WO2013062373A1 - Mixture of multi-layered graphene for adsorbing organic material - Google Patents

Mixture of multi-layered graphene for adsorbing organic material Download PDF

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WO2013062373A1
WO2013062373A1 PCT/KR2012/008898 KR2012008898W WO2013062373A1 WO 2013062373 A1 WO2013062373 A1 WO 2013062373A1 KR 2012008898 W KR2012008898 W KR 2012008898W WO 2013062373 A1 WO2013062373 A1 WO 2013062373A1
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graphene
mixture
layered graphene
oil
graphite oxide
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French (fr)
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Shi Choon Lee
Cheol Min Shin
Tai Seong LEE
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Idt International Co., Ltd.
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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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness

Definitions

  • the present invention relates to a multi-layered graphene mixture produced for adsorbing an organic materialby applying a thermal shock to graphite oxide.
  • a graphene sheet may have defects caused by oxidation during a production process, a great amount of oxygen groups may remain, and the used oxidizer or solvent may remain. Thus, a quality of the graphene may be degraded.
  • the remaining oxygen groups increase miscibility with ceramic or a polymer used as a base material.
  • Korean Patent Application No. 2010-76871 and its Divisional Application No. 2011-24855 the present inventors describes an apparatus in which graphite oxide is dropped in a vertical fluidized bed furnace and separately collected to produce graphene. Further, in Korean Patent Application No. 2011-53787, the present inventors describes an apparatus in which graphite oxide is adsorbed in a reflow furnace to produce a graphene-structured material.
  • the present inventors have found that a multi-layered graphene mixture produced by chemical exfoliation, and particularly, by applying a thermal shock to graphite oxide has a high selective adsorptivity with respect to an organic material as well as specific thermal, electrical, and mechanical properties of graphene and thus completed the present invention.
  • the present invention provides a multi-layered graphene mixture for adsorbing an organic material having a selective adsorptivity with respect to an organic material.
  • a multi-layered graphene mixture for adsorbing an organic material, wherein the multi-layered graphene mixture is produced by passing graphite oxide having a carbon/oxygen ratio of from about 1/1 to about 50/1 through a fluidized bed furnace maintained at from about 300°C to about 1200°C and applying a thermal shock thereto.
  • graphite oxide having a carbon/oxygen ratio of from about 1/1 to about 50/1
  • a fluidized bed furnace maintained at from about 300°C to about 1200°C and applying a thermal shock thereto.
  • An average surface area of the multi-layered graphene mixture is in a range of from about 200 m 2 /g to about 2600 m 2 /g.
  • the multi-layered graphene mixture of the present invention is produced by exfoliating graphite oxide as described in pending Korean Patent Application No. 2011-53787 filed by the present inventors.
  • a functional group such as a hydroxyl group, a carboxylic acid group, and an epoxy group is formed at each layer through an oxidation reaction.
  • a gap between layers in graphite powder as a source is increased from about 3.4 ⁇ to about 7 ⁇ .
  • Such graphite oxide can be exfoliated rapidly, uniformly, and sufficiently by intercalating an oxidizer between layers of graphite and adding a thermal shock thereto. If the carbon/oxygen ratio of the graphite oxide is smaller than about 1/1, graphene is split into small pieces, and if the carbon/oxygen ratio is greater than about 50/1, an amount of exfoliation is decreased. In order to increase efficiency of exfoliation, ultrasonication may be performed during an oxidation process or an exfoliation process using a thermal shock.
  • the graphite oxide is exfoliated by a thermal shock and transformed into a multi-layered graphene mixture while rising in a vertical fluidized bed furnace.
  • the vertical fluidized bed furnace can be heated by a conventional method using a heater or by a method using microwaves.
  • a temperature within the vertical fluidized bed furnace is maintained in a range of from about 300°C to about 1200°C, and desirably, from about 500°C to about 1200°C.
  • the average number of layers in the multi-layered graphene mixture is in a range of from about 3 to about 20.
  • the multi-layered graphene mixture of the present invention has numerous spaces between graphene layers, which results in a high adsorptivity with respect to an organic material.
  • the graphene used herein has a surface area of about 400 m 2 /g and a carbon/oxygen ratio of about 25/1.
  • An accordion-like surface is exfoliated well and the average number of layers is about 5.
  • the multi-layered graphene mixture can be used as an absorbent contained in fine felt. Otherwise, a binder may be mixed therein and the mixture may be press-molded and carbonized to obtain a pack-shaped absorbent.
  • the pack-shaped absorbent is used particularly as an absorbent of spilled oil or waste oil.
  • a multi-layered graphene mixture applied with a thermal shock in accordance with the present invention has a high adsorptivity with respect to an organic material unlike graphite oxide or graphite.
  • the multi-layered graphene mixture has an oil adsorptivity two or more times higher than expanded graphite, carbon nanotubes or graphene produced by other methods and fifty or more times higher than commercial oil-absorbing pads.
  • the multi-layered graphene mixture is excellent as an organic material absorbent.
  • Fig. 1 provides electron micrographs of n-barotech graphene ER-2510.
  • Fig. 2 provides electron micrographs of typical expanded graphite.
  • n-dodecane was used as an adsorption target material.
  • Fig. 1 shows electron micrographs of n-barotech graphene ER-2510 produced by applying a thermal shock to graphite oxide. It can be seen that there were numerous spaces between graphene layers.
  • graphene (graphene produced by chemical exfoliation without an oxidation reaction) available from XG Science, Inc. of U.S. (Comparative example 1), graphene (high quality graphene having about 10 layers or less and produced by chemical vapor deposition) available from Graphene Supermarket of U.S. (Comparative example 2), graphite QKG-296 available from Qingdao Kropfmuehl Graphite Co., Ltd. of China (Comparative example 3), QKG-299 (Comparative example 4), n-barotech graphite oxide GO-3510 (Comparative example 5), expanded graphite available from Samjung C&G Co., Ltd.
  • Fig. 2 provides electron micrographs of the expanded graphite available from Samjung C&G Co., Ltd. (Comparative example 6). Unlike Fig. 1, any gap between graphene layers was not observed.
  • the graphite hardly adsorbed oil and the expanded graphite or the carbon nanotubes adsorbed oil to a certain degree. It could be seen that the graphene mixture applied with the thermal shock had an oil adsorptivity two or more times higher than the expanded graphite or the carbon nanotubes.
  • the commercial oil-absorbing pad adsorbed the crude oil in the amount of about seven times greater than the weight of the oil-absorbing pad.
  • the tea bag containing n-barotech graphene was used as an oil-absorbing pad, the tea bag adsorbed the crude oil in the amount of about sixty five or more times greater than a weight of the graphene used.

