WO2018079604A1 - Membrane de séparation de nanocarbone, membrane de séparation de nanocarbone composite, et procédé de production de membrane de séparation de nanocarbone - Google Patents

Membrane de séparation de nanocarbone, membrane de séparation de nanocarbone composite, et procédé de production de membrane de séparation de nanocarbone Download PDF

Info

Publication number
WO2018079604A1
WO2018079604A1 PCT/JP2017/038512 JP2017038512W WO2018079604A1 WO 2018079604 A1 WO2018079604 A1 WO 2018079604A1 JP 2017038512 W JP2017038512 W JP 2017038512W WO 2018079604 A1 WO2018079604 A1 WO 2018079604A1
Authority
WO
WIPO (PCT)
Prior art keywords
separation membrane
graphene oxide
mass
nanocarbon
membrane
Prior art date
Application number
PCT/JP2017/038512
Other languages
English (en)
Japanese (ja)
Inventor
知行 福世
ゴメス アーロン モレロス
シルバ ロドルフォ クルス
遠藤　守信
Original Assignee
昭和電工株式会社
国立大学法人信州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工株式会社, 国立大学法人信州大学 filed Critical 昭和電工株式会社
Priority to JP2018547721A priority Critical patent/JP6679117B2/ja
Publication of WO2018079604A1 publication Critical patent/WO2018079604A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • 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
    • C01B32/198—Graphene oxide

