KR20160002532A - Method for manufacturing porous graphene filter, porous graphene filter manufactued using the method, and filter apparatus using the porous graphene filter - Google Patents

Abstract

The present invention provides a manufacturing method of a porous graphene filter and a porous graphene filter manufactured by using the same. Very small-sized holes are artificially formed in graphene having a carbon monoatomic layer structure, and a certain material of a mixed material, produced by mixing a plurality of materials, can be selectively filtered by using a plurality of porous graphene filters having the holes artificially formed in the graphene. The manufacturing method of the porous graphene filter comprises the following steps: substituting some of carbon atoms with a substitution atom which is produced from a substitution source while film-forming the graphene with carbon atoms produced from a carbon source, and forming a first graphene filter where first holes having a first size are formed in the graphene; substituting some of the carbon atoms with the substitution atom produced from the substitution source while film-forming the graphene with the carbon atoms produced from the carbon source, and forming a second graphene filter where second holes having a second size which is larger than the first size are formed in the graphene; and arranging the first and second graphene filters inside a filter body where an inlet and an outlet are formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a porous graphene filter, a porous graphene filter manufactured using the same, and a filter device using the porous graphene filter. [0002]

The present invention relates to a method of manufacturing a porous graphene filter and a porous graphene filter manufactured using the porous graphene filter. More particularly, the present invention relates to a porous graphene filter using porous graphene, The present invention relates to a method for manufacturing a porous graphene filter capable of selectively filtering a material, a porous graphene filter manufactured using the same, and a filter device using the same.

Recently, the development of graphene technology including a carbon monomolecular layer has been progressing rapidly.

Graphene has a single atomic layer in which carbon atoms are formed in a single layer. The conductivity of graphene is very superior to that of copper. The electron mobility of graphene is faster than that of silicon, and graphene has a very high strength Graphene has been applied to various fields such as ultra-high speed semiconductor, flexible display using transparent electrode, computer parts, and high efficiency solar cell.

BACKGROUND ART Conventionally, graphene used in semiconductors, displays, computer parts, and solar cells has been developed in the technical direction of preventing defects such as through holes from being formed in graphene.

Patent No. 10-2013-0033794 A method for manufacturing a filter and a filter manufactured thereby (2013.04.04)

The present invention relates to a method of forming graphene having a carbon monomolecular layer structure by artificially forming very small holes in graphene and using a plurality of porous graphene filters having artificially formed holes in graphene, A porous graphene filter capable of selectively filtering a specific material among mixed materials in which materials are mixed, a porous graphene filter manufactured using the same, and a filter device using the same.

In one embodiment, a method of making a porous graphene filter comprises substituting some carbon atoms with substituting atoms generated from a substitution source during deposition of the graphene with carbon atoms generated from the carbon source to form graphene having a first size Forming a first graphene filter having first holes formed therein; The second hole having a second size larger than the first size is formed in the graphene by replacing some carbon atoms with substitution atoms generated from the substitution source during deposition of the graphene with carbon atoms generated from the carbon source, Forming a graphene filter; And disposing the first and second graphene filters inside a filter body having an inlet and an outlet.

The substitution source forming the first holes in the first graphene filter and the substitution source forming the second holes in the second graphene filter comprise nitrogen atoms.

In the step of forming the first graphene filter, the amount of the substitutional source is smaller than the amount of the substitutional source in the step of forming the second graphene filter.

The carbon source is methane (CH _4), methanol (CH ₃ OH), carbon monoxide (CO), ethane (C ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H ₂ ), acetone (CH ₃ COCH _3), propane _{(CH 3 CH 2 CH 3)} , propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), polymethylpentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), cyclohexane (C ₆ H _12), benzene (C ₆ H _6), toluene (C ₇ H ₈₎ and And xylene (C ₆ H ₄ (CH ₃ ) ₂ ).

The substitution source may be selected from the group consisting of ammonia, polypyrrole, polyvinyl-pyrrolidone, phtnipropanolamine, pyridine, pyrimidine, polyacrylonitrile, 4-vinylpyridine, polyaniline, poly-4-vinylpyridine, poly (butadiene-b-4-vinylpyridine) Poly (p-phenylenevinylenimine), phenol formaldehyde resin, polyacetonitrile and poly (aniline-co-N-propylbenzenesulfonate-aniline) N-propylbenzenesulfonic acid-aniline).

When forming the first and second graphene filters, the carbon source and the substitution source are respectively vaporized at the same time to provide a deposition furnace in which the first and second graphene filters are formed.

In one embodiment, the porous graphene filter includes a first graphene filter in which first holes having a first size are formed by replacing a carbon atom having a crystal defect in a covalent bond portion of carbon atoms constituting graphene with a substitution atom; A second graphene filter in which second holes having a second size are formed by replacing a carbon atom having a crystal defect in a covalent bond portion among carbon atoms constituting graphene with a substitution atom; And a filter body into which mixed materials in which a plurality of materials are mixed are introduced and which fixes the first and second graphene filters on the movement path of the mixed materials.

The first and second graphene filters of the porous graphene filter are formed in a film shape or a cylindrical shape.

In one embodiment, the filter device includes: a mixed material supply device for intermittently providing an amount of mixed material mixed with materials having different sizes; A filter body having an inlet provided with the mixed material and having at least two outlets on a side thereof, at least one filter disposed inside the filter body and having holes for separating the substances contained in the mixed material, A graphene filter including a graphene thin film; And a recovery unit connected to each of the outlets for recovering respective materials separated from the mixed material.

The mixed substance supply device of the filter device may further comprise: a mixed substance supply unit for providing the mixed substance; A storage container for storing a predetermined amount of the mixed material; And a discharge unit for discharging the mixed substance stored in the storage container.

The discharge unit of the filter device includes a blower for providing air or an inert gas to the storage container.

