WO2012067394A2 - Filtre viral à membrane en nanocarbone ayant une grande résistance et procédé de fabrication associé - Google Patents

Filtre viral à membrane en nanocarbone ayant une grande résistance et procédé de fabrication associé Download PDF

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WO2012067394A2
WO2012067394A2 PCT/KR2011/008685 KR2011008685W WO2012067394A2 WO 2012067394 A2 WO2012067394 A2 WO 2012067394A2 KR 2011008685 W KR2011008685 W KR 2011008685W WO 2012067394 A2 WO2012067394 A2 WO 2012067394A2
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carbon
nanoparticle
mold
nanoporous
nanoparticles
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PCT/KR2011/008685
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English (en)
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WO2012067394A3 (fr
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Woon-Jung Kim
Seung Ho Lee
Dong-Young Kang
Se-Young Ahn
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Hannam University Institute For Industry-Academia Cooperation.
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Priority claimed from KR1020110118354A external-priority patent/KR101276556B1/ko
Application filed by Hannam University Institute For Industry-Academia Cooperation. filed Critical Hannam University Institute For Industry-Academia Cooperation.
Publication of WO2012067394A2 publication Critical patent/WO2012067394A2/fr
Publication of WO2012067394A3 publication Critical patent/WO2012067394A3/fr

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    • 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
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
    • B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
    • B01D67/00413—Inorganic membrane manufacture by agglomeration of particles in the dry state by agglomeration of nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0058—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B01D69/144—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers" containing embedded or bound biomolecules
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • 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
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/301—Polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02831—Pore size less than 1 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • 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
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a carbon nanoporous membrane virus filter having high strength and a method for manufacturing the same and, more specifically, to a carbon nanoporous membrane virus filter having high strength, which is used to selectively filter various microorganisms including viruses and bacteria therethrough and has a uniform pore size of 5 to 500 nm with a margin of error of + 10%, and a method for manufacturing the same.
  • Table 2 schematically shows a type of enterovirus providing pathogenicity to humans and an infection symptom thereof.
  • the virus diseases are caused when contaminated raw water is not treated or when insufficient treatment is performed in private and small-scale filtration plants. In the case of a large-scale tap water supply system, the diseases are typically caused by secondary contamination in a conduit line. For reference, almost all viruses are detected in sewage throughout the year, an amount thereof is 10,000 to 100,000 infective units per 1 liter, and infectiousness may be maintained for several months in water or soil.
  • the virus may move depending on the movement of a body of water. Soil adsorbing viruses prevents the viruses from moving, but the viruses easily move in a sandy soil area and an area having high rainfall density and a water purifier largely attracts a consumer's interest with respect to drinking water.
  • a reverse osmotic pressure type having a market share of nearly 95% has problems frequently generated.
  • Makers of a reverse osmotic pressure type of water purifier insist that viruses from tap water are completely removed as compared to a hollow fiber membrane type or a natural filtration type.
  • water is filtered through ultra-fine pore having the size of about 0.1 nm, inorganic materials such as minerals are removed to form ultra-pure water, and all minerals are filtered to change drinking water into weak acidic water having the same property as distilled water.
  • the weak acidic water is known to have a pH of about 6.0 to 6.5, which is weak acidity, but it is reported that weak alkali water is better for a typical human body having acidity due to gastric acid and having a pH of blood of about 7.8.
  • a nanoporous membrane having uniform nanosized pores has been extensively studied to avoid the above problem, but there is a limit in that it is very difficult to manufacture a nanocarbon porous membrane having a uniform nanoparticle size of 90% or more in practice.
  • the degree of fractionation of the nanoparticles using a known centrifugal sedimentation or extraction method after synthesis of the nanoparticles (typically, uniformity is 50 to 60% ) is currently at a level of about 70%, and most inorganic filters has low strength, which form cracks during penetration of water, thus hindering purification of water.
  • a nano-scale filter having a pore size of 5 to 65 nm and a method for manufacturing the same are known to avoid the above disadvantage, but have other disadvantages in that a pore range of the nanocarbon filter is not wide as 5 to 65 nm and a pore distribution is nonuniform, which may allow a predetermined type of virus to pass therethrough.
  • a ceramic filter for filtration needs to have small and uniform pores, be porous, and have strength enough to endure predetermined pressure.
  • the pore size determining the filtration ability of the ceramic filter is very important, including a uniform distribution of pores.