Definitions

  • the present invention relates to a nanocarbon separation membrane, a nanocarbon composite separation membrane, and a method for producing a nanocarbon separation membrane.
  • Separation membranes used for water treatment include UF membranes (Ultrafiltration Membrane), NF membranes (Nanofiltration Membrane), RO membranes (Reverse Osmosis Membrane), and There are FO membranes (Forward Osmosis Membrane). Separation membranes are not limited to water treatment, and are widely used for gas separation and the like.
  • Non-Patent Document 1 describes a separation membrane produced by subjecting a dispersion in which graphene oxide pieces are dispersed under reduced pressure.
  • Non-Patent Document 2 describes a separation membrane in which graphene oxide pieces are cross-linked with 1,3,5-benzenetricarbonyl trichloride (TMC).
  • TMC 1,3,5-benzenetricarbonyl trichloride
  • Non-Patent Document 3 describes a method of producing an NF film by filtering a dispersion in which graphene oxide pieces and multi-wall carbon nanotubes (hereinafter referred to as MWCNT) are dispersed under reduced pressure on a porous substrate. ing.
  • MWCNT multi-wall carbon nanotubes
  • the separation membranes described in Non-Patent Document 1 and Non-Patent Document 3 also have a problem that the graphene oxide pieces peel off during use. This is because the graphene oxide pieces are easily dispersed in water or the like.
  • the separation membrane described in Non-Patent Document 2 graphene oxide pieces are cross-linked. Therefore, it is difficult for the graphene oxide pieces to be separated from each other. However, since it is crosslinked by organic molecules, the robustness of the separation membrane cannot be sufficiently increased.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a nanocarbon separation membrane excellent in both water permeability and separation performance.
  • the present inventors have found that a nanocarbon separation membrane having excellent separation performance can be obtained by crosslinking a plurality of graphene oxide pieces with divalent cations and inserting double wall carbon nanotubes between the layers. It was. That is, this invention provides the following means in order to solve the said subject.
  • the first aspect of the present invention is a nanocarbon separation membrane described in the following (1).
  • the nanocarbon separation membrane according to the first aspect of the present invention includes a plurality of graphene oxide pieces that are present so as to overlap each other when viewed in the thickness direction and are cross-linked with each other by a divalent cation, and the plurality of graphene oxide pieces Double wall carbon nanotubes inserted between the layers, wherein the mass ratio of the graphene oxide pieces to the total mass of the graphene oxide pieces and the double wall carbon nanotubes is greater than 0% by mass and less than 70% by mass, The mass ratio is 30% by mass or more and less than 100% by mass.
  • the mass ratio of the graphene oxide pieces to the total mass of the graphene oxide pieces and the double wall carbon nanotubes is 30% by mass to 70% by mass, and the double wall carbon 30 mass% or more and 70 mass% or less may be sufficient as the mass ratio of a nanotube.
  • the divalent cation may be a calcium ion.
  • the second aspect of the present invention is the following nanocarbon composite separation membrane described in (4).
  • a nanocarbon composite separation membrane according to the second aspect of the present invention is disposed on the one surface side of the nanocarbon separation membrane according to any one of (1) to (3) above. And a porous membrane that supports the nanocarbon separation membrane.
  • the nanocarbon separation membrane and the porous membrane may be bonded.
  • the nanocarbon separation membrane and the porous membrane may be bonded together by a polyvinyl alcohol membrane.
  • a third aspect of the present invention is a method for producing a nanocarbon separation membrane described in the following (7).
  • a method for producing a nanocarbon separation membrane according to a third aspect of the present invention includes a step of applying a dispersion in which graphene oxide pieces and double-walled carbon nanotubes are dispersed and drying to form a carbon membrane. Immersing the carbon film in a solution in which divalent cations are dissolved.
  • the nanocarbon separation membrane according to the first aspect of the present invention is excellent in separation performance.
  • FIG. 1 It is a perspective schematic diagram which shows the preferable example of the nanocarbon composite separation membrane which concerns on the 1st aspect of this invention. It is a cross-sectional schematic diagram which shows the preferable example of the nanocarbon composite separation membrane which concerns on the 1st aspect of this invention. It is a scanning electron microscope (SEM) image of a graphene oxide piece simple substance. It is a transmission electron microscope (TEM) image of a graphene oxide piece simple substance. It is a transmission electron microscope (TEM) image of a nanocarbon separation membrane. It is a transmission electron microscope (TEM) image of a nanocarbon separation membrane. It is the figure which showed typically the manufacturing method of the nanocarbon composite separation membrane concerning this embodiment.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • TEM transmission electron microscope
  • TEM transmission electron microscope
  • TEM transmission electron microscope
  • TEM transmission electron microscope
  • the results of FTIR measurement of Reference Comparative Examples 2, 2-1, and 2-2 are shown.
  • the results of Raman spectroscopic measurements of Reference Comparative Examples 2, 2-1, and 2-2 are shown.
  • required by the XPS measurement of the reference comparative example 2-1 is shown.
  • required by the XPS measurement of the reference comparative example 2-2 is shown.
  • required by the XPS measurement of the reference comparative example 2 is shown.
  • required by the XPS measurement of the reference comparative example 2 is shown.
  • required by the XPS measurement of the reference comparative example 2 is shown.
  • Example 4 is a photograph of the surface of a carbon nanocomposite separation membrane after the treatment of Example 4.
  • 2 is a photograph of the surface of the carbon nanocomposite separation membrane after the treatment of Example 1. The result of having performed FTIR measurement before the heating of a polyvinyl alcohol film and after a heating is shown.
  • FIG. 1 is a schematic perspective view of a nanocarbon composite separation membrane according to the first embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the nanocarbon composite separation membrane according to the first embodiment of the present invention. In FIG. 1, each component is illustrated separately for easy understanding.
  • the nanocarbon separation membrane 10 is a functional membrane having a high filtration function.
  • the porous membrane 30 is a support membrane that supports the nanocarbon separation membrane 10 and increases the mechanical strength of the nanocarbon composite separation membrane 100 as a whole.