The filter device comprising: electromagnetic valves coupled to the mixed material supply device, the graphene filter, and the collection device; And a valve controller for controlling the solenoid valves.

The graphene filter of the filter device comprising: a first graphene filter disposed on an inner surface of the filter body and having first holes having a first size; And a second graphene filter disposed on the inner surface of the filter body so as to face the first graphene filter and having second holes having a second size.

The method of manufacturing a porous graphene filter according to the present invention and the porous graphene filter fabricated using the method can form artificially small holes in a graphene thin film while forming a graphene thin film having a carbon mono-element layer structure, The present invention has an effect of selectively filtering and separating a specific substance from a mixed substance in which a plurality of substances are mixed by using a porous graphene filter having holes formed artificially in graphene.

1 is a flowchart illustrating a method of manufacturing a porous graphene filter according to an embodiment of the present invention.
FIG. 2 is a plan view showing the first graphene filter of FIG. 1; FIG.
3 is a plan view showing the second graphene filter of FIG.
4 is a block diagram showing an apparatus for manufacturing the first graphene filter or the second graphene filter shown in FIG.
5 is a cross-sectional view illustrating a porous graphene filter according to an embodiment of the present invention.
6 is a conceptual diagram showing a filtering process of the porous graphene filter of FIG.
FIGS. 7 and 8 are perspective views showing that the first and second graphene filters are formed into a film shape or a cylindrical shape.
9 is a block diagram showing a filter device according to another embodiment of the present invention.

In the following description, only parts necessary for understanding the embodiments of the present invention will be described, and the description of other parts will be omitted so as not to obscure the gist of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor is not limited to the meaning of the terms in order to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

The term "graphene " which is frequently used in the present invention is formed into a film-like structure in which carbon atoms form a one atomic layer, Is defined as six repeating units covalently bonded in a ring shape.

However, in the present invention, a monolayer structure in which five carbon atoms are mutually covalent bonds as basic repeating units or 7 carbon atoms are covalently bonded as basic repeating units can also be defined as "graphene ".

The term " crystal defect or defect " which is frequently used in the present invention refers to a state in which a part of carbon atoms of graphene is substituted for a nitrogen atom or the like to replace a carbon atom constituting graphene It is defined as breaking at least one of the bonds.

1 is a flowchart illustrating a method of manufacturing a porous graphene filter according to an embodiment of the present invention. FIG. 2 is a plan view showing the first graphene filter of FIG. 1; FIG. 3 is a plan view showing the second graphene filter of FIG.

1 and 2, in order to fabricate a porous graphene filter, first a first graphene filter 1 having first holes H1 having an average size of first size S1 is formed. Step S10)

In step S10, in order to form the first graphene filter 1 on which the first holes H1 having the first size S1 are formed on an average, first, graphene is decomposed into carbon atoms and hydrogen atoms at a high temperature A step of vaporizing a carbon source comprising a carbon precursor is performed.

In an embodiment of the present invention, when a carbon source is vaporized and provided as a deposition furnace, the porous graphene filter can be produced by a very simple process.

In an embodiment of the present invention, examples of materials that can be used as the carbon source for forming the first graphene filter 1 include methane (CH ₄ ), methanol (CH ₃ OH), carbon monoxide (CO), ethane ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H _2), acetone (CH ₃ COCH _3), propane _{(CH 3 CH 2 CH 3)} , propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), Carbon atoms separated by carbon atoms and hydrogen atoms such as cyclohexane (C ₆ H ₁₂ ), benzene (C ₆ H ₆ ), toluene (C ₇ H ₈ ) and xylene (C ₆ H ₄ (CH ₃ ) ₂ ) Hydrocarbons can be mentioned.

Further, in order to vaporize the carbon source and simultaneously form first holes H1 having a first size (S1) on the graphene while forming the graphene by the carbon source, the carbon atoms A step of vaporizing a substitution source (or a doping source) for forming a crystal defect in some of the carbon atoms and substituting a substitution atom for the covalent bond portion broken by the crystal defect is carried out.

In one embodiment of the present invention, as the substitution source, a nitrogen precursor including a nitrogen compound may be used.

First graphene filter 1 of the first hole (H1) examples include ammonia (NH ₄₎ a nitrogen compound which can be used as the substitution source for forming the, polypyrrole (polypyrrole), polyvinyl pyrrolidone (polyvinyl-pyrrolidone) Pyridine, polyacrylonitrile, polyaniline, poly-4-vinylpyridine, poly (4-vinylpyridine), poly (Butadiene-b-4-vinylpyridine), poly (p-phenylenevinylenimine), phenol formaldehyde resin, ), Polyacetonitrile, and a nitrogen compound such as poly (aniline-co-N-propylbenzenesulfonic acid-aniline).

In one embodiment of the present invention, a carbon source providing the carbon atoms forming the first graphene filter 1 and a first carbon film 1 having an average first size S1 during formation of the first graphene filter 1 Substitution sources for forming the holes H1 are vaporized in a simultaneous vaporization manner in different vessels in order to produce a first quality graphene filter.

The carbon source and the substitution source vaporized in a simultaneous vaporization manner to form the first graphene filter 1 are each provided inside a deposition func- tion in which process conditions suitable for forming the graphene are formed, The carbon source and the vaporized substitution source are mixed in the interior of the deposition furnace.

The carbon source provided to the inside of the deposition furnace is thermally decomposed into carbon atoms and hydrogen atoms inside the deposition furnace and the hydrogen atoms are exhausted to the outside of the deposition furnace and the carbon atoms are deposited in the monolayer structure on the substrate disposed inside the deposition furnace .

When the carbon atoms are deposited on the substrate in the interior of the deposition furnace, the substitution source provided inside the deposition furnace is decomposed into nitrogen atoms inside the deposition furnace, and the nitrogen atoms act on the covalently bonded portions of some carbon atoms of the carbon atoms Doped) to induce crystal defects, and the nitrogen atoms are bonded to the broken covalent bond portion of the carbon atoms in which the crystal defects are generated.