  • a known ceramic filter for filtration is disadvantageous in that there is no variation in a type and a size of material powder to prevent the pore size from being easily and freely controlled and provide limited porosity of 50% or less and a nonuniform pore size.
  • performance of the filter may be evaluated by removal and concentrating abilities of fine materials depending on the pore size and a throughput per unit hour, and when the pore size is reduced, the throughput per unit hour is reduced even though the removal ability of the fine materials is increased, accordingly, it is important to appropriately control the pore size of the filter.
  • There is a problem in manufacturing an optimum ceramic filter that is useful for a predetermined process because the filter does not have a material having various ceramic particle sizes even though the filter has many advantages.
  • An object of the present invention is to provide a carbon nanoporous membrane virus filter having high strength, used to selectively filter various microorganisms including viruses and bacteria, and pores having a uniform size of 5 to 500 nm with a margin of error of ⁇ 10%, and a method for manufacturing the same.
  • One general aspect provides a carbon nanoporous membrane virus filter having high strength including a three-dimensional conjunction nanoporous carbon separation membrane having a pore size freely and easily controlled using silica particles such as fumed silica or colloidal silica and pores having a uniform pore size with a margin of error of + 10%; and a method for manufacturing the same.
  • the general aspect provides a carbon nanoporous membrane virus filter having high strength, used to selectively filter various microorganisms including viruses and bacteria, and including a three-dimensional conjunction nanoporous carbon separation membrane having pores having a uniform pore size with a margin of error of + 10% and a virus-antibody adsorbed on a surface of the three- dimensional conjunction nanoporous carbon separation membrane, and a method for manufacturing the same.
  • a carbon nanoporous membrane virus filter having high strength includes a three-dimensional conjunction nanoporous carbon separation membrane having nanoparticles having the uniform size of 5 to 500 nm with a margin of error of ⁇ 10% using a sequential fractionation process of a field-flow fractionation (FFF) and a split-flow thin fractionation (SF).
  • FFF field-flow fractionation
  • SF split-flow thin fractionation
  • a carbon nanoporous membrane virus filter having high strength includes a three-dimensional conjunction nanoporous carbon separation membrane having pores having a uniform pore size of 5 to 500 nm with a margin of error of ⁇ 10%, and a virus-antibody adsorbed on a surface of the three- dimensional conjunction nanoporous carbon separation membrane.
  • the present invention provides a carbon nanoporous membrane virus filter having high strength, including a three-dimensional conjunction nanoporous carbon separation membrane having pores having a uniform pore size of 5 to 500 nm with a margin of error of + 10%, and a virus-antibody adsorbed on a surface of the three-dimensional conjunction nanoporous carbon separation membrane.
  • the three-dimensional conjunction nanoporous carbon separation membrane is manufactured using a method including fractionating nanoparticles having a size of 5 to 500 nm to obtain nanoparticles having the uniform nanoparticle size with a margin of error of + 10% using a field-flow fractionation (FFF), a split-flow thin fractionation (SF), and a centrifuge, sintering the fractionated nanoparticles to manufacture a nanoparticle mold having a three-dimensional close-packed structure, dispersing a carbon precursor in the manufactured nanoparticle mold to manufacture a nanoparticle mold/carbon precursor complex, heat treating the nanoparticle mold/carbon precursor complex in a non-oxidizing atmosphere at 600 to 2000 °C for 1 to 60 hours to manufacture a nanoparticle mold/carbon complex, and treating the nanoparticle mold/ carbon complex using an acid to remove the nanoparticle mold accompanied by drying to manufacture the separation membrane.
  • FFF field-flow fractionation
  • SF split-flow thin fractionation
  • centrifuge sintering the fractionated nanoparticles to
  • the nanoparticles include fumed silica or colloidal silica.
  • the nanoparticles fractionated to have a uniform size in margin of error of ⁇ 10% are sintered to melt bond conjunction sites of the
  • the carbon nanoporous membrane virus filter having high strength may be used in electrical and electronic components, electrodes for fuel cells, membrane-electrodes for fuel cells, medical scaffolds, porous membranes for filters, coating materials, organic light emitting diodes (OLED), plasma display panels (PDP), biodegradable polymer porous continuous membranes, displays, gas masks, or porous membranes used in filters blocking viruses in the air according to the pore size of the filter.