  • the nanocarbon composite separation membrane 100 can be used for both gas phase separation and liquid phase separation depending on the application. Hereinafter, the description will focus on liquid phase separation.
  • the nanocarbon separation membrane 10 includes a graphene oxide (GO (abbreviation of graphene oxide)) piece 1 and a double wall carbon nanotube (hereinafter referred to as “DWCNT” (abbreviation of double wall carbon nanotube)) 2.
  • DWCNT2 is a carbon nanotube having a two-layer structure. DWCNT may have a structure in which at least two carbon nanotubes having different inner diameters overlap each other. Existence of graphene oxide so as to overlap each other when viewed from the thickness direction may mean that at least a part thereof overlaps each other when viewed from the thickness direction.
  • FIG. 3 is a scanning electron microscope (SEM) image of the graphene oxide piece 1 in a single state.
  • FIG. 4 is a transmission electron microscope (TEM) image of the graphene oxide piece 1 in a single state.
  • the graphene oxide piece 1 is a piece of graphene oxide.
  • Graphene oxide is a material in which an oxygen-containing functional group selected from an epoxy group, a carboxyl group, a carbonyl group, a hydroxyl group, and the like is bonded to a monolayer of graphene.
  • Graphene oxide is also known as a material that becomes graphite when reduced.
  • the thickness of the graphene oxide piece 1 is one carbon atom and is about 1 to 1.5 nm.
  • the size of the graphene oxide piece 1 in the in-plane direction can be designed as appropriate.
  • the average diameter in the in-plane direction of the graphene oxide piece 1 shown in FIG. 3 is 12 ⁇ m.
  • the average diameter was determined as follows. First, the dispersion liquid in which the graphene oxide pieces 1 are dispersed is dropped on the Si substrate and dried. Next, the Si substrate is observed with an SEM, and a circumscribed ellipse of the graphene oxide piece 1 is drawn. At this time, the graphene oxide pieces 1 that do not aggregate and cannot draw a circumscribed ellipse are not selected. Then, the major axis of the circumscribed ellipse obtained is measured. The same operation was performed on 90 graphene oxide pieces 1 and the average value was calculated to obtain the average diameter.
  • the graphene oxide piece 1 is partially perforated (see the dotted area in FIG. 4). In other words, one or more holes (openings) may be provided on the surface of the graphene oxide piece 1. This hole functions as a flow path for fluid passing through the nanocarbon separation membrane 10.
  • the diameter and the amount of the holes formed in the graphene oxide piece 1 can be arbitrarily selected, and can be controlled by changing the degree of oxidation of the graphene oxide piece 1.
  • the average diameter of the holes formed in the graphene oxide piece 1 is preferably 0.5 nm or more and 5 nm or less, and more preferably 1 nm or more and 3 nm or less.
  • the area of the pores is preferably 0.5% or more and 5% or less in the area of graphene oxide (GO).
  • FIG. 5 is a transmission electron microscope (TEM) image of a nanocarbon separation membrane, which is a preferred example of the present invention.
  • TEM transmission electron microscope
  • FIG. 6 is a transmission electron microscope (TEM) image of the nanocarbon separation membrane, and is an enlarged view of a part of FIG.
  • TEM transmission electron microscope
  • a part of DWCNT 2 can be confirmed through a hole (see the dotted line region in FIG. 6), and the other part can be confirmed through a carbon atom constituting graphene oxide piece 1. That is, the DWCNT 2 is present behind the graphene oxide piece 1.
  • the hole portion there is a portion where a dot of carbon atoms is confirmed inside the hole. That is, the graphene oxide piece 1 is present behind the DWCNT 2 in the drawing. That is, the DWCNT 2 is sandwiched between the graphene oxide pieces 1 that are present so as to overlap each other when viewed from the thickness direction.
  • DWCNT 2 has a diameter of about several nanometers to several tens of nanometers and is thicker than the thickness of the graphene oxide piece 1. Therefore, when at least one DWCNT 2 is sandwiched between the plurality of graphene oxide pieces 1, the interval between the stacked graphene oxide pieces 1 increases.
  • the diameter of DWCNT2, the innermost inner diameter of DWCNT2, and the length of DWCNT2 may be arbitrarily selected.
  • the average inter-plane distance of the graphene oxide piece is 7.7 mm.
  • the average inter-surface distance becomes 7.7 mm or more.
  • the average inter-surface distance is obtained from a peak value obtained by X-ray diffraction. Note that the average inter-plane distance of the graphene oxide pieces in the nanocarbon separation membrane of the present invention can be arbitrarily changed by changing conditions and the like.
  • the flow path of the fluid passing through the nanocarbon separation membrane 10 increases. That is, in the case of liquid phase separation, water permeability increases.
  • the spread of the average inter-surface distance is in units of ridges and is slight. Therefore, it is possible to avoid the deterioration of the separation characteristics of the separation object.
  • the mass ratio of the graphene oxide piece 1 to the total mass of the graphene oxide pieces and the double wall carbon nanotubes is 70% by mass or less and greater than 0% by mass. Moreover, the mass ratio of DWCNT2 with respect to the total mass of a graphene oxide piece and a double wall carbon nanotube is 30 to 100 mass%. When the ratio of the graphene oxide piece 1 and the DWCNT 2 is within this range, it is possible to avoid that the performance of one of the water permeability or the separation characteristic of the separation object is significantly deteriorated.
  • the mass ratio of the graphene oxide piece 1 to the total mass of the graphene oxide pieces and the double wall carbon nanotubes is preferably 30% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 70% by mass or less. More preferably, the content is 50% by mass or more and 70% by mass or less.
  • the mass ratio of DWCNT2 to the total mass of graphene oxide pieces and double-walled carbon nanotubes is preferably 30% by mass to 70% by mass, more preferably 30% by mass to 60% by mass, and more preferably 30% by mass. More preferably, the content is from 50% to 50% by weight.
  • the sum total of the mass ratio of the graphene oxide piece 1 and DWCNT2 will be 100 mass%.
  • the plurality of graphene oxide pieces 1 are cross-linked with each other by a divalent cation.
  • the graphene oxide piece 1 has at least one oxygen-containing functional group selected from an epoxy group, a carboxyl group, a carbonyl group, a hydroxyl group, and the like.
  • the divalent cation is coordinated in the vicinity of the oxygen-containing functional group of the graphene oxide pieces 1 and bridges adjacent graphene oxide pieces 1.
  • the graphene oxide piece 1 is highly dispersible in water. Therefore, if the graphene oxide pieces 1 are simply laminated, the graphene oxide pieces 1 may be separated from the nanocarbon separation film 10 when water is passed through. In particular, in the case of cross flow in which water flows in a direction parallel to the membrane surface of the nanocarbon separation membrane 10, the graphene oxide piece 1 is easily peeled off.