Abstract

The present invention relates to a multi-layered graphene mixture produced by applying a thermal shock to graphite oxide for adsorbing an organic material.

Description

MIXTURE OF MULTI-LAYERED GRAPHENE FOR ADSORBING ORGANIC MATERIAL
The present invention relates to a multi-layered graphene mixture produced for adsorbing an organic materialby applying a thermal shock to graphite oxide.
In 2004, Professor Andre Geim et al. from the University of Manchester first mechanically delaminated graphene from graphite by using "Scotch tape method" and found excellent electric conductivity of graphene through the study of a quantum hall effect by using the delaminated graphene.
Longitudinal scission of a carbon nanotube makes a graphene structure and infinite enlargement of a wall diameter makes a carbon nanotube similar to graphene. Therefore, electrical conductivity and thermal and mechanical properties of graphene are expected to be comparable to or superior to those of carbon nanotubes. Therefore, such graphene has been studied to be used as a conductive material and a strength reinforcing material. By way of example, there have been made a lot of studies for substitution of graphene for indium tin-oxide (ITO) typically used as a transparent electrode and application as a semiconducting material. Further, it has been known that graphene has the highest surface area among the existing materials (Novoselov, K. S., Geim, A.K. et al. Science 306, 666, 2004), which shows that the graphene can be used as an electrode material of an energy storage device such as a super capacitor or a secondary cell due to its high conductivity and high surface area (Stoller, M.D., Park, S., Zhu, Y., An, J., Ruoff, R. S., Nano Lett. 8, 3498-3502).
For preparation of graphene, there have been known mechanical exfoliation of graphite crystals as carried out by Professor Andre Geim et al. in the scotch tape method, chemical vapor deposition on a substrate, and chemical exfoliation in which an oxidizer and/or a reducer is added to graphite and the graphite is delaminated by a thermal shock or a chemical reaction. Graphene produced by the chemical exfoliation is different in structure from graphene produced by the mechanical exfoliation or the chemical vapor deposition. In particular, graphene produced by applying a thermal shock to graphite oxide and exfoliating the graphite oxide is also called "reduced graphene oxide". According to the exfoliation of the graphite oxide with the thermal shock, a graphene sheet may have defects caused by oxidation during a production process, a great amount of oxygen groups may remain, and the used oxidizer or solvent may remain. Thus, a quality of the graphene may be degraded. However, it is possible to produce graphene flakes in large amounts, so that the graphene flakes can be appropriately applied to production of super capacitors or polymer composite products processed in flakes. Further, the remaining oxygen groups increase miscibility with ceramic or a polymer used as a base material.
As a method of chemical exfoliation for producing graphene by applying a thermal shock to graphite oxide, in Korean Patent Application No. 2010-76871 and its Divisional Application No. 2011-24855, the present inventors describes an apparatus in which graphite oxide is dropped in a vertical fluidized bed furnace and separately collected to produce graphene. Further, in Korean Patent Application No. 2011-53787, the present inventors describes an apparatus in which graphite oxide is adsorbed in a reflow furnace to produce a graphene-structured material.
The present inventors have found that a multi-layered graphene mixture produced by chemical exfoliation, and particularly, by applying a thermal shock to graphite oxide has a high selective adsorptivity with respect to an organic material as well as specific thermal, electrical, and mechanical properties of graphene and thus completed the present invention.
The present invention provides a multi-layered graphene mixture for adsorbing an organic material having a selective adsorptivity with respect to an organic material.
