 mm, about 10 μm to about 50 mm, about 50 μm to about 50 mm, about 100 μm to About 50 mm, about 500 μm to about 50 mm, about 1 mm to about 50 mm, about 10 mm to about 50 mm, about 1 μm to about 10 mm, about 1 μm to about 1 mm, about 1 μm to about 500 Μm, about 1 μm to about 100 μm, about 1 μm to about 50 μm, or about 1 μm to about 10 μm or less, but is not limited thereto. For example, the channel may include, but is not limited to, a tubular reactor having one or more of excellent thermal conductivity, corrosion resistance, and acid resistance. The channel should be able to maintain the reaction mixture preferably at 20 ° C. to 35 ° C. to prevent explosion due to local overheating, and for reaction efficiency and safety, the inner diameter is several tens of mm or less, preferably the inner diameter is about 1 μm to It should be 1 mm. The reaction mixture may move in the channel at a speed of several cm to several m per second, preferably several cm to several tens of cm per second, but is not limited thereto.
상기 흑연 슬러리, 상기 KMnO4 황산 용액, 및 상기 과산화수소 수용액은 각각 정량펌프에 의하여 채널에 공급될 수 있다. 상기 흑연 슬러리 및 상기 KMnO4 황산 용액은 상기 채널 내에서 반응 혼합물이 와류를 형성할 수 있도록 상기 정량펌프에 의하여 충분한 압력 및/또는 속도로 상기 채널에 공급될 수 있다. 상기 과산화수소 수용액이 공급됨으로써 상기 흑연 슬러리에 포함된 여분의 KMnO4이 환원되고, 이에 의하여 반응이 종결된 반응 혼합물은 상기 반응기의 출구로 배출될 수 있다. 상기 반응기 출구로 배출된 반응이 종결된 반응 혼합물은, 건조되기 전에 4급 암모늄염을 포함하는 양이온 계면활성제 용액을 처리함으로써 세척될 수 있으나, 이에 제한되는 것은 아니다.The graphite slurry, the KMnO 4 sulfuric acid solution, and the aqueous hydrogen peroxide solution may be supplied to the channel by a metering pump, respectively. The graphite slurry and the KMnO 4 sulfuric acid solution may be supplied to the channel at a sufficient pressure and / or speed by the metering pump so that the reaction mixture forms a vortex in the channel. By supplying the aqueous hydrogen peroxide solution, the excess KMnO 4 contained in the graphite slurry is reduced, whereby the reaction mixture in which the reaction is terminated may be discharged to the outlet of the reactor. The reaction mixture in which the reaction discharged to the reactor outlet is terminated may be washed by treating the cationic surfactant solution including the quaternary ammonium salt before drying, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 흑연 슬러리로부터 산화흑연을 분리하는 단계 후에, 상기 산화흑연을 계면활성제 용액을 이용하여 세척하는 단계를 추가로 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, after the step of separating the graphite oxide from the graphite slurry, the graphite oxide may further include the step of washing with a surfactant solution, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 계면활성제는, 4급 암모늄염을 포함하는 양이온 계면활성제를 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, the surfactant may include a cationic surfactant including a quaternary ammonium salt, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 산화흑연과 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계 후에, 체(sieve)를 이용하여 상기 제올라이트를 제거함으로써 상기 산화흑연을 수득하는 단계를 추가로 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다.According to one embodiment of the present application, after the step of mixing and / or stirring the graphite oxide and zeolite to remove the residual metal ions contained in the graphite oxide, the graphite oxide by removing the zeolite using a sieve (sieve) It may be to include a further step to obtain, but is not limited thereto.
본원의 일 구현예에 따르면, 상기 제올라이트를 제거한 후에 회수하는 것을 추가로 포함하는 것일 수 있으나, 이에 제한되는 것은 아니다. 예를 들어, 상기 회수된 제올라이트는 다른 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계에서 사용될 수 있으나, 이에 제한되는 것은 아니다. According to one embodiment of the present application, the zeolite may further include recovering after removing the zeolite, but is not limited thereto. For example, the recovered zeolite may be used in the step of removing residual metal ions contained in other graphite oxide, but is not limited thereto.
이하, 본원에 대하여 실시예를 이용하여 보다 더 구체적으로 설명하지만, 본원이 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present application is not limited thereto.