As the covalent bonds of carbon atoms are replaced with nitrogen atoms, a first graphene filter (1) having first holes (H1) having an average size of first size (S1) is formed on the substrate disposed inside the deposition furnace do.

In one embodiment of the present invention, when the number of covalent bonds of carbon atoms increases and more nitrogen atoms are bonded to crystal defect portions of the carbon atom, the first holes (H1 The larger the first size S1 of the first and second lens groups.

That is, the number of the first holes H1 formed in the first graphene filter 1 and the average first size S1 of the first holes H1 are set to the ratio of the carbon source and the substitution source or the concentration of the substitution source .

When the amount of substitution source is increased with respect to a certain amount of carbon source, crystal defects are generated in a larger number of carbon atoms in graphene and nitrogen atoms are bonded to carbon atoms in which crystal defects are generated, The average first size S1 of the first holes H1 of the first graphene filter 1 is increased.

Conversely, when reducing the amount of substitutional source for a certain amount of carbon source, crystal defects are generated at a smaller number of carbon atoms in graphene, and the crystal defects are bonded to the generated carbon atoms by nitrogen atoms, The average first size S1 of the first holes H1 of the first graphene filter 1 is reduced because the number of the first holes H1 is reduced.

In one embodiment of the present invention, the data of the average first size S1 of the first holes H1 formed in the graphene, the first size S1 of the first holes H1, Can be obtained by experimenting while changing the ratio of the substitution source.

1 and 3, a second hole H2 having an average second size S2 is formed after the first graphene filter 1 is formed or when the first graphene filter 1 is formed. A second graphene filter 2 is formed. (Step S20)

In order to form the second graphene filter 2 formed with the second holes H2 having an average second size S2 in step S20 of Fig. 1, first, a carbon precursor for forming graphene A step of vaporizing the carbon source is performed.

In one embodiment of the present invention, examples of materials that can be used as the carbon source for forming the second graphene filter 2 include methane (CH ₄ ), methanol (CH ₃ OH), carbon monoxide (CO), ethane ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H _2), acetone (CH ₃ COCH _3), propane _{(CH 3 CH 2 CH 3)} , propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), Carbon atoms separated by carbon atoms and hydrogen atoms such as cyclohexane (C ₆ H ₁₂ ), benzene (C ₆ H ₆ ), toluene (C ₇ H ₈ ) and xylene (C ₆ H ₄ (CH ₃ ) ₂ ) Hydrocarbons can be mentioned.

In one embodiment of the present invention, the carbon source used in forming the second graphene filter 2 may be the same as or different from the carbon source used in forming the first graphene filter 1.

Also included in the graphene layer to form the second holes H2 having an average second size S2 during vaporization of the carbon source and forming the second graphene filter 2 by the carbon source, A step of vaporizing a substitution source (or a doping source) for forming crystal defects in some carbon atoms of the carbon atoms and substituting substituted atoms for covalent bond portions broken by crystal defects is performed.

In one embodiment of the present invention, as the substitution source of the second graphene filter 2, a nitrogen precursor including a nitrogen compound may be used.

Examples of nitrogen compounds which can be used as the substitution source of the second graphene filter 2 include ammonia (NH ₄ ), polypyrrole, polyvinyl-pyrrolidone, phenylpropanolamine, pyridine, pyrimidine, polyacrylonitrile, polyaniline, poly-4-vinylpyridine, poly (butadiene-b-4-vinylpyridine) poly (p-phenylenevinylenimine), phenol formaldehyde resin, polyacetonitrile, and poly (p-phenylene-vinylene) (Aniline-co-N-propylbenzenesulfonic acid-aniline) and the like.

In one embodiment of the present invention, the substitution source for forming the second graphene filter 2 and the substitution source for forming the first graphene filter 1 may be the same or different.

In one embodiment of the present invention, a carbon source providing the carbon atoms forming the second graphene filter 2 and a second carbon film 2 having an average second size S2 during formation of the second graphene filter 2, Substitution sources for forming the holes H2 are vaporized in a simultaneous vaporization manner in different vessels for mass production of the second graphene filter 2.

The carbon source and the substitution source vaporized by the simultaneous vaporization method to form the second graphene filter 2 are each independently formed into a deposition process in which process conditions suitable for forming the graphene of the second graphene filter 2 are formed , And the vaporized carbon source and the vaporized substitution source are mixed inside the vapor deposition furnace.

The carbon source provided to the inside of the deposition furnace is thermally decomposed into carbon atoms and hydrogen atoms inside the deposition furnace and the hydrogen atoms are exhausted to the outside of the deposition furnace and the carbon atoms are deposited in the monolayer structure on the substrate disposed inside the deposition furnace .

When the carbon atoms are deposited on the substrate in the interior of the deposition furnace, the substitution source provided inside the deposition furnace is decomposed into nitrogen atoms inside the deposition furnace, and the nitrogen atoms act on the covalently bonded portions of some carbon atoms of the carbon atoms Doped) to induce crystal defects, and the nitrogen atoms are bonded to the broken covalent bond portion of the carbon atoms in which the crystal defects are generated.

The second graphene filter 2 formed with the second holes H2 having the second size S2 on the average is formed on the substrate disposed inside the deposition furnace as the portion where the covalent bonds of the carbon atoms are replaced with nitrogen atoms do.

In an embodiment of the present invention, the number of second holes H2 formed in the second graphene filter 2 and the average second size S2 of the second holes H2 are set such that the ratio of the carbon source and the substitution source Or the concentration of the substitution source.

Specifically, when increasing the amount of the substitution source provided for a certain amount of carbon source, a greater number of carbon atoms in graphene are substituted with nitrogen atoms, thereby increasing the number of second holes (H2) (S2) is increased.