In accordance with an illustrative embodiment of the present invention, there is provided a multi-layered graphene mixture for adsorbing an organic material, wherein the multi-layered graphene mixture is produced by passing graphite oxide having a carbon/oxygen ratio of from about 1/1 to about 50/1 through a fluidized bed furnace maintained at from about 300℃ to about 1200℃ and applying a thermal shock thereto. In the multi-layered graphene mixture, it can be determined that as a peak becomes minimized at 2θ = 26.5° on graphite and 2θ = 12.7° on graphite oxide, an amount of exfoliation is increased. An average surface area of the multi-layered graphene mixture is in a range of from about 200 m2/g to about 2600 m2/g.
Desirably, the multi-layered graphene mixture of the present invention is produced by exfoliating graphite oxide as described in pending Korean Patent Application No. 2011-53787 filed by the present inventors. The graphite oxide used herein has a carbon/oxygen ratio in a range of from about 1/1 to about 50/1 according to an elemental analyzer and has a maximum peak around 2θ = 12° according to an XRD analysis. In the graphite oxide, a functional group such as a hydroxyl group, a carboxylic acid group, and an epoxy group is formed at each layer through an oxidation reaction. Thus, a gap between layers in graphite powder as a source is increased from about 3.4 Å to about 7 Å. The graphite oxide has a peak of a trace around 2θ = 26° which is one of characteristics of graphite powder and has a peak around 2θ = 12.7° according to an XRD analysis. Such graphite oxide can be exfoliated rapidly, uniformly, and sufficiently by intercalating an oxidizer between layers of graphite and adding a thermal shock thereto. If the carbon/oxygen ratio of the graphite oxide is smaller than about 1/1, graphene is split into small pieces, and if the carbon/oxygen ratio is greater than about 50/1, an amount of exfoliation is decreased. In order to increase efficiency of exfoliation, ultrasonication may be performed during an oxidation process or an exfoliation process using a thermal shock. The graphite oxide is exfoliated by a thermal shock and transformed into a multi-layered graphene mixture while rising in a vertical fluidized bed furnace. The vertical fluidized bed furnace can be heated by a conventional method using a heater or by a method using microwaves. A temperature within the vertical fluidized bed furnace is maintained in a range of from about 300℃ to about 1200℃, and desirably, from about 500℃ to about 1200℃. Desirably, the average number of layers in the multi-layered graphene mixture is in a range of from about 3 to about 20.
It can be seen from a photo of Fig. 1 that the multi-layered graphene mixture of the present invention has numerous spaces between graphene layers, which results in a high adsorptivity with respect to an organic material. The graphene used herein has a surface area of about 400 m2/g and a carbon/oxygen ratio of about 25/1. An accordion-like surface is exfoliated well and the average number of layers is about 5.
The multi-layered graphene mixture can be used as an absorbent contained in fine felt. Otherwise, a binder may be mixed therein and the mixture may be press-molded and carbonized to obtain a pack-shaped absorbent. The pack-shaped absorbent is used particularly as an absorbent of spilled oil or waste oil.
A multi-layered graphene mixture applied with a thermal shock in accordance with the present invention has a high adsorptivity with respect to an organic material unlike graphite oxide or graphite. The multi-layered graphene mixture has an oil adsorptivity two or more times higher than expanded graphite, carbon nanotubes or graphene produced by other methods and fifty or more times higher than commercial oil-absorbing pads. Thus, the multi-layered graphene mixture is excellent as an organic material absorbent.
Fig. 1 provides electron micrographs of n-barotech graphene ER-2510.
Fig. 2 provides electron micrographs of typical expanded graphite.
Hereinafter, examples of the present invention will be described in detail.
[Example 1]
As a substitute for crude oil, n-dodecane was used as an adsorption target material.
Fig. 1 shows electron micrographs of n-barotech graphene ER-2510 produced by applying a thermal shock to graphite oxide. It can be seen that there were numerous spaces between graphene layers.
About 0.5 g n-barotech graphene ER-2510 as a multi-layered graphene mixture and about 10 g n-dodecane were put in a 5 L container. After oil was sufficiently adsorbed for about 30 minutes, a resultant product was transferred to a vacuum filtering container. After filtering, non-adsorbed oil was removed by applying a sound pressure for about 10 minutes and a total weight including a weight of filter paper was measured. The amount of the oil adsorbed to an adsorption material was measured by subtracting a previously measured weight of the filter paper and a weight of the graphene from the total weight of the resultant product including the adsorbed oil. An adsorptivity was calculated as follows. The adsorptivity was provided in Table 1.