  • the divalent cation is not particularly limited as long as it can contribute to crosslinking. From the viewpoint of availability, at least one of calcium ions and magnesium ions is preferable.
  • the nanocarbon separation membrane 10 according to this embodiment is excellent in both water permeability and separation characteristics of the separation object as a separation membrane.
  • the graphene oxide pieces 1 are cross-linked with a divalent cation. For this reason, peeling of the graphene oxide piece 1 is suppressed during use. Therefore, the solution can be supplied to the nanocarbon separation membrane 10 by crossflow.
  • the thickness of the nanocarbon separation membrane may be arbitrarily selected.
  • the porous membrane 30 is disposed on one side of the nanocarbon separation membrane 10.
  • the porous membrane 30 supports the nanocarbon separation membrane 10 and increases the mechanical strength of the nanocarbon composite separation membrane 100 as a whole.
  • the porous film 30 has a hole 31 therein.
  • the hole 31 By having the hole 31 inside, it has water permeability in the thickness direction.
  • the hole part 31 does not need to be a hole part extended in the thickness direction as shown to a figure.
  • a connecting hole in which a plurality of minute holes are connected may be used.
  • porous membrane 30 a known porous substrate can be selected and used as long as it has water permeability and mechanical strength.
  • a resin film made of polyimide, polysulfone, polyethersulfone, or the like and having communication holes, porous alumina, or the like can be used as the porous film 30.
  • the adhesive layer 20 described later is formed by crosslinking with heat or light, it is particularly preferable to use polysulfone having high heat resistance.
  • the thickness of the porous membrane may be arbitrarily selected.
  • the adhesive layer 20 adheres the nanocarbon separation membrane 10 and the porous membrane 30.
  • a material capable of adhering the nanocarbon separation membrane 10 and the porous membrane 30 without significantly inhibiting water permeability can be used.
  • the adhesive layer material can be selected arbitrarily.
  • polyvinyl alcohol or the like can be used. Uncrosslinked polyvinyl alcohol is provided between the nanocarbon separation membrane 10 and the porous membrane 30, and these can be bonded by crosslinking the polyvinyl alcohol.
  • the nanocarbon separation membrane 10 When performing a dead-end flow in which liquid is passed from a direction perpendicular to the in-plane direction of the nanocarbon composite separation membrane 100, the nanocarbon separation membrane 10 hardly peels from the porous membrane 30. On the other hand, when performing the cross flow which lets a liquid flow from a parallel direction with respect to the in-plane direction of the nanocarbon composite separation membrane 100, the nanocarbon separation membrane 10 becomes easy to peel from the porous membrane 30. Therefore, in the case where liquid is passed through the nanocarbon composite separation membrane 100 by crossflow, it is particularly preferable to provide the adhesive layer 20.
  • the thickness of the adhesive layer may be arbitrarily selected.
  • the nanocarbon composite separation membrane 100 includes the nanocarbon separation membrane 10 having excellent water permeability and separation characteristics of the separation object. For this reason, it has excellent separation characteristics.
  • the mechanical strength of the nanocarbon composite separation membrane 100 can be increased by supporting one surface of the nanocarbon separation membrane 10 with the porous membrane 30. Furthermore, by bonding the nanocarbon separation membrane 10 and the porous membrane 30 with the adhesive layer 20, it is possible to prevent the nanocarbon separation membrane 10 from being peeled off during use.
  • FIG. 7 is a view schematically showing a method for producing a nanocarbon composite separation membrane according to the present embodiment.
  • the nanocarbon composite separation membrane 100 includes a step of forming the adhesive layer 20 on one surface of the porous membrane 30, and an adhesive layer 20. Forming a nanocarbon separation membrane 10 on the surface on which is formed.
  • the nanocarbon separation membrane 10 includes a step of applying a dispersion liquid in which graphene oxide pieces 1 and DWCNT2 are dispersed to the surface of the porous membrane 30 on which the adhesive layer 20 is formed, and drying to form a carbon membrane; Dipping the membrane in a solution in which divalent cations are dissolved.
  • the thickness of the graphene oxide piece 1 used for production can be arbitrarily selected, but is preferably about 1 to 1.5 nm. You may select arbitrarily the average diameter (outer diameter) of DWCNT2 used for manufacture. Further, the innermost inner diameter of the DWCNT 2 may be arbitrarily selected. The length of DWCNT2 may be arbitrarily selected.
  • the mass ratio of the graphene oxide piece 1 to the total mass of the graphene oxide piece 1 and the DWCNT 2 can be arbitrarily selected, but is preferably 30% by mass or more and 70% by mass or less, for example, 40% by mass or more and 70% More preferably, it is 50 mass% or less, and it is especially preferable that it is 50 to 70 mass%.
  • the mass ratio of DWCNT2 to the total mass of graphene oxide pieces and double-walled carbon nanotubes can be arbitrarily selected, but is preferably 30% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass. Is more preferable, and 30% by mass or more and 50% by mass or less is particularly preferable.
  • a porous film 30 is prepared.
  • the porous membrane 30 is selected from the above-described ones.
  • the adhesive layer 20 is formed on one surface of the porous film 30.
  • the adhesive layer 20 can be formed by means such as coating.
  • the adhesive layer 20 can be formed on one surface of the porous film 30 by immersing the porous film 30 in an aqueous polyvinyl alcohol solution, or applying the aqueous solution to the film and drying it.
  • the dispersion 11 in which the graphene oxide pieces 1 and the DWCNTs 2 are dispersed is applied to the surface on which the adhesive layer 20 is formed.
  • the application method is not particularly limited. You may use it arbitrarily selecting from well-known methods. For example, when spray coating is performed from the nozzle, a shearing force is applied to the dispersion 11 at the nozzle tip, and the dispersibility of the graphene oxide pieces 1 and the DWCNT 2 is increased.
  • the dispersion 11 is obtained, for example, by mixing a first dispersion in which the graphene oxide pieces 1 are dispersed and a second dispersion in which DWCNT2 is dispersed.
  • the first dispersion is obtained by the following procedure, for example.
  • the graphene oxide piece 1 is obtained by a known method (for example, a method described in Patent Document 1 or Non-Patent Document 4) using graphite as a raw material.
  • the graphene oxide piece 1 is highly dispersible in water. For this reason, a 1st dispersion liquid is obtained only by adding to water.
  • DWCNT2 is produced.
  • DWCNT2 can be produced by a general synthesis method.