Conversely, if the amount of substitution source is reduced for a certain amount of carbon source, a smaller number of carbon atoms are substituted with nitrogen atoms in graphene to reduce the number of second holes (H 2) The average second size S2 is reduced.

The data of the average second size S2 of the second holes H2 formed in the graphene and the deviation data of the second size S2 of the second holes H2 are obtained from the carbon source And the ratio of the substitution source.

In one embodiment of the present invention, the average second size S2 of the second holes H2 of the second graphene filter 2 formed in step S20 is smaller than the average second size S2 of the first graphene filter 1 formed in step S10 May be less than or equal to an average first size (S1) of the first holes (H1).

The second hole H2 having the largest size among the second holes H2 of the second graphene filter 2 is the smallest one of the first holes H1 of the first graphene filter 1, Or less.

Although the average second size S2 of the second holes H2 of the second graphene filter 2 formed in step S20 is smaller than the average second size S2 of the first graphene filter 1 in step S10, The average second size S2 of the second holes H2 of the second graphene filter 2 is smaller than the average first size S1 of the first holes H1, May be equal to or larger than an average first size (S2) of the first holes (H1) of the first graphene filter (1).

In one embodiment of the present invention, a first graphene filter 1 having first holes H1 with an average first size S1 and a second hole H2 having an average second size S2, May be sequentially formed in one deposition furnace or may be formed separately in different deposition furnaces.

The first graphene filter 1 having the first holes H1 having the first size S1 on the average is formed in step S10 and the second holes H1 having the second size S2 on the average are formed in the step S20, S2 are formed, the first and second graphene filters 1, 2 are mounted on the filter body to produce a porous graphene filter (step S30).

The first graphene filter 1 manufactured in Step S10 and the second graphene filter 2 manufactured in Step S20 are provided in the filter body 2, The first holes H1 and the second holes H2 of the first and second graphene filters 1 and 2 are used to separate the materials from the mixed material. Respectively.

For example, when a porous graphene filter is used, the carbon dioxide contained in the air is selectively filtered, the impurities contained in the water are selectively filtered, the specific substance is selectively filtered from the automobile exhaust gas, the impurities contained in the blood Or specific substances contained in the blood can be selectively filtered.

4 is a block diagram showing an apparatus for manufacturing the first graphene filter or the second graphene filter shown in FIG.

Referring to FIG. 4, an apparatus 700 for manufacturing a porous graphene filter fabricates a first graphene filter and a second graphene filter shown in FIG.

In one embodiment of the present invention, the first graphene filter 1 and the second graphene filter 2 may all be manufactured from one porous graphene filter manufacturing apparatus 700. Alternatively, the first graphene filter 1 or the second graphene filter 2 may be manufactured from a different porous graphene filter manufacturing apparatus 700.

The porous graphene filter manufacturing apparatus 700 includes a sample supply apparatus 200, a synchronous vaporizer 300, and a deposition furnace 400. In addition, the porous graphene member manufacturing apparatus 700 may further include a carrier gas supply unit 500.

The sample supply device 200 includes a first sample supply device 210 and a second sample supply device 220.

The first sample supply device 210 provides a carbon source for forming the graphene to the first vaporizer 310 of the simultaneous vaporizer 300 to be described later.

The carbon source provided from the first sample supply device 210 to the first vaporizer 310 may be a carbon precursor containing hydrocarbons decomposed into carbon atoms and hydrogen atoms inside the deposition furnace 400. [

Examples of carbon precursors provided from the first sample supply device 210 include carbon (CH ₄ ), methanol (CH ₃ OH), carbon monoxide (CO), ethane (C ₂ H ₆ ), ethylene (CH ₂ ), ethanol ₂ H _5), acetylene (C ₂ H _2), acetone (CH ₃ COCH _3), propane _{(CH 3 CH 2 CH 3)} , propylene (C ₃ H _6), butane (C ₄ H _10), pentane (CH _{3 (CH 2) 3 CH 3} ), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), cyclohexane (C ₆ H _12), benzene (C ₆ H ₆ ), toluene (C ₇ H ₈ ), xylene (C ₆ H ₄ (CH ₃ ) ₂ ), and the like.

In one embodiment of the present invention, when the gaseous carbon precursor is stored in the first sample supply device 210, the gaseous carbon precursor provided from the first sample supply 210 is supplied to the first vaporizer 300 of the simultaneous vaporizer 300, May be provided to the deposition furnace 400 by bypassing the deposition chamber 310.

The second sample supply device 220 provides a replacement source (or doping source) that forms a through-hole in the graphene to a second vaporizer 320 of a simultaneous vaporizer 300, which will be described later.

In one embodiment of the present invention, a sample conditioning device 225 for precisely controlling the concentration of the displacement source and the amount of the displacement source is coupled to the second sample supply device 220 that provides the displacement source to the vaporizer 300 .

The sample conditioning supply device 225 can be used to change the supply amount of the substitution source provided to the second vaporizer 320 so that the first holes H1 having the first size S1 shown in FIG. It is possible to form the second graphene filter 2 having the first graphene filter 1 and the second holes H2 having the second size S2 shown in Fig.

Although control of the concentration of the substitution source supplied from the second sample supply device 220 to the second vaporizer 320 and the supply amount of the substitute source by the sample adjusting device 225 in an embodiment of the present invention, Alternatively, the first and second sample supply devices 210 and 220 may be provided with a solenoid valve or a flow rate controller (MFC) for individually controlling the amount of the carbon source and the displacement source, respectively.

The displacement source provided from the second sample supply device 220 to the second vaporizer 320 may be a nitrogen precursor comprising a nitrogen compound.