[실시예]EXAMPLE
[산화흑연의 제조][Manufacture of Graphite Oxide]
황산 탱크로부터 공급되는 황산 및 흑연 분말을 각각 액체용 정량펌프와 분말용 정량펌프로부터 공급받아 준비되는 황산 흑연 슬러리는 프리믹서에 의하여 혼합되었으며, 이후 믹서에서 과망간산칼륨(KMnO4)이 주입되었고 반응열이 미세하게 조절되도록 튜브반응기를 통하여 대용량 프리믹서에 저장되었다. 준비된 상기 흑연 슬러리는 이후 액체용 정량펌프를 통하여 물과 혼합되었으며, 혼합시의 온도는 0℃ 내지 35℃의 비교적 낮은 온도로 운영되었다. 이어서, 과산화수소를 정량펌프를 통하여 투입시킴으로써 최종적으로 산화반응을 종결시켰다. The graphite sulfate slurry prepared by receiving sulfuric acid and graphite powder from the sulfuric acid tank from the liquid metering pump and the powder metering pump, respectively, was mixed by a premixer, and then potassium permanganate (KMnO 4 ) was introduced into the mixer and the reaction heat was reduced. It was stored in a large capacity premixer via a tube reactor to finely adjust. The prepared graphite slurry was then mixed with water through a liquid metering pump, and the temperature at the time of mixing was operated at a relatively low temperature of 0 ° C to 35 ° C. Subsequently, hydrogen peroxide was introduced through the metering pump to finally terminate the oxidation reaction.
이어서 과산화수소 혼합 탱크의 출구로부터 배출되는 반응 혼합물을 필터링 하여 산 및 미반응 산화제를 제거하고, 생성된 산화흑연 케이크 100 g에 제올라이트 (Synthetic, A-4, Beads, 8~12 mesh, Wako) 10 g을 첨가하여 1 일 내지 2 일 동안 천천히 교반 및 혼합하였다. 이후, 체(sieve)를 이용하여 상기 산화흑연을 분리하여 세척을 종결하였다. 상기와 같은 세척공정을 거친 산화흑연을 약 60℃ 이하에서 48 시간 이내에서 감압 건조하여 산화흑연을 제조하였다.The reaction mixture discharged from the outlet of the hydrogen peroxide mixing tank was then filtered to remove acid and unreacted oxidant, and 10 g of zeolite (Synthetic, A-4, Beads, 8-12 mesh, Wako) was added to 100 g of the resulting graphite oxide cake. Was added and stirred and mixed slowly for 1 to 2 days. Thereafter, the graphite oxide was separated using a sieve to terminate the washing. Graphite oxide was dried under reduced pressure within 48 hours at about 60 ° C. or less after passing through the washing process as described above.
[제조된 산화흑연의 잔류 금속 이온 농도 측정][Measurement of Residual Metal Ion Concentration in Prepared Graphite Oxide]
본 실시예에서는 제조된 산화흑연의 잔류 금속 이온 농도를 무기원소분석(ICP) 방법을 이용하여 측정하여 비교하였다. 기존의 필터프레스 방법 및 원심분리 방법에 의하여 잔류 금속 이온이 제거된 산화흑연, 및 제올라이트를 이용하여 잔류 금속 이온이 제거된 산화흑연의 잔류 금속 이온 농도가 하기 표 1에 표시되었다. 본 실시예에서 무기원소분석은 ICP-AES (iCAP-6000 SERIES, Thermo electron) 장비를 이용하여 수행되었으며, 전처리로서 3 mL의 염산, 1 mL의 질산, 및 1 mL의 불산을 사용하여 처리되었다. 시료는 0.1 g 이상 테플론 용기를 사용하여 채취되었으며, 1차 희석비는 25 mL이었고, 2차 희석비는 50 mL이었다.In this example, the residual metal ion concentration of the prepared graphite oxide was measured and compared by using an inorganic element analysis (ICP) method. The residual metal ion concentrations of the graphite oxide from which residual metal ions were removed by the conventional filter press method and the centrifugal separation method, and the graphite oxide from which residual metal ions were removed using zeolite are shown in Table 1 below. Inorganic element analysis in this example was performed using ICP-AES (iCAP-6000 SERIES, Thermo electron) equipment, and was treated with 3 mL of hydrochloric acid, 1 mL of nitric acid, and 1 mL of hydrofluoric acid as pretreatment. Samples were taken using a Teflon vessel of at least 0.1 g with a first dilution of 25 mL and a second dilution of 50 mL.
표 1
Figure PCTKR2013010222-appb-T000001
 Table 1
Figure PCTKR2013010222-appb-T000001
상기 표 1에 나타난 바에 따르면, 필터프레스 방법 또는 원심분리 방법에 의하여 잔류 금속이온이 제거된 산화흑연에 비하여, 제올라이트를 이용하여 잔류 금속 이온이 제거된 산화흑연의 잔류 금속 이온 농도가 현저히 낮은 것으로 나타났다. 이는, 제올라이트 처리를 포함하는 본원의 산화흑연의 제조 방법에 의하여 제조된 산화흑연은 기존의 방법에 의하여 제조된 산화흑연에 비하여 현저히 낮은 잔류 금속 이온 농도를 가지는 우수한 품질의 산화흑연임을 의미하는 것이다.As shown in Table 1, the residual metal ion concentration of the graphite oxide from which residual metal ions were removed using zeolite was significantly lower than that of the graphite oxide from which residual metal ions were removed by a filter press method or a centrifugation method. . This means that the graphite oxide prepared by the method of producing graphite oxide of the present application including zeolite treatment is graphite oxide of good quality having a significantly lower residual metal ion concentration than the graphite oxide prepared by the conventional method.