  • OLED organic light emitting diodes
  • PDP plasma display panels
  • biodegradable polymer porous continuous membranes displays
  • gas masks or porous membranes used in filters blocking viruses in the air according to the pore size of the filter.
  • the filter is manufactured using a method including immersing the three-dimensional conjunction nanoporous carbon separation membrane having the uniform pore size with a margin of error of + 10% in the antibody aqueous solution and has an advantage in that the filter is useful to manage water used in various fields including weak alkali drinking water, industrial water, and agricultural water having no microorganisms including viruses and bacteria detected therein and the air.
  • the present invention provides a method for manufacturing a carbon nanoporous membrane virus filter having high strength, the method including a) fractionating nanoparticles having a size of 5 to 500 nm to obtain nanoparticles having the uniform nanoparticle size with a margin of error of ⁇ 10% using a field-flow fractionation (FFF), a split-flow thin fractionation (SF), and a centrifuge, b) sintering the fractionated nanoparticles to manufacture a nanoparticle mold having a three-dimensional close-packed structure, c) dispersing a carbon precursor in the manufactured nanoparticle mold to manufacture a nanoparticle mold/carbon precursor complex, d) heat treating the nanoparticle mold/carbon precursor complex in a non-oxidizing atmosphere of argon or nitrogen at 600 to 2000°C for 1 to 60 hours to manufacture a nanoparticle mold/carbon complex, e) treating the nanoparticle mold/carbon complex using an acid to remove the nanoparticle mold accompanied by drying to manufacture the separation membrane, and f) immersing the manufactured
  • the nanoparticles having a size of 5 to 500 nm in step a) are synthesized using a known sol-gel synthesis method in the fractionating of
  • the sol-gel synthesis method is a low temperature synthesis method for forming ceramic powder in a solution or a colloid suspension.
  • the sol is in a suspension state including dispersed colloid or inorganic solid uni- molecules, and the dispersed solid molecules are polymerized as the reaction progresses to form a continuous solid network structure, thus forming a gel state having no fluidity. Further, heat treatment may be performed in the sol state to form powder or a thin film via the gel state.
  • the nanoparticles may be fumed silica or colloidal silica in step a).
  • the fumed silica is produced using a process including a flame hydrolysis reaction of silicon tetrachloride in an atmosphere including oxygen and hydrogen to produce fine spherical silica particles, and commercial products having a particle size of a few nm to about 40 nm are selling (manufactured by Degussa Co., Ltd., Cabot Co., Ltd., and Wacker Co., Ltd.).
  • alkoxysilane compounds such as sodium silicates, potassium silicates, tetramethyl orthosilicates, or tetraethyl orthosilicates are subjected to a hydrolysis reaction in the presence of an acidic or basic catalyst to produce a colloidal sol including silica particles having a size of 5 to 500 nm.
  • the nanoparticles in the sol state partially agglomerate to each other while being mixed with the carbon precursor, such that a final pore size of manufactured carbon is larger than that of carbon in the sol state. Accordingly, if necessary, the nanoparticles needs to be stabilized in the sol state to prevent the agglomeration, and the stabilization of the sol is important from the standpoint of controlling and uniformalization of the pore size.
  • the nanoparticle sol using a stabilizer such as a surfactant during the production of the colloidal sol.
  • a stabilizer such as a surfactant
  • the pore size is more uniform as compared to the case where the nanoparticle sol stabilized using the surfactant is not used.
  • Cationic surfactants such as alkyl trimethylammonium halides, neutral surfactants such as oleic acids and alkyl amines, and anionic surfactants such as sodium alkyl sulfates and sodium alkyl phosphates may be used as the surfactant.
  • the cationic surfactant may be used because the surfaces of the particles are formed of anions, and examples of thereof include cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride
  • CTAB cetyltrimethylammonium bromide
  • cetyltrimethylammonium chloride cetyltrimethylammonium chloride
  • CCTAC tetradecyltrimethylammonium bromide
  • tetradecyltrimethylammonium chloride dodecyltrimethylammonium bromide
  • dodecyltrimethylammonium chloride dodecyltrimethylammonium chloride
  • Tergitol NP-9 Tergitol NP-9. Any surfactants suitable to the constitution of the present invention may be used besides the examples.
  • the FFF in step a) is one of the processes of fractionating particles and is called a field-flow fractionation or a single-phase chromatography.