Examples of the nitrogen precursor which is the substitution source provided from the second sample supply device 220 shown in FIG. 4 include ammonia (NH ₄ ), polypyrrole, polyvinyl-pyrrolidone, Pyridine, pyrimidine, poly (acrylonitrile), polyaniline, poly-4-vinylpyridine, poly (butadiene-b-4) Butadiene-b-4-vinylpyridine, poly (p-phenylenevinylenimine), phenol formaldehyde resin, polyacetonitrile polyacetonitrile) and poly (aniline-co-N-propylbenzenesulfonic acid-aniline).

In one embodiment of the present invention, when a gaseous nitrogen precursor is provided from the second sample supply device 220, the gaseous nitrogen precursor provided from the second sample supply 220 is supplied to the second vaporizer 300 of the simultaneous vaporizer 300, May be provided to the deposition furnace 400 by bypassing the deposition chamber 320.

The simultaneous vaporizer 300 includes a first vaporizer 310 and a second vaporizer 350.

The first vaporizer 310 is in communication with the first sample supply device 210 so that the first vaporizer 310 is provided with a carbon precursor which is, for example, a carbon source from the first sample supply device 210 .

The first vaporizer 310 includes a vessel including an inlet through which a carbon precursor to be vaporized flows and an outlet through which a vaporized carbon precursor is discharged, the inlet communicates with the first sample supply device 210, And communicates with the inside of the deposition furnace 400.

A first heating furnace 315 is disposed outside the first vaporizer 310 to heat the carbon precursor provided to the first carburetor 310 by heat and a heat generated inside the first heating furnace 315 Heat lines 316 may be disposed. In the first heating furnace 315, various heat generating devices other than the heating line 316 may be disposed.

The second vaporizer 320 is in communication with the second sample supply device 220 so that the second vaporizer 320 is supplied from the second sample supply device 220 with a nitrogen precursor, .

The second vaporizer 320 includes a vessel including an inlet through which a nitrogen precursor to be vaporized is supplied and an outlet through which a vaporized nitrogen precursor is discharged, the inlet communicates with the second sample supply device 220, And communicates with the inside of the deposition furnace 400.

The second heating furnace 325 is disposed outside the second vaporizer 320 to vaporize the nitrogen precursor provided to the second vaporizer 320 by heat and the heat generated inside the second heating furnace 325 Heat lines 326 are disposed. In the second heating furnace 325, various heat generating devices other than the heat ray 326 may be arranged.

Although one embodiment of the present invention uses first and second heating furnaces 315 and 325 that include heat lines 316 and 326 to vaporize the carbon precursor and the nitrogen precursor respectively provided in the first and second vaporizers 310 and 320 Alternatively, the carbon precursor and the nitrogen precursor may be chemically vaporized by providing a reaction gas to the carbon precursor and the nitrogen precursor.

In order to transport the carbon precursor vaporized from the first vaporizer 310 and the nitrogen precursor vaporized from the second vaporizer 320 to the vaporization furnace 400, the first vaporizer 310 and the second vaporizer 320 The carrier gas supply unit 500 is communicated.

The carrier gas supply unit 500 supplies an inert gas such as nitrogen or argon to the first vaporizer 310 and the second vaporizer 320 and the carbon precursor vaporized in the first vaporizer 310 and the second vaporizer 320, The vaporized nitrogen precursor is transported to the deposition furnace 400 by the inert gas provided from the carrier gas supply unit 500, respectively.

The carrier gas supply unit 500 and the first vaporizer 310, the carrier gas supply unit 500 and the second vaporizer 320 are communicated with the inert gas supply pipes 510 and 520, respectively. A mass flow controller (MFC) may be coupled to each of the inert gas supply pipes 510 and 520 to control the flow rate of the inert gas.

In an embodiment of the present invention, the flow rate of the inert gas supplied to the first vaporizer 310 and the second vaporizer 320 is controlled differently in the carrier gas supply unit 500, thereby obtaining the first size S1 shown in FIG. 2 The first graphene filter 1 having the first holes H1 having the first size H1 and the second holes H2 having the second size S2 shown in FIG. .

4, the outlet of the first vaporizer 310 through which the vaporized carbon precursor is discharged from the first vaporizer 310 is communicated with the first pipe 317, and the nitrogen vaporized from the second vaporizer 320 The outlet of the second vaporizer 320 through which the precursor is discharged is communicated with the second pipe 327.

The first piping 317 and the second piping 318 communicate with the common piping 330 and the common piping 330 communicates with the deposition path 400.

The vaporized carbon precursor provided through the first pipe 317 and the vaporized nitrogen precursor provided through the second pipe 327 are mixed in the common pipe 330 and then supplied to the deposition furnace 400, The vaporized carbon and nitrogen precursors may be provided uniformly mixed into the deposition furnace 400.

In one embodiment of the present invention, the temperature of the vaporized nitrogen precursors provided to the common line 330 through the second line 327 and the vaporized carbon precursor provided to the common line 330 through the first line 317 A heating unit 335 may be mounted on the common line 330 to prevent the carbon and nitrogen precursors vaporized by the change from re-liquefying or being deposited on the inner walls of the first and second lines 317 and 327.

The heating unit 335 may include, for example, a heating line that consumes electrical energy to generate heat and the heating unit 335 heats the common line 330 to generate a temperature change of the vaporized carbon and nitrogen precursors .

In one embodiment of the present invention, it is shown and described that a heating unit 335 is formed in a common pipe 330 where the vaporized carbon precursor and the vaporized nitrogen precursor are combined, And may further be installed in the pipe 317 and the second pipe 327.

4, the deposition furnace 400 includes the carbon precursor and the second vaporizer 320 provided in the first vaporizer 310, the first pipe 317 and the common pipe 330, the second pipe 327, And a space for forming the first and second graphene filters 1 and 2 shown in FIGS. 2 and 3 and a space for forming the first and second graphene filters 1 and 2 using the nitrogen precursor provided in the common pipe 330 , 2) to form the process conditions and the process atmosphere.