  • CVD methods include a substrate method and a gas phase flow method.
  • the substrate method includes a method of synthesizing carbon nanotubes on a substrate on which a metal layer having a thickness of several nanometers to several ⁇ m is deposited, and a method of synthesizing carbon nanotubes by supporting transition metal part particles on a simple substance such as zeolite or ceramic. .
  • the gas phase flow method is a method of synthesizing carbon nanotubes by reacting catalyst fine particles and a raw material gas in a high temperature zone in a reaction tube.
  • the catalyst fine particles are obtained by spraying the precursor compound onto the reaction tube and thermally decomposing the precursor compound at the reaction tube inlet.
  • the catalyst fine particles and the raw material gas are sent into the reaction tube by the carrier gas.
  • a method for producing DWCNT described in Patent Document 2, Patent Document 3, and the like is given as an example.
  • the DWCNT 2 thus produced is added to an aqueous solution selected as necessary to obtain a second dispersion.
  • aqueous solution for example, a sodium polystyrene sulfonate (PSS) aqueous solution, a sodium dodecyl sulfate aqueous solution, a sodium deoxycholate aqueous solution, or the like can be used.
  • PSS sodium polystyrene sulfonate
  • a sodium dodecyl sulfate aqueous solution a sodium deoxycholate aqueous solution, or the like
  • the first dispersion and the second dispersion are mixed and diluted if necessary to obtain the dispersion 11.
  • the coated dispersion 11 is dried, for example, naturally dried to obtain a carbon film.
  • the carbon film is preferably heated together with the porous film 30.
  • the adhesive layer is cross-linked by heat
  • polyvinyl alcohol when used as the adhesive layer, the polyvinyl alcohol of the adhesive layer 20 is cross-linked by heating, and the adhesion between the carbon film and the porous film 30 is increased. Also exhibits water resistance. Also, excess water can be removed.
  • the carbon film formed by applying the dispersion 11 is immersed in a solution in which divalent cations are dissolved.
  • divalent cations for example, when calcium ions are used as divalent cations, they are immersed in a solution in which calcium chloride is dissolved.
  • the solvent of the solution may be arbitrarily selected.
  • the divalent cation can be arbitrarily selected, and examples thereof include calcium ions and magnesium ions.
  • a predetermined nanocarbon separation membrane can be easily obtained.
  • a nanocarbon composite separation membrane can be easily obtained by using this method for producing a nanocarbon separation membrane.
  • the fluid of the nanocarbon separation membrane can be obtained simply by mixing the first dispersion in which the graphene oxide pieces 1 are dispersed and the second dispersion in which the DWCNT2 is dispersed. It is possible to control the flow path through which the gas flows. That is, the water permeability and separation performance of the nanocarbon separation membrane can be easily controlled.
  • the nanocarbon separation membrane can be produced by applying a dispersion liquid. Therefore, it is easy to increase the area of the nanocarbon separation membrane.
  • the nanocarbon separation membrane, the nanocarbon composite separation membrane, and the method for producing the nanocarbon separation membrane have been described above.
  • the present invention may be variously modified without changing the gist of the invention.
  • Example 1 As Example 1, a nanocarbon composite separation membrane having a nanocarbon separation membrane composed of 30% by mass of graphene oxide pieces and 70% by mass of DWCNT was prepared. Specifically, the nanocarbon composite separation membrane of Example 1 was produced by the following procedure.
  • a first dispersion in which graphene oxide pieces having an average diameter of 12 ⁇ m were dispersed was prepared using graphite (product number 332461 manufactured by Sigma-Aldrich) as a raw material.
  • the first dispersion was prepared as follows.
  • the liquid that was allowed to stand was separated into a supernatant and a precipitate.
  • the supernatant was removed by decantation to obtain a precipitate.
  • the obtained precipitate was added to a 5% by mass H 2 SO 4 aqueous solution (1 L) and dispersed.
  • the operation of adding the dispersion into pure water, centrifuging, and then dispersing in pure water was repeated 5 times to clean the dispersion medium.
  • the precipitate after centrifugation becomes two layers.
  • the lower layer was graphite that was not exfoliated from each other, and the upper layer was that the exfoliated graphene oxide pieces absorbed water.
  • a first dispersion having a solid content concentration of 0.9% by mass was obtained.
  • the obtained first dispersion was diluted with water and dropped onto the Si substrate and dried, the sample was observed by SEM. As a result, the average diameter of the graphene oxide pieces was 12 ⁇ m.
  • DWCNT outer diameter 1.8 nm, inner diameter 1.2 nm by TEM observation
  • the diameter of DWCNT in the second dispersion was about several nm.
  • the obtained first dispersion and second dispersion were mixed and diluted to obtain a dispersion.
  • nanocarbon composed of graphene oxide pieces and DWCNT is dispersed.
  • the composition ratio of the nanocarbon in the dispersion was 30% by mass for graphene oxide pieces and 70% by mass for DWCNT.
  • the concentration of nanocarbon relative to the solvent was 0.8 mg / mL.
  • a commercially available polysulfone membrane (Alfa Label: GR40PP, size 50 mm ⁇ 50 mm) was prepared as a porous membrane. Then, the polysulfone film was immersed in a 1% by mass aqueous polyvinyl alcohol solution (manufactured by Sigma-Aldrich: molecular weight 31,000-50,000, 98-99% saponified product) for 1 hour. The polysulfone membrane after immersion was air-dried in an upright state. As a result, polyvinyl alcohol was coated on the surface of the polysulfone film.
  • the dispersion was sprayed onto the porous film coated with polyvinyl alcohol using an air brush (manufactured by Anest Iwata: HP-BCS). Thereafter, the porous film was dried in an air atmosphere at 100 ° C. for 1 hour. At this time, the polyvinyl alcohol was cross-linked, and the porous film and the carbon film formed by drying the dispersion were adhered.
  • the obtained laminated film was immersed in a calcium chloride solution for 1 hour.
  • the calcium chloride solution had a calcium chloride concentration of 5% by mass, and the solvent of the calcium chloride solution was a mixture of ethanol and water in a volume ratio of 1: 3.
  • the laminated film after immersion was dried. The drying was performed by air-drying, then immersed in ethanol for 1 hour and then air-dried again.
  • Example 2 nanocarbon composite separation membranes were prepared in the same procedure as in Example 1 except that the mixing ratio of the first dispersion and the second dispersion was changed.
  • the composition ratio of the obtained nanocarbon separation membrane is as follows.
  • Example 2 Graphene oxide pieces (50 mass%), DWCNT (50 mass%)
  • Example 3 Graphene oxide pieces (70 mass%), DWCNT (30 mass%)