Q = (filter paper, graphene, adsorption amount - filter paper and graphene)/ graphene * 100(%)
[Comparative examples 1 to 7]
In comparative examples 1 to 7, instead of the multi-layered graphene mixture, graphene (graphene produced by chemical exfoliation without an oxidation reaction) available from XG Science, Inc. of U.S. (Comparative example 1), graphene (high quality graphene having about 10 layers or less and produced by chemical vapor deposition) available from Graphene Supermarket of U.S. (Comparative example 2), graphite QKG-296 available from Qingdao Kropfmuehl Graphite Co., Ltd. of China (Comparative example 3), QKG-299 (Comparative example 4), n-barotech graphite oxide GO-3510 (Comparative example 5), expanded graphite available from Samjung C&G Co., Ltd. (Comparative example 6), and carbon nanotubes (CNT) CM-95 available from Hanwha Nanotech Corp. (Comparative example 7) were used, and adsorptivities were listed in Table 1. Fig. 2 provides electron micrographs of the expanded graphite available from Samjung C&G Co., Ltd. (Comparative example 6). Unlike Fig. 1, any gap between graphene layers was not observed.
Table 1 Result of adsorption experiment using n-dodecane
Example 1 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7
Graphene (graphite oxide with thermal shock Graphene (chemical exfoliation without oxidation reaction) Graphene Graphite Graphite Graphite oxide Expanded graphite Carbon nanotubes
Material used (unit: gram) N-barotech graphene ER-2510 XG Science, Inc. (U.S.) Graphene Supermarket (U.S.) Qingdao Kropfmuehl Graphite QKG-296 Qingdao Kropfmuehl Graphite QKG-299 GO-3510 from N-barotech Co., Ltd. ES-100 from Samjung C&G Co., Ltd. CM-95 from Hanwha Nanotech Corp.
Composition Accordion shape, Fig. 1 20 layers or more Chemical vapor deposition, 99 % or more of carbon 96 % or more of carbon, specific gravity of 0.37 99 % or more of carbon, specific gravity of 0.23 55 % of carbon, 40 % of oxygen, average particle size of 100 ㎛ 95 % or more of carbon, average particle size of 100 ㎛ Produced by chemical vapor deposition, 95 % or more of carbon, diameter of 10 nm to 15 nm
Amount of adsorbed oil (g) 1.431 0.077 0.424 0 0 0 0.715 0.748
Adsorptivity (Q) 1,200 0 100 0 0 0 500 400
It could be seen that the graphite hardly adsorbed oil and the expanded graphite or the carbon nanotubes adsorbed oil to a certain degree. It could be seen that the graphene mixture applied with the thermal shock had an oil adsorptivity two or more times higher than the expanded graphite or the carbon nanotubes.
[Comparative example 8]
Water was put into a container and crude oil was poured on the water. A commercial oil-absorbing pad (SJ-M100 from Sejong) was immersed therein. Then, the amount of the oil adsorbed onto the oil-absorbing pad was measured. Filter paper was not used. An adsorptivity was measured by subtracting a weight of the oil-absorbing pad from a total amount of adsorption in the same manner as Example 1. A result thereof was provided in Table 2.
[Example 2]
An experiment was carried out in the same manner as Comparative example 8 using an oil-absorbing pad which was prepared by putting graphene in a tea bag. An oil adsorptivity was measured. A result thereof was provided in Table 2.
The commercial oil-absorbing pad adsorbed the crude oil in the amount of about seven times greater than the weight of the oil-absorbing pad. However, it could be seen that if the tea bag containing n-barotech graphene was used as an oil-absorbing pad, the tea bag adsorbed the crude oil in the amount of about sixty five or more times greater than a weight of the graphene used.
Table 2 Result of adsorption experiment using crude oil
Comparative example 8 Example 2
Oil-absorbing pad SJ-M100 from Sejong Weight (g) N-barotech graphene ER-2510 Weight (g)
Weight of oil-absorbing pad before experiment, M1 0.395
Weight of oil-absorbing pad after experiment, M2 3.292
Weight of oil adsorbed onto oil-absorbing pad 2.897
Tea bag x 5 weight 1.63
Weight of graphene used, M 0.10
Weight of oil adsorbed onto tea bag, M1 7.90
Weight of oil after adsorption, M2 14.77
Weight of oil adsorbed onto graphene 6.87
Adsorptivity (Q) 730% 6,550%
(M2-M1)/M1 (M2-M1)/M1