The deposition furnace 400 for forming the process conditions and the process atmosphere for forming the first and second graphene filters 1 and 2 may be formed by a chemical vapor deposition equipment, The thermal chemical vapor deposition equipment, the rapid thermal chemical vapor deposition equipment, the inductively coupled plasma chemical vapor deposition equipment, the atomic layer deposition equipment, equipment may be used.

In one embodiment of the present invention, atomic layer deposition (ALD) is preferably used because it forms a monolayer layer graphene on a substrate disposed within the deposition furnace 400.

The substrate 410, which is disposed inside the deposition furnace 400 and on which the first and second graphene filters 1 and 2 are deposited, may be formed on the substrate 410 by, for example, 2 graphene filters 1 and 2 are made of a metal material which is easily separated from the substrate 410 and does not cause shape deformation in high-temperature heat.

The metal material disposed in the interior of the deposition furnace 400 may include, for example, a copper plate or a copper plated plate having weak adhesion to the first and second graphene filters 1 and 2.

Although the substrate on which the first and second graphene filters 1 and 2 are formed is a copper plate or a copper plated plate disposed inside the deposition furnace 400 in an embodiment of the present invention, The substrate disposed within the furnace 400 may include a variety of metal materials suitable for easily peeling the first and second graphene filters 1,2 from the substrate.

5 is a cross-sectional view illustrating a porous graphene filter according to an embodiment of the present invention. 6 is a conceptual diagram showing a filtering process of the porous graphene filter of FIG.

Referring to FIGS. 5 and 6, the porous graphene filter 800 includes a first graphene filter 1, a second graphene filter 2, and a filter body 750.

Referring to FIGS. 2 and 5, the first graphene filter 1 includes a method of manufacturing the first and second graphene filters 1 and 2 shown in FIG. 1 and a method of manufacturing the porous graphene filter shown in FIG. And the first graphene filter 1 has a structure as shown in Fig.

The first graphene filter 1 forms a crystal defect in some carbon atoms of carbon atoms by providing nitrogen atoms serving as a substitution source to the graphenes formed during the formation of carbon atoms formed by decomposing the carbon source into graphene And a crystal defect is formed by replacing the generated carbon atom with a nitrogen atom.

The first graphene filter 1 includes first holes H1 having a first size S1 as shown in Fig.

The first graphene filter 1 may be formed in a film shape as shown in Fig. 7, and when the first graphene filter 1 is formed in a film shape, the rim of the first graphene filter 1 A square frame is combined.

By coupling the first graphene filter 1 to the square frame, the first graphene filter 1 has a very high tensile strength and compressive strength.

In one practical example of the present invention, the first graphene filter 1 may be formed into a cylindrical shape as shown in FIG. 8, and when the first graphene filter 1 is formed into a cylindrical shape, A ring-shaped frame is coupled to both ends of the graphene filter 1.

By combining the first graphene filter 1 having a cylindrical shape with the ring-shaped frame, the first graphene filter has a very high tensile strength and compressive strength.

Referring to FIGS. 2 and 5, the second graphene filter 2 is formed by the method of manufacturing the first and second graphene filters 1 and 2 shown in FIG. 1 and the method of manufacturing the porous graphene filter shown in FIG. And the second graphene filter 2 has a structure as shown in Fig.

The second graphene filter (2) forms a crystal defect in some carbon atoms of the carbon atoms by providing nitrogen atoms serving as a substitution source to the graphenes formed during the film formation of the carbon atoms formed by decomposing the carbon source And a crystal defect is formed by replacing the generated carbon atom with a nitrogen atom.

The second graphene filter 2 includes second holes H2 having a second size S2 as shown in Figure 3 and the second holes H2 of the second graphene filter 2 The second size S2 is formed to be larger than the first size S1 of the first holes H1 of the first graphene filter 1.

In one embodiment of the present invention, the second size S2 of the second hole H2 of the second graphene filter 2 is changed by changing the concentration of the substitution source and the amount of the substitution source supplied to the carbon source do.

The second graphene filter 2 may be formed in a film shape as shown in Fig. 7, and when the second graphene filter 2 is formed in a film shape, the rim of the second graphene filter 2 A square frame is combined. By coupling the second graphene filter 2 to the square frame, the second graphene filter 2 has a very high tensile strength and compressive strength.

In a practical example of the present invention, the second graphene filter 2 may be formed into a cylindrical shape as shown in FIG. 8, and when the second graphene filter 2 is formed into a cylindrical shape, At both ends of the graphene filter 2, frames having a ring shape are joined.

The second graphene filter 2 has a very high tensile strength and compressive strength by combining the second graphene filter 2 having a cylindrical shape with the ring-shaped frame.

In one embodiment of the present invention, the first and second graphene filters 1, 2 are formed in a film shape, for example, as shown in Fig. 8, and the first and second grains A rectangular frame is coupled to each of the rims of the pin filters 1 and 2.

In an embodiment of the present invention, the first and second graphene filters 1 and 2 are each formed in a rectangular film shape, and a rectangular frame is coupled to the edges of the first and second graphene filters 1 and 2. [ The first and second graphene filters 1 and 2 are formed in a disc shape and the first and second graphene filters 1 and 2 having a disc shape are respectively formed into a circular shape Frames may be combined.

The first and second graphene filters 1 and 2 coupled to the square frame are each coupled to the interior of the filter body 750 and the first and second graphene filters 1 and 2 are spaced apart from each other .

The filter body 750 may be formed in a cylindrical shape having both ends open or closed at one end.

The filter body 750 is formed in a cylindrical shape having openings at both ends including an inlet portion 752 and a discharge portion 754 opposed to the inlet portion 751, for example. The filter body 750 may be formed of, for example, a highly rigid metal material or a synthetic resin material.

Mixed materials in which at least two substances are mixed are introduced into the inlet portion 752 of the filter body 750 and the filtered material is discharged from the mixed materials through the outlet portion 754 of the filter body 750.