  • Comparative Example 1 a nanocarbon composite separation membrane was prepared in the same procedure as in Example 1 except that the mixing ratio of the first dispersion and the second dispersion was changed.
  • the composition ratio of the nanocarbon separation membrane of Comparative Example 1 was 90% by mass of graphene oxide pieces and 10% by mass of DWCNT.
  • Comparative Example 2 In Comparative Example 2, a nanocarbon composite separation membrane was prepared in the same procedure as in Example 1 except that only the first dispersion was used and the second dispersion was not used. That is, the composition ratio of the nanocarbon separation membrane of Comparative Example 2 was 100% by mass of graphene oxide pieces.
  • Comparative Example 3 a nanocarbon composite separation membrane was prepared in the same procedure as in Example 1 except that only the second dispersion liquid was used and the first dispersion liquid was not used. That is, the composition ratio of the nanocarbon separation membrane of Comparative Example 3 was set to 100% by mass of DWCNT.
  • the water permeability was calculated from the results of water permeability measurement at a pressure of 5.0 MPa.
  • the NaCl removal rate was obtained by cutting out the membrane into a circle having a diameter of 25 mm and using a cross flow filter (manufactured by Tosk Corporation).
  • NaCl removal rate [%] ⁇ 1-NaCl concentration of permeated water [mass%] / NaCl concentration of raw water [mass%] ⁇ ⁇ 100
  • Table 1 shows the measurement results.
  • GO indicates graphene oxide pieces
  • DWCNT indicates double wall carbon nanotubes
  • PVA indicates polyvinyl alcohol.
  • the nanocarbon composite separation membranes of Examples 1 to 3 in which the ratio of the graphene oxide pieces to DWCNT is in a predetermined range are more permeable than the nanocarbon composite separation membranes of Comparative Examples 1 and 2.
  • the amount was greatly improved.
  • the NaCl removal rate slightly decreased, depending on the application, about 40% was sufficient, and a sufficient NaCl removal rate was exhibited.
  • Applications include, for example, nanofiltration membranes for divalent ion removal and organic matter separation. In Comparative Example 3 consisting only of DWCNT, water freely flowed and no desalting performance was confirmed.
  • Reference Comparative Example 2-1 The sample of Reference Comparative Example 2 was immersed before being immersed in the calcium chloride solution, and the sample was heated at 100 ° C. (hereinafter referred to as Reference Comparative Example 2-2: No immersion in the calcium chloride solution) ) And three samples.
  • Reference Comparative Example 2 the dispersion used in Comparative Example 2 was applied on a Si substrate instead of the porous film, and the same procedure including immersion in a calcium chloride solution was performed. A separation membrane was formed.
  • a reference comparative example what was formed on the Si substrate will be referred to as a reference comparative example.
  • Reference Comparative Example 2 corresponds to one produced under the same conditions as Comparative Example 2, and the other reference examples and reference comparative examples also have the same correspondence.
  • FIG. 8 shows the results of FTIR measurement of Reference Comparative Examples 2, 2-1, and 2-2.
  • FTIR was performed by the total reflection measurement (ATR) method.
  • the comparative example 2 in which the CaCl 2 treatment was performed has the intensity of the C—O and C ⁇ O peaks compared to the reference comparative example 2-1 before the treatment. It's down. This is because the relative intensity of C—O and C ⁇ O peak with respect to the C ⁇ C peak is reduced by coordination of Ca 2+ ions with oxygen ions.
  • FIG. 9 shows the results of Raman spectroscopic measurement in Reference Comparative Examples 2, 2-1, and 2-2.
  • the D (1350 cm ⁇ 1 ) / G (1600 cm ⁇ 1 ) ratio in the result of Raman spectroscopic measurement was 0.92 in Reference Comparative Example 2-1, 0.84 in Reference Comparative Example 2-2, and 0 in Reference Comparative Example 2. .87.
  • Reference Comparative Example 2-2 is obtained by heating Reference Comparative Example 2-1 at 100 ° C., and it is considered that a part of the graphene oxide was reduced by heating and approached the graphite structure.
  • the D / G ratio of the reference comparative example 2 is large. It is considered that the disorder of the crystal arrangement was caused by the coordination of calcium ions.
  • 10A to 10C show analysis results of C1s spectra obtained by XPS measurement in Reference Comparative Examples 2, 2-1, and 2-2.
  • 10A shows the analysis result of Reference Comparative Example 2-1
  • FIG. 10B shows the analysis result of Reference Comparative Example 2-2
  • FIG. 10C shows the analysis result of Reference Comparative Example 2.
  • FIG. 11A and 11B show the analysis results of the Cl2p spectrum and Ca2p spectrum obtained by XPS measurement in Reference Comparative Example 2.
  • FIG. 11A shows the analysis result of the Cl2p spectrum
  • FIG. 11B shows the analysis result of the Ca2p spectrum.
  • Example 4 differs from Example 1 in that the polysulfone film is not immersed in an aqueous polyvinyl alcohol solution in the production process of Example 1.
  • a 0.2% concentration sodium chloride aqueous solution was fed to the carbon nanocomposite separation membranes of Example 1 and Example 4 at a flow rate of 300 ml / min at a pressure of 2 to 5 MPa by cross flow.
  • FIG. 12A and 12B are photographs of the surface of the carbon nanocomposite separation membrane after the treatment in Example 1 and Example 4.
  • FIG. 12A is a photograph of the surface of the carbon nanocomposite separation membrane of Example 4 23 hours after the start of supplying the sodium chloride aqueous solution.
  • FIG. 12B is a surface photograph of the carbon nanocomposite separation membrane of Example 1 after 70 hours from the start of supply of the sodium chloride aqueous solution.
  • the carbon nanoseparation membrane is peeled off by the flow of the supplied liquid (portion shown by the arrow in FIG. 12A).
  • the carbon nanocomposite separation membrane of Example 1 did not peel off.
  • the adhesive layer it is possible to suppress the separation of the carbon nanoseparation membrane from the carbon nanocomposite separation membrane.
  • the liquid is supplied to the carbon nanocomposite separation membrane by crossflow, it is preferable to provide an adhesive layer.
  • a liquid or gas is supplied in a dead end flow, it can be used without an adhesive layer.
  • FIG. 13 shows the results of FTIR measurement before and after heating polyvinyl alcohol. As shown in FIG. 13, when normalized by the 854 cm ⁇ 1 peak, the peak at 1141 cm ⁇ 1 increased. This indicates the curing of the polyvinyl alcohol film by heat. That is, the polyvinyl alcohol film is sufficiently crosslinked when it is dried for 1 hour in an atmosphere of 100 degrees.
  • An object of the present invention is to provide a nanocarbon separation membrane excellent in both water permeability and separation performance.
  • Nanocarbon separation membrane 1 Graphene oxide pieces, 2 Double wall carbon nanotube (DWCNT), 10 Nanocarbon separation membrane, 11 Dispersion 20 Adhesive layer, 30 porous membrane, 31 holes, 100 Nanocarbon composite separation membrane