  • a sample is added to a band-shaped groove, and operational force (acceleration, potential gradient, magnetic gradient, or thermal gradient) is perpendicularly applied to the surface of the groove to form a concentration gradient of solute particles in a depth direction, and the concentrations are fractionated with parabolic layers of a moving phase.
  • the SF is similar to the field-flow fractionation as a fractionation principle of the FFF, but different from the FFF in that large and small particles start to move si- multaneously and then exit via two different outlets at different sedimentation velocities depending on the size of the particles due to gravity.
  • the sintering in step b) melt bonds conjunction sites of the nanoparticles to stabilize the three-dimensional close-packed structure.
  • the sintering means consolidation of strongly compacted powder when the powder is subjected to compression molding into a predetermined shape and then heated, and it is preferable that the sintering is performed using an oil-hydraulic press at 100 to 500°C while force of 5 to 15 ton is applied thereto in the present invention.
  • the carbon precursor in step c) is one or more selected from polyvinyl chloride, polyvinylpyrrolidone, polyvinyl alcohol, monosaccharide, oligomer, and polysaccharide.
  • any one or mixtures of two or more selected from polyvinyl chlorides (PVC), polyvinylpyrrolidones (PVP), polyvinyl alcohols (PVA), glucoses, fructoses, galactoses, sucroses, arabinoses, mannoses, xyloses, phenol resins, ketone resins, maleic resins, and acryl resins may be dissolved in a solvent to form the carbon precursor.
  • Any one or a mixture of two or more selected from distilled water, methanol, and ethanol may be used as the solvent.
  • the present invention further includes, after step c, aging and drying the reactant at 50 to 150°C and washing the unreactant using distilled water after the drying.
  • the aging means maintaining the reactant at 50 to 150°C for a predetermined time. It is preferable that the dried reactant after the aging is washed using distilled water to remove the unreactant.
  • the carbon precursor dispersed in the solvent may be aged using the above procedure to be more uniformly dispersed, thus preventing a crack from being formed after the sintering and forming the uniform porous membrane.
  • the inorganic mold particles are removed using an acid in step e) to generate a carbon material having nanopores, and when the inorganic mold particles are made of silica, a hydrofluoric acid (HF) solution or a sodium hydroxide solution may be used as a removal solvent.
  • a hydrofluoric acid (HF) solution or a sodium hydroxide solution may be used as a removal solvent.
  • the silica mold particle/carbon complex may be agitated in the 20 to 60% hydrofluoric acid solution at normal temperature for 30 min to 50 hours to dissolve the silica mold in order to be removed.
  • one or more selected from polyvinyl chlorides one or more selected from polyvinyl chlorides,
  • polyvinylpyrrolidones polyvinyl alcohols, monosaccharides, oligomers, and polysaccharides may be used as the carbon precursor in step c), and any carbon precursor may be used in the method of the present invention as long as the carbon precursor can disperse the inorganic mold particles well in the inorganic mold/carbon precursor complex and be carbonized during the calcination.
  • the carbon precursor of the nanoparticle mold/carbon complex carbonized during the calcination is carbonized to form micropores having the size of 1 nm or less, a hydrofluoric acid or sodium hydroxide easily moves through the micropores to dissolve the nanoparticle mold, and a space occupied by the nanoparticle mold becomes a pore of carbon. Therefore, the shape and the size of the used nanoparticle mold are the same as those of the pore of the manufactured carbon.
  • a surface area, a pore volume, and a pore size of the carbon nanoporous membrane virus filter having high strength manufactured by using the method of the present invention were measured, and the number of cracks formed in the porous membrane after penetration of water was counted, resulting in the confirmation that the carbon nanoporous membrane virus filter having high strength of the present invention did not generate cracks even though the reverse osmotic pressure or hollow fiber membrane methods were not used. Further, it could be confirmed that the separation membrane having the uniform pore size was manufactured to manufacture the filter having the wide and uniform adsorption surface area and high strength and minerals passed through the filter to obtain weak alkali drinking water.
  • the carbon nanoporous membrane virus filter having high strength has high strength and significantly contributes to managing and utilizing water used in various fields including weak alkali drinking water, industrial water, and agricultural water having no microorganisms including viruses and bacteria detected therein.
  • the carbon nanoporous membrane virus filter having high strength has a uniform pore size with a margin of error of + 10% to be extensively used in a gas mask, an electronic sensor, a fuel cell, biological, and medical fields as well as in a water-related field.