Referring to FIG. 6, the first and second graphene filters 1 and 2 are disposed apart from each other in the filter body 750, and the first and second graphene filters 1 and 2 are connected to the inlet portion 752 of the filter body 750, A material having a size larger than the average first size S1 of the first hole H1 of the pin filter 1 and the average first size H1 of the first graphene filter 1 B material having a size smaller than the average second size S2 of the second hole H2 of the second graphene filter 2 and smaller than the second hole S2 of the second graphene filter 2, The C material, which is the target material, is introduced into the first graphene filter 1 when the mixed material having the size smaller than the average second size S2 of the first graphene filter H2 is introduced, While the A material and the B material pass through the first hole H1 of the first and second graphene filters 2 and 2 and the second hole H2 of the second graphene filter 2, It is impossible to pass through the first and second holes H1 and H2.

9 is a block diagram showing a filter device according to another embodiment of the present invention.

The filter device according to Fig. 9 allows for the recovery of the respective substances from mixed materials in which at least two substances having different sizes are mixed.

The filter device 900 includes a mixture supply device 910, a graphene filter 950, a collection unit 960, a blower 970 and a valve controller 980.

Mixture feeder 910 provides a mixture of at least two materials having different sizes to a graphene filter 950, described below.

The mixture supply device 910 includes a mixed substance supply unit 912, a storage container 914, a discharge unit 916, and a solenoid valve 918,919 in which the mixed materials are provided.

The mixed substance supply unit 912 may be, for example, an A material having a first size on average, a B material having a second size smaller than the first size on average and a third material having an average size smaller than the second size C material is supplied from the outside and supplied to the storage container 914. [

The mixed material supply unit 912 and the storage container 914 are connected to each other by a pipe 913 and the pipe 913 is provided with a mixed material to the storage container 914 or a mixed material is supplied to the storage container 914 And the solenoid valve 918 is opened and closed by a control signal provided from a valve controller 980 to be described later.

The storage container 914 is connected to the pipe 913, and the storage container 914 serves to temporarily store a certain amount of mixed material.

A discharge pipe 915 for discharging a predetermined amount of the mixed substance temporarily stored in the storage container 914 is connected to the discharge pipe 915 and a solenoid valve 919 is coupled to the discharge pipe 915. The electromagnetic valve 919 prevents a certain amount of mixed substance temporarily stored in the storage container 914 from being supplied to the graphene filter 950 to be described later.

The electromagnetic valve 919 is opened and closed by a control signal provided from the valve controller 980 to be returned.

The discharge unit 916 serves to supply the mixed material temporarily stored in the storage container 914 to the graphene filter 950 to be described later.

The discharge unit 916 may be connected to the pipe 913 for example to provide air or inert gas to the storage container 914 so as to store the air in the storage container 914 And a blur to force the mixed material stored therein to the graphene filter 950.

The graphene filter 950 includes a filter body 920 and graphene films 930 and 940 having an inlet 921 and outlet 922,924,926 coupled to a discharge tube 915 connected to the containment vessel 914.

The filter body 920 is formed in a cylindrical shape with both ends closed and an inlet 921 communicating with the discharge pipe 915 of the storage container 914 is formed at the upper end of the filter body 920. The mixed material stored in the storage container 914 through the inlet 921 flows into the interior of the filter body 920.

The filter body 920 is formed with outlet ports 922, 924, and 926 corresponding to the number of materials mixed in the mixed material.

 In one embodiment of the present invention, the filter body 920 is formed with three outlets 922, 924, and 926 because the mixed material is composed of materials A, B, and C, and the outlets 922, 924, .

The graphene films 930 and 940 are manufactured by the method shown in FIGS. 1 to 4, and the description of the structure and manufacturing method of the graphene films 930 and 940 will be omitted.

One of the graphene films 930 and 940 is disposed inside the filter body 920 and disposed in such a manner as to block the inside of the filter body 920. [

The graphene thin film 930 has, for example, first holes of a first size through which the A material contained in the mixed material can not pass and the B material and the C material pass through.

The graphene film 930 is disposed between the outlets 922 and 924.

A graphene film 940 of one of the graphene films 930 and 940 is disposed inside the filter body 920 and the graphene film 940 is disposed on the filter body 920 in the form of facing the graphene film 930. [ As shown in Fig.

The graphene thin film 940 has second holes of a second size, for example, the B material contained in the mixed material can not pass through and the C material passes through.

The graphene film 940 is disposed between the outlets 924 and 926.

The collection unit 960 is connected to the outlets 922, 924, and 926, respectively, to collect and store A material, B material, and C materials separated from the mixed materials.

Collection unit 960 includes solenoid valves 962, 964, 966 to selectively collect and store A, B, and C materials.

The valve controller 980 provides a control signal to selectively open or close the solenoid valves 918, 919, 962, 964, and 966 so that each of the materials separated from the mixed material can be separated.

The graphene filter shown in Fig. 6 is suitable for selectively filtering or separating any one of substances A, B, and C, while it is difficult to separately separate A, B and C substances. And the filter device described, the A, B and C materials of different sizes can be individually filtered or separated.

Hereinafter, the process of individually separating or filtering each substance from the mixed substance by the filter device shown in FIG. 9 will be described.

First, a mixed material obtained by mixing A material, B material and C material is supplied to the storage container 914 through a pipe 913 from a mixed material supply unit 912 of the mixed material supply device 910. [

At this time, the valve controller 980 applies a control signal for opening the solenoid valve 918 to the solenoid valve 918 for a predetermined time so that a certain amount of mixed material is supplied to the storage container 914 through the pipe 913 .

The valve controller 980 applies a control signal to the solenoid valve 918 to close the solenoid valve 918 to supply the mixed material to the storage container 914 .

