KR20170006928A - Floating Transparent Film for Water Purification - Google Patents
Floating Transparent Film for Water Purification Download PDFInfo
- Publication number
- KR20170006928A KR20170006928A KR1020150098357A KR20150098357A KR20170006928A KR 20170006928 A KR20170006928 A KR 20170006928A KR 1020150098357 A KR1020150098357 A KR 1020150098357A KR 20150098357 A KR20150098357 A KR 20150098357A KR 20170006928 A KR20170006928 A KR 20170006928A
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- South Korea
- Prior art keywords
- water
- photocatalyst
- transparent film
- resin
- silica particles
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000007667 floating Methods 0.000 title abstract description 11
- 238000000746 purification Methods 0.000 title abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920001225 polyester resin Polymers 0.000 claims abstract description 22
- 239000004645 polyester resin Substances 0.000 claims abstract description 22
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000011325 microbead Substances 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- -1 benzene 1 Chemical compound 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- CQSQUYVFNGIECQ-UHFFFAOYSA-N 1-n,4-n-dimethyl-1-n,4-n-dinitrosobenzene-1,4-dicarboxamide Chemical compound O=NN(C)C(=O)C1=CC=C(C(=O)N(C)N=O)C=C1 CQSQUYVFNGIECQ-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical class CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical class FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B01J35/004—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
본 발명은 수질정화용 투명 필름에 관한 것으로, 더욱 자세하게는 광촉매를 함유하여 수면에 부유하면서 태양광에 의해 수질을 정화하는 투명 필름에 관한 것이다.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent film for water purification, and more particularly, to a transparent film containing a photocatalyst and floating on the water surface and purifying the water quality by sunlight.
일반적으로 양식장, 수족관, 저수조 등 물을 저장하는 장소의 수질정화를 위해 수질 정화 장치나 수질정화를 위한 화학물질, 미생물 등을 사용하고 있다. 이러한 물을 저장하는 장소는 주로 야외에 위치하고 있으므로, 자연광을 이용하여 물의 오염의 원인이 되는 유기물이나 미생물을 분해하기 위하여 광촉매를 사용하는 기술도 개발되고 있다. 광촉매를 사용하는 기술은 광화학 반응을 이용하여 오염수를 처리하는 방식으로 상온에서 완전분해가 가능하며, 환경에 유해한 부반응이 일어나지 않아 효율적으로 수질정화를 수행할 수 있는 기술이다.Generally, water purification facilities, chemical substances and microorganisms for water purification are used to purify the water at places where water is stored, such as farms, aquariums, and water tanks. Since the place for storing such water is mainly located in the outdoors, a technique of using a photocatalyst to decompose organic matter or microorganisms that cause pollution of water by using natural light is also being developed. Technology using photocatalyst is a technology that treats polluted water using photochemical reaction and can completely decompose at room temperature. It is a technology that can efficiently purify water because no side reaction harmful to the environment occurs.
이러한 예로는, 대한민국 공개특허공보 10-2008-0073893호에서 은나노 성분이 첨가된 광촉매를 수족관 내부에 수용되는 바닥재에 코팅함으로써 수족관의 항균 및 수질 정화 기능을 얻고 있다. 그러나 이러한 바닥재에 코팅된 광촉매의 촉매반응을 일이키기 위해서는 물 속까지 광에너지가 전달될 수 있도록 자외선 램프 등의 광원을 설치해야 하므로, 자연광만으로는 효율적인 수질정화가 어려워 넓은 장소에서 사용하기 곤란한 문제가 있다.For example, in Korean Patent Laid-Open Publication No. 10-2008-0073893, a photocatalyst having a silver nano component added thereto is coated on a flooring material contained in an aquarium, thereby obtaining an antibacterial and water purification function of an aquarium. However, since a light source such as an ultraviolet lamp must be installed so that the photon energy can be transferred to the water in order to achieve the catalytic reaction of the photocatalyst coated on the bottom material, it is difficult to efficiently purify the water by using only natural light, have.