  • FIG. 1 is a SEM picture of particles of silica powder in a colloidal sol, which are fractionated to have a uniform nanoparticle size with a margin of error of + 10% according to the present invention.
  • FIG. 2 is a picture of a nanoparticle mold/carbon precursor complex manufactured after sintering according to the present invention.
  • FIG. 3 is a SEM picture of a nanoparticle mold/carbon precursor complex manufactured after sintering according to the present invention.
  • FIG. 4 is a picture of a nanoparticle mold/carbon complex manufactured after calcination according to the present invention.
  • FIG. 5 is a SEM picture of a nanoparticle mold/carbon complex manufactured after calcination according to the present invention.
  • FIG. 6 is a SEM picture of a three-dimensional conjunction nanoporous carbon separation membrane according to the present invention.
  • the cyclohexane solvent was removed from the reactor using the rotary vacuum evaporator to produce the colloidal silica solution.
  • 400 mL of 99.9% ethyl alcohol (absolute ethanol) was added to the colloidal silica solution and sufficiently agitated to be well dispersed.
  • the centrifugation was then performed using the centrifuge at about 5000 to 6000 rpm to separate ethanol and colloidal silica from each other.
  • the separated ethanol solution was removed and drying was performed in the oven at 100?C to obtain silica powder having the average particle diameter of 58 nm.
  • the margin of error of the average particle diameter of the silica powder was + 50%.
  • the obtained silica powder was fractionated using the SPLITT fractionation (SF) to form silica powder having the average particle diameter of 58 nm.
  • the margin of error of the average particle diameter of the silica powder was + 10%. See FIG. 1.
  • the silica powder was sintered to form a three-dimensional structure including micropores having a desired size and regularly arranged.
  • the sintering was performed using the oil-hydraulic press at 150?C under force of 10 tons for 10 mins to manufacture the nanoparticle mold. See FIG. 2 and 3.
  • the manufactured nanoparticle mold and 10 mL of the carbon medium (0.01M PVC aqueous solution) were added to the Teflon beaker, heated at 100?C, and agitated.
  • the viscosity of the carbon medium measured using the Brookfield viscometer was 30,000 mPa.s (at No.4 Spindle) during the agitation, the resulting mold was put into the oven at 160°C, and removed from the oven when the PVC aqueous solution was completely removed.
  • the nanoparticle mold removed from the oven was washed with distilled water to remove PVC from the surface thereof, and calcined in the quartz tube in the tube furnace. After argon gas was blown into the furnace to allow the furnace to be in an argon atmosphere, the temperature was increased to 1000°C while the argon gas was continuously blown at a low rate to perform calcination for 5 hours.
  • the silica nanoparticle mold/carbon complex was put into the Teflon vial to remove the silica nanoparticle mold from the manufactured silica nanoparticle mold/carbon complex, the 48% hydrofluoric acid was added depending on the amount of the complex, and the vial was shaken using the shaker for 10 hours.
  • the hydrofluoric acid was filtered using the cellulose nitrate membrane filter, sufficient washing was performed using distilled water to remove the residual hydrofluoric acid, and drying was performed to manufacture the three-dimensional conjunction nanoporous carbon separation membrane. See FIG. 6.
  • the manufactured three-dimensional conjunction nanoporous carbon separation membrane was immersed using the acrylic acid dip coating method for one day in advance to be combined with the MS2 virus antibody.
  • the immersed three-dimensional conjunction nanoporous carbon separation membrane was immersed in the MS2 virus antibody aqueous solution for additional one day to manufacture the carbon nanoporous membrane virus filter having high strength including the MS2 virus- antibody adsorbed on the surface of the three-dimensional conjunction nanoporous carbon separation membrane.
  • ethyl alcohol 500 mL of 99.9% ethyl alcohol was added to the reactor having the volume of 1 L, and 60 mL of 28% ammonium hydroxide and 20 mL of tertiary distilled water were added thereto to hydrolyze silica ions, and agitated to produce the mixture solution. After the produced mixture solution was strongly sufficiently agitated to be homogenized, finally, 60 mL of 98% tetraethyl orthosilicate (TEOS) was added as the silicon alkoxide unit precursor. The agitation was continuously performed at room temperature for about 20 hours to sufficiently hydrolyze the silicon alkoxide ions in the mixture solution and grow particles having the uniform size.