전술한 본원의 설명은 예시를 위한 것이며, 본원이 속하는 기술분야의 통상의 지식을 가진 자는 본원의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수도 있다.The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본원의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위, 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본원의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims (11)

  1. 흑연, 알칼리 금속염, 및 용매를 포함하는 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계;Oxidizing the graphite in a graphite slurry comprising graphite, an alkali metal salt, and a solvent;
    상기 흑연 슬러리로부터 산화흑연을 분리하는 단계; 및Separating graphite oxide from the graphite slurry; And
    상기 산화흑연과 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계Mixing and / or stirring the graphite oxide and zeolite to remove residual metal ions contained in the graphite oxide
    를 포함하는,Including,
    산화흑연(graphite oxide)의 제조방법.Method for producing graphite oxide.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 용매는, 질산, 황산, 염산, 또는 이들의 혼합물을 포함하는 것인, 산화흑연의 제조방법.The solvent, nitric acid, sulfuric acid, hydrochloric acid, or a mixture thereof, the method of producing graphite oxide.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 알칼리 금속염은, 염소산칼륨, 과망간산칼륨, 질산나트륨, 차아염소산리튬, 과염소산리튬, 망간산리튬, 질산리튬, 질산세슘, 및 이들의 조합들로 이루어지는 군으로부터 선택되는 것을 포함하는 것인, 산화흑연의 제조방법.The alkali metal salt is one selected from the group consisting of potassium chlorate, potassium permanganate, sodium nitrate, lithium hypochlorite, lithium perchlorate, lithium manganate, lithium nitrate, cesium nitrate, and combinations thereof. Manufacturing method.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 흑연 슬러리는, 상기 흑연 1 중량부에 대하여 상기 용매를 10 중량부 내지 100 중량부 포함하는 것인, 산화흑연의 제조방법.The graphite slurry is a method for producing graphite oxide containing 10 parts by weight to 100 parts by weight of the solvent relative to 1 part by weight of the graphite.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 흑연 슬러리는, 상기 알칼리 금속염 2 중량부에 대하여, 상기 용매를 10 중량부 내지 100 중량부 포함하는 것인, 산화흑연의 제조방법.The graphite slurry is a method for producing graphite oxide containing 10 parts by weight to 100 parts by weight of the solvent relative to 2 parts by weight of the alkali metal salt.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 흑연은 분말 형태인 것인, 산화흑연의 제조방법.The graphite is in the form of a powder, a method of producing graphite oxide.
  7. 제 6 항에 있어서,The method of claim 6,
    상기 흑연의 분말은 직경이 200 ㎛ 이하인 것을 포함하는 것인, 산화흑연의 제조방법.The graphite powder is a method of producing a graphite oxide containing a diameter of 200 ㎛ or less.
  8. 제 1 항에 있어서,The method of claim 1,
    상기 흑연 슬러리 내에서 상기 흑연을 산화시키는 단계 후에, 상기 흑연 슬러리에 과산화수소 수용액을 첨가하는 단계를 추가로 포함하는, 산화흑연의 제조방법.After the step of oxidizing the graphite in the graphite slurry, further comprising the step of adding an aqueous hydrogen peroxide solution to the graphite slurry.
  9. 제 1 항에 있어서,The method of claim 1,
    상기 흑연 슬러리로부터 산화흑연을 분리하는 단계 후에, 상기 산화흑연을 계면활성제 용액을 이용하여 세척하는 단계를 추가로 포함하는, 산화흑연의 제조방법.After separating graphite oxide from the graphite slurry, further comprising washing the graphite oxide with a surfactant solution.
  10. 제 1 항에 있어서,The method of claim 1,
    상기 산화흑연과 제올라이트를 혼합 및/또는 교반하여 상기 산화흑연에 함유된 잔류 금속 이온을 제거하는 단계 후에, 체(sieve)를 이용하여 상기 제올라이트를 제거함으로써 상기 산화흑연을 수득하는 단계를 추가로 포함하는, 산화흑연의 제조방법.After the step of mixing and / or stirring the graphite oxide and zeolite to remove residual metal ions contained in the graphite oxide, further comprising obtaining the graphite oxide by removing the zeolite using a sieve. A method of producing graphite oxide.
  11. 제 10 항에 있어서,The method of claim 10,
    상기 제올라이트를 제거한 후에 회수하는 것을 추가로 포함하는, 산화흑연의 제조방법.The method of producing graphite oxide further comprising recovering the zeolite after removing the zeolite.
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