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Cette membrane de séparation de nanocarbone est pourvue d'une pluralité de pièces d'oxyde de graphène qui sont disposées de manière à se chevaucher mutuellement lorsqu'elles sont vues depuis la direction de l'épaisseur et qui sont réticulées ensemble par des cations divalents, et des nanotubes de carbone à double paroi qui sont insérés entre les couches de la pluralité de pièces d'oxyde de graphène. Par rapport à la masse totale des pièces d'oxyde de graphène et des nanotubes de carbone à double paroi, le rapport en masse des pièces d'oxyde de graphène est supérieur à 0 % en masse à 70 % en masse, et le rapport en masse des nanotubes de carbone à double paroi est de 30 % en masse à moins de 100 % en masse.
PCT/JP2017/038512 2016-10-26 2017-10-25 Membrane de séparation de nanocarbone, membrane de séparation de nanocarbone composite, et procédé de production de membrane de séparation de nanocarbone WO2018079604A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018547721A JP6679117B2 (ja) 2016-10-26 2017-10-25 ナノカーボン分離膜、ナノカーボン複合分離膜及びナノカーボン分離膜の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-209841 2016-10-26
JP2016209841 2016-10-26

Publications (1)

Publication Number Publication Date
WO2018079604A1 true WO2018079604A1 (fr) 2018-05-03

Family

ID=62024955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/038512 WO2018079604A1 (fr) 2016-10-26 2017-10-25 Membrane de séparation de nanocarbone, membrane de séparation de nanocarbone composite, et procédé de production de membrane de séparation de nanocarbone

Country Status (2)

Country Link
JP (1) JP6679117B2 (fr)
WO (1) WO2018079604A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722198A (zh) * 2018-05-29 2018-11-02 华中科技大学 一种全碳复合膜的制备方法及其产品
CN110479108A (zh) * 2019-07-18 2019-11-22 北京工业大学 一种高效去除痕量有机污染物的cnt-go复合膜的制备方法
JP2021505359A (ja) * 2018-12-18 2021-02-18 大連理工大学 導電性ポリマー／カーボンナノチューブ複合ナノろ過膜の作製方法及び応用
CN115650224A (zh) * 2022-11-10 2023-01-31 杭州嘉悦智能设备有限公司 一种高导热氮掺杂石墨烯-碳纳米管复合膜及其制备方法
WO2023022084A1 (fr) * 2021-08-19 2023-02-23 東レ株式会社 Membrane de séparation de fluide
WO2023157844A1 (fr) * 2022-02-17 2023-08-24 株式会社ナノメンブレン Film mince composite polymère, dispositif de séparation de gaz pourvu dudit film mince composite polymère, et procédé de production d'un film mince composite polymère
JP7470348B2 (ja) 2022-09-22 2024-04-18 崑山科技大学 土粘土及び酸化グラフェンで成長させた三次元カーボンナノチューブの作製と応用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102333293B1 (ko) * 2021-05-28 2021-12-01 국방과학연구소 탄소계 지지체 및 분리층을 포함하는 선택투과성 분리막의 제조방법
KR102488108B1 (ko) * 2021-06-01 2023-01-13 연세대학교 산학협력단 극성 탄소나노튜브 분산액 및 극성 1차원 탄소체를 기반으로 하는 분리막의 제조방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012500179A (ja) * 2008-08-19 2012-01-05 ウィリアム・マーシュ・ライス・ユニバーシティ カーボンナノチューブからのグラフェンナノリボンの製造
JP2012031024A (ja) * 2010-08-02 2012-02-16 Fuji Electric Co Ltd グラフェン薄膜の製造方法
WO2014021257A1 (fr) * 2012-07-30 2014-02-06 国立大学法人信州大学 Procédé de production de film composite comprenant des nanotubes de graphène et de carbone
WO2014038600A1 (fr) * 2012-09-05 2014-03-13 独立行政法人物質・材料研究機構 Empilements liés de graphène partiellement réduit, procédé de production d'empilements liés de graphène partiellement réduit, poudre comprenant des empilements liés de graphène partiellement réduit, film comprenant des empilements liés de graphène partiellement réduit, film d'électrode en graphène, procédé de production d'un film d'électrode en graphène, et condensateur à graphène
JP2014169193A (ja) * 2013-03-01 2014-09-18 Nec Corp ナノカーボンとグラフェンまたはグラファイトが複合した炭素材料及びその製造方法
JP2014231453A (ja) * 2013-05-29 2014-12-11 株式会社船井電機新応用技術研究所 多孔質複合カーボン材及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012500179A (ja) * 2008-08-19 2012-01-05 ウィリアム・マーシュ・ライス・ユニバーシティ カーボンナノチューブからのグラフェンナノリボンの製造
JP2012031024A (ja) * 2010-08-02 2012-02-16 Fuji Electric Co Ltd グラフェン薄膜の製造方法
WO2014021257A1 (fr) * 2012-07-30 2014-02-06 国立大学法人信州大学 Procédé de production de film composite comprenant des nanotubes de graphène et de carbone
WO2014038600A1 (fr) * 2012-09-05 2014-03-13 独立行政法人物質・材料研究機構 Empilements liés de graphène partiellement réduit, procédé de production d'empilements liés de graphène partiellement réduit, poudre comprenant des empilements liés de graphène partiellement réduit, film comprenant des empilements liés de graphène partiellement réduit, film d'électrode en graphène, procédé de production d'un film d'électrode en graphène, et condensateur à graphène
JP2014169193A (ja) * 2013-03-01 2014-09-18 Nec Corp ナノカーボンとグラフェンまたはグラファイトが複合した炭素材料及びその製造方法
JP2014231453A (ja) * 2013-05-29 2014-12-11 株式会社船井電機新応用技術研究所 多孔質複合カーボン材及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAN YI ET AL.: "High-Flux Graphene Oxide Nanofiltration Membrane Intercalated by Carbon Nanotubes", ACS APPL. MATER. INTERFACES, 2 April 2015 (2015-04-02), pages 8147 - 8155, XP055606737 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722198A (zh) * 2018-05-29 2018-11-02 华中科技大学 一种全碳复合膜的制备方法及其产品
JP2021505359A (ja) * 2018-12-18 2021-02-18 大連理工大学 導電性ポリマー／カーボンナノチューブ複合ナノろ過膜の作製方法及び応用
CN110479108A (zh) * 2019-07-18 2019-11-22 北京工业大学 一种高效去除痕量有机污染物的cnt-go复合膜的制备方法
WO2023022084A1 (fr) * 2021-08-19 2023-02-23 東レ株式会社 Membrane de séparation de fluide
WO2023157844A1 (fr) * 2022-02-17 2023-08-24 株式会社ナノメンブレン Film mince composite polymère, dispositif de séparation de gaz pourvu dudit film mince composite polymère, et procédé de production d'un film mince composite polymère
JP7418758B2 (ja) 2022-02-17 2024-01-22 株式会社ナノメンブレン 高分子複合薄膜、この高分子複合薄膜を備えるガス分離装置、並びに高分子複合薄膜の製造方法
JP7470348B2 (ja) 2022-09-22 2024-04-18 崑山科技大学 土粘土及び酸化グラフェンで成長させた三次元カーボンナノチューブの作製と応用
CN115650224A (zh) * 2022-11-10 2023-01-31 杭州嘉悦智能设备有限公司 一种高导热氮掺杂石墨烯-碳纳米管复合膜及其制备方法