  • TEOS tetraethyl orthosilicate
  • the colloidal silica ethanol suspension solution was centrifuged using the centrifuge at about 4000 rpm for 30 min to separate colloidal silica from the ethanol solution. After the separated ethanol solution was removed, the procedure that the remaining colloidal silica was washed using tertiary distilled water and centrifuged was repeated two and three times, and drying was performed in the oven at 100°C to obtain the silica powder having the average particle diameter of 110 nm. The margin of error of the average particle diameter of the silica powder was ⁇ 50%.
  • the obtained silica powder was fractionated using the SPLITT fractionation (SF) to form silica powder having the average particle diameter of 110 nm.
  • the margin of error of the average particle diameter of the silica powder was + 10%.
  • the silica powder was sintered to form a three-dimensional structure including micropores having a desired size and regularly arranged.
  • the sintering was performed using the oil-hydraulic press at 150°C under force of 10 tons for 10 mins to manufacture the nanoparticle mold.
  • the three-dimensional conjunction nanoporous carbon separation membrane and the carbon nanoporous membrane virus filter having high strength was manufactured using the same method as example 1.
  • the silica powder having the average particle diameter of 58 nm was synthesized using the same method as example 1.
  • the margin of error of the average particle diameter of the silica powder was + 50%.
  • the three-dimensional conjunction nanoporous carbon separation membrane and the carbon nanoporous membrane virus filter having high strength were manufactured using the same method as example 1 , except that the manufactured silica powder was not fractionated using the SPLITT fractionation (SF).
  • the silica powder having the average particle diameter of 110 nm was synthesized using the same method as example 2.
  • the margin of error of the average particle diameter of the silica powder was ⁇ 50%.
  • the three-dimensional conjunction nanoporous carbon separation membrane and the carbon nanoporous membrane virus filter having high strength were manufactured using the same method as example 1, except that the manufactured silica powder was not fractionated using the SPLITT fractionation (SF).
  • the following test was performed to confirm effective selective removal of the virus as the water-borne microorganism with respect to the carbon nanoporous membrane virus filters of examples 1 and 2 and comparative examples 1 and 2.
  • the hollow fiber membrane filter and the reverse osmotic membrane filter used in the typical water purifying filter were used as the control group.
  • the carbon nanoporous membrane virus filters of examples 1 and 2 and comparative examples 1 and 2 and the fluorescent detector were connected to the FFF system shown in FIG. 10, the Alexa 542 fluorescent dye was injected into the MS2 virus to be adsorbed thereon to increase the concentration sensitivity of the fluorescent detector to the MS2 virus, and the degree of detection was examined using the fluorescent detector (O: detected well, ⁇ : normally detected, and x: poorly detected).
  • Phthalocyanine blue pigment having the fixed size of 20 to 300 nm
  • MS2 virus Cultivated MS2 virus having the non-fixed size of 20 to 250 nm
  • the carbon nanoporous membrane virus filters of examples 1 and 2 have an excellent selective removal effect with respect to a virus having a non-fixed size as well as an inorganic pigment having a fixed size as compared to a hollow fiber membrane filter and a reverse osmotic membrane filter including a typical water purifying filter.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Filtering Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un filtre viral à membrane nanoporeuse en carbone présentant une grande résistance. La présente invention concerne en outre un procédé de fabrication associé. Le filtre viral à membrane nanoporeuse en carbone possédant une grande résistance possède une grande résistance et contribue considérablement à la gestion et à l'utilisation de l'eau utilisée dans différents domaines, y compris l'eau potable faiblement alcaline, l'eau industrielle, et l'eau agricole, pas de microorganismes, y compris des virus et des bactéries, n'y étant détectés, ni dans l'air, contrairement à un filtre connu.
PCT/KR2011/008685 2010-11-15 2011-11-15 Filtre viral à membrane en nanocarbone ayant une grande résistance et procédé de fabrication associé WO2012067394A2 (fr)

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KR1020110118354A KR101276556B1 (ko) 2010-11-15 2011-11-14 고강도 탄소 나노 기공막 바이러스 필터 및 이의 제조방법

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JPH06269645A (ja) * 1993-03-17 1994-09-27 Kitz Corp ウィルス分離用膜及びその製造方法
KR20020097295A (ko) * 2001-06-20 2002-12-31 주식회사 파인셀 졸-겔 반응의 무기물 주형을 사용한 나노세공 탄소재료의제조방법
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CN108310988A (zh) * 2018-01-31 2018-07-24 天津科技大学 高性能pu/pvb/ff过滤膜

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