Claims (4)

  1. A multi-layered graphene mixture for adsorbing an organic material, wherein the multi-layered graphene mixture is produced by passing graphite oxide having a carbon/oxygen ratio of from about 1/1 to about 50/1 through a fluidized bed furnace maintained at from about 300℃ to about 1200℃ to apply a thermal shock thereto.
  2. The multi-layered graphene mixture for adsorbing an organic materialof claim 1, wherein the graphite oxide has a carbon/oxygen ratio of from about 1/1 to about 50/1 as an analysis result of an elemental analyzer and a maximum peak around 2θ = 10° according to an XRD analysis, and the multi-layered graphene mixture has an average surface area of from about 200 m2/g to about 2600 m2/g.
  3. The multi-layered graphene mixture for adsorbing an organic materialof claim 1, wherein the organic material is crude oil.
  4. A pack-shaped crude oil absorbent produced by mixing a binder with a multi-layered graphene mixture which is produced by passing graphite oxide through a fluidized bed furnace maintained at from about 300℃ to about 1200℃ to apply a thermal shock thereto, and press-molding and carbonizing a resultant mixture including the binder and the multi-layered graphene mixture.
PCT/KR2012/008898 2011-10-26 2012-10-26 Mixture of multi-layered graphene for adsorbing organic material WO2013062373A1 (en)

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CN103521199A (en) * 2013-10-26 2014-01-22 天津工业大学 Preparation method of hollow tubular composite oil absorption material
CN103801274A (en) * 2014-02-28 2014-05-21 天津工业大学 Preparation method of oil-absorbing hollow fiber porous membrane
CN104525107A (en) * 2014-12-03 2015-04-22 杜茂龙 Graphene-based haze-resisting mask filtering material and preparation method thereof

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CA2962721C (en) * 2014-10-10 2020-07-14 Toray Industries, Inc. Graphene powder, electrode paste for lithium ion battery and electrode for lithium ion battery
KR101950579B1 (en) * 2017-05-12 2019-02-20 고려대학교 산학협력단 Absorbent For Carbon Dioxide and Method for Manufacturing The Same

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JPH0596157A (en) * 1991-10-04 1993-04-20 Nippon Kasei Chem Co Ltd Production of oil adsorbent
US20110114897A1 (en) * 2008-02-05 2011-05-19 The Trustees Of Princeton University Functionalized graphene sheets having high carbon to oxygen ratios
KR101053933B1 (en) * 2009-08-10 2011-08-04 엔바로테크 주식회사 Graphite oxide manufacturing method and apparatus for producing nano-sized graphene structural material

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Publication number Priority date Publication date Assignee Title
JPH0531360A (en) * 1991-07-31 1993-02-09 Nippon Carbon Co Ltd Adsorbent for collecting extremetly small quantity of component
JPH0596157A (en) * 1991-10-04 1993-04-20 Nippon Kasei Chem Co Ltd Production of oil adsorbent
US20110114897A1 (en) * 2008-02-05 2011-05-19 The Trustees Of Princeton University Functionalized graphene sheets having high carbon to oxygen ratios
KR101053933B1 (en) * 2009-08-10 2011-08-04 엔바로테크 주식회사 Graphite oxide manufacturing method and apparatus for producing nano-sized graphene structural material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521199A (en) * 2013-10-26 2014-01-22 天津工业大学 Preparation method of hollow tubular composite oil absorption material
CN103521199B (en) * 2013-10-26 2015-08-26 天津工业大学 A kind of preparation method of hollow tubular composite oil absorption material
CN103801274A (en) * 2014-02-28 2014-05-21 天津工业大学 Preparation method of oil-absorbing hollow fiber porous membrane
WO2015127792A1 (en) * 2014-02-28 2015-09-03 天津工业大学 Method for preparing oil-absorbing hollow fiber porous membrane
CN104525107A (en) * 2014-12-03 2015-04-22 杜茂龙 Graphene-based haze-resisting mask filtering material and preparation method thereof

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