Also Published As

Publication number Publication date
JP6679117B2 (ja) 2020-04-15
JPWO2018079604A1 (ja) 2019-06-24

Similar Documents

Publication Publication Date Title
WO2018079604A1 (fr) Membrane de séparation de nanocarbone, membrane de séparation de nanocarbone composite, et procédé de production de membrane de séparation de nanocarbone
Al Aani et al. Thin Film Nanocomposite (TFN) membranes modified with polydopamine coated metals/carbon-nanostructures for desalination applications
Shao et al. Self-cleaning nanofiltration membranes by coordinated regulation of carbon quantum dots and polydopamine
Emadzadeh et al. Synthesis, modification and optimization of titanate nanotubes-polyamide thin film nanocomposite (TFN) membrane for forward osmosis (FO) application
Cheng et al. Synthesis of graphene oxide/polyacrylamide composite membranes for organic dyes/water separation in water purification
US10953371B2 (en) Thin film composites having graphene oxide quantum dots
Lou et al. A facile way to prepare ceramic-supported graphene oxide composite membrane via silane-graft modification
Lecaros et al. Tunable interlayer spacing of composite graphene oxide-framework membrane for acetic acid dehydration
Bhadra et al. Flux enhancement in direct contact membrane distillation by implementing carbon nanotube immobilized PTFE membrane
Sonawane et al. Nanomaterials for membrane synthesis: Introduction, mechanism, and challenges for wastewater treatment
CA2831579C (fr) Membranes contenant des nanotubes asymetriques
JP2021504135A (ja) グラフェン又はグラフェン誘導体膜
Yuan et al. Stable cation-controlled reduced graphene oxide membranes for improved NaCl rejection
Phao et al. A nitrogen-doped carbon nanotube enhanced polyethersulfone membrane system for water treatment
KR101381890B1 (ko) 나노복합체 초박형 분리막 및 이의 제조방법
JP5518186B2 (ja) 薄膜含有パーベーパレーション膜
US20150068972A1 (en) Nanocomposite membranes
EP2983808A1 (fr) Membranes comprenant du graphène
Li et al. Perforative pore formation on nanoplates for 2D porous MXene membranes via H2O2 mild etching
WO2009001970A1 (fr) Complexe membranaire de séparation, et procédé de production d'un complexe membranaire de séparation
Yu et al. Structure-performance relationships between amino acid-functionalized graphene quantum dots and self-cleaning nanofiltration membranes
JP6679118B2 (ja) ナノカーボン分離膜、ナノカーボン複合分離膜及びナノカーボン分離膜の製造方法
US11786870B2 (en) CMS membrane, method for the production thereof and use thereof
Park et al. Fabrication of thin film composite polyamide membrane for water purification via inkjet printing of aqueous and solvent inks
Nakamura et al. Preparation of amorphous carbon membranes synthesized via a glucose-solution hydrothermal method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17865864

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018547721

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17865864

Country of ref document: EP

Kind code of ref document: A1