The valve controller 980 opens the solenoid valve 919 connected to the discharge pipe 915 of the storage container 914 from the discharge unit 916 to the storage container 914 while supplying the mixed substance to the storage container 914. [ Air or an inert gas is supplied to the interior of the storage container 914 so as to be supplied into the interior of the graphene filter 950.

The mixed material provided from the storage container 914 to the interior of the graphene filter 950 through the inlet portion 921 of the graphene filter 950 is introduced into the graphene thin film 930 formed with the first holes having the first size The B material and the C materials constituting the mixed material pass through the first holes of the graphene thin film 930 and the A material does not pass through the graphene thin film 930 and the upper part of the graphene thin film 930 .

The B material and the C material constituting the mixed material passing through the graphene thin film 930 reach the graphene thin film 940 having the second holes of the second size and the second hole of the graphene thin film 940 C material passes and the B material remains on top of the graphene film 940.

Therefore, when a certain amount of mixed material is supplied from the storage container 914 to the graphene filter 950, the A material, the B material, and the C material are separated in the respective graphene films 930 and 940 of the graphene filter 950 State.

In this state, the A material, the B material, and the C material are separated from the graphene films 930 and 940, respectively, so that the A material is discharged through the discharge port 922, the B material is discharged through the discharge port 924, And the valve controller 980 supplies control signals to the respective solenoid valves 962, 964, and 966 connected to the respective outlets 922, 924, and 926 And controls the opening and closing of the respective solenoid valves 962, 964, and 966 individually.

In one embodiment of the invention, the mixed material may comprise gaseous materials having different sizes, liquid materials having different sizes, or solid materials having different sizes.

In one embodiment of the present invention, the filter device can be widely used in medical fields such as hemodialysis, filter fields such as specific gas separation.

As described in detail above, when a graphene thin film having a carbon monomolecular layer structure is formed, artificially small holes are formed in the graphene thin film, and a porous graphene filter having holes formed therein artificially It is possible to selectively filter and separate a specific substance from a mixed substance in which a plurality of substances are mixed.

It should be noted that the embodiments disclosed in the drawings are merely examples of specific examples for the purpose of understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

Claims (13)

During the formation of graphene by depositing carbon atoms generated from a carbon source, some carbon atoms are substituted with substituted atoms generated from a substitution source to form a first graphene filter having first holes having a first size formed in the graphene ;
Wherein carbon atoms generated from a carbon source are deposited to form graphene, and a part of carbon atoms are substituted with substituted atoms generated from a substitution source to form second holes having a second size larger than the first size in the graphene Forming a second graphene filter; And
And disposing the first and second graphene filters within a filter body having an inlet and an outlet. The method according to claim 1,
Wherein the substitution source forming the first holes in the first graphene filter and the substitution source forming the second holes in the second graphene filter comprise nitrogen atoms. The method according to claim 1,
Wherein the supply amount of the substitution source in the step of forming the first graphene filter is smaller than the supply amount of the substitution source in the step of forming the second graphene filter. The method according to claim 1,
The carbon source is methane (CH _4), methanol (CH ₃ OH), carbon monoxide (CO), ethane (C ₂ H _6), ethylene (CH _2), ethanol (C ₂ H _5), acetylene (C ₂ H ₂ ), acetone (CH ₃ COCH _3), propane _{(CH 3 CH 2 CH 3)} , propylene (C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), polymethylpentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), cyclohexane (C ₆ H _12), benzene (C ₆ H _6), toluene (C ₇ H ₈₎ and Xylene (C ₆ H ₄ (CH ₃ ) ₂ ). The method according to claim 1,
The substitution source may be selected from the group consisting of ammonia, polypyrrole, polyvinyl-pyrrolidone, phtnipropanolamine, pyridine, pyrimidine, polyacrylonitrile, 4-vinylpyridine, polyaniline, poly-4-vinylpyridine, poly (butadiene-b-4-vinylpyridine) Poly (p-phenylenevinylenimine), phenol formaldehyde resin, polyacetonitrile and poly (aniline-co-N-propylbenzenesulfonate-aniline) N-propylbenzenesulfonic acid-aniline). ≪ / RTI > The method according to claim 1,
Wherein the carbon source and the substitution source are vaporized at the same time to form the first and second graphene filters, respectively, to form a porous graphene filter Way. A first graphene filter in which first holes having a first size are formed by substituting a carbon atom having a crystal defect in a covalent bond portion among carbon atoms constituting graphene with a substitution atom;
A second graphene filter in which second holes having a second size are formed by replacing a carbon atom having a crystal defect in a covalent bond portion among carbon atoms constituting graphene with a substitution atom; And
And a filter body into which the mixed materials mixed with the plurality of materials are introduced and which fixes the first and second graphene filters on the movement path of the mixed materials. 8. The method of claim 7,
Wherein the first and second graphene filters are formed in a film or cylindrical shape. A mixed material supply device for intermittently providing an amount of mixed material in which materials having different sizes are mixed;
A filter body having an inlet provided with the mixed material and having at least two outlets on a side thereof, at least one filter disposed inside the filter body and having holes for separating the substances contained in the mixed material, A graphene filter including a graphene thin film; And
And a collection unit connected to the outlets for collecting each of the materials separated from the mixed material. 10. The method of claim 9,
Wherein the mixed substance supply device comprises: a mixed substance supply unit for supplying the mixed substance;
A storage container for storing a predetermined amount of the mixed material;
And a discharge unit for discharging the mixed substance stored in the storage container. 11. The method of claim 10,
Wherein the discharge unit comprises a blower for providing air or inert gas to the containment vessel. 10. The method of claim 9,
Solenoid valves coupled to the mixed material supply device, the graphene filter, and the collection device; And
And a valve controller for controlling the solenoid valves. 10. The method of claim 9,
A first graphene filter disposed on an inner surface of the filter body and having first holes having a first size; And
And a second graphene filter disposed on the inner surface of the filter body and facing the first graphene filter and having second holes having a second size.

Images