또한, 대한민국 등록특허공보 10-0981910호에서는 광촉매를 폐목탄에 침투결착시켜 수질정화 카본 콘크리트 구조물을 제조함으로써 수질정화 및 식생을 가능하게 하는 기술이 개시되어 있다. 그러나 이러한 구조물도 블록, 관 등의 구조체를 형성하게 되므로, 양식장, 수족관, 저수조 등에 설비해야 하는 문제가 있다.Also, Korean Patent Registration No. 10-0981910 discloses a technique for purifying water and making vegetation possible by producing a water-purifying carbon concrete structure by infiltrating and binding a photocatalyst to waste charcoal. However, since such a structure also forms a structure such as a block and a tube, there is a problem that it is required to be installed in a farm, aquarium, and water tank.
따라서 설비가 필요없고, 양식장, 수족관, 저수조 등의 물을 저장하는 장소에 두는 것만으로 수질정화를 할 수 있는 방법이 요구되고 있다.
Therefore, there is a need for a method that can purify the water by simply placing it in a place where water such as a farm, aquarium, and water tank is stored.
본 발명은 이러한 종래기술의 문제점을 해결하기 위한 것으로, 양식장, 수족관, 저수조 등의 물을 저장하는 장소에 적용이 가능하며 수면 위에 부유하도록 두는 것만으로 자연광을 이용하여 수질정화를 할 수 있는 수면 부유형 투명 필름을 제공하는 것을 목적으로 한다.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide a water surface treatment device capable of being applied to a place for storing water such as a farm, aquarium and water tank, Type transparent film.
상기 과제를 해결하기 위한 본 발명의 수질정화용 수면 부유형 투명 필름은 폴리에스테르 수지 및 폴리올레핀 수지를 포함하는 표면 수지층, 중간층, 수면과 접하는 이면 수지층이 적층된 수면 부유형 투명 필름으로서, 상기 중간층은 광촉매가 담지된 메조포러스 실리카 입자를 함유하는 수지로 이루어지며, 상기 이면 수지층은 광촉매가 담지된 매크로포러스 실리카 입자를 함유하는 것을 특징으로 한다.In order to solve the above-mentioned problems, the waterproof type waterproof type transparent film of the present invention is a waterproof type transparent film laminated with a surface resin layer including a polyester resin and a polyolefin resin, an intermediate layer, and a back side resin layer contacting the water surface, Is composed of a resin containing mesoporous silica particles carrying a photocatalyst, and the above-mentioned backside resin layer contains macroporous silica particles carrying a photocatalyst.
이때, 상기 매크로포러스 실리카 입자는 실리카 마이크로비드에 의해 형성되며, 2차 입자의 평균입경이 5~20㎛인 것이며, 상기 메조포러스 실리카는 블록공중합체를 주형으로 하여 제조되며, 평균입경이 1~10㎛ 것을 특징으로 한다.The mesoporous silica particles are prepared by using silica micro beads and have an average particle diameter of 5 to 20 μm. The mesoporous silica is prepared using a block copolymer as a template, 10 mu m.
또한, 상기 광촉매는 1~5wt%의 조촉매가 담지된 것을 특징으로 한다.
Further, the photocatalyst is characterized in that 1 to 5 wt% of co-catalyst is supported.
본 발명의 수면 부유형 투명 필름은 별도의 설비나 공사없이 양식장, 수족관, 저수조 등의 물을 저장하는 장소에 부유하도록 두는 것만으로 자연광을 이용하여 수질정화를 할 수 있어, 사용이 편리하고, 사용후 회수가 간편하고, 환경친화적으로 수질정화가 가능한 효과를 얻을 수 있다.
The waterproof type transparent film of the present invention can be purified by using natural light only by floating it in a place where water such as a farm, an aquarium, and water tank is stored without a separate facility or work, It is possible to obtain an effect that the water recovery can be simplified and the water quality can be environmentally friendly.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 수면 부유형 투명 필름은 수면에 부유할 수 있는 필름이어야 하며, 동시에 태양광을 흡수하여 광촉매 반응을 일으키면서도 나머지 태양광을 물 속으로 투과시킬 수 있는 투명 필름이어야 한다.The waterproof type transparent film of the present invention should be a film that can float on the water surface and must be a transparent film capable of absorbing sunlight to cause photocatalytic reaction while allowing the remaining sunlight to penetrate into water.
따라서 본 발명의 폴리에스테르 수지 및 폴리올레핀 수지를 포함하는 표면 수지층, 중간층, 수면과 접하는 이면 수지층이 적층된 수면 부유형 투명 필름은 밀도가 0.96 g/㎤ 이하인 다공성 필름인 것이 바람직하다.Therefore, it is preferable that the waterproof type transparent film laminated with the surface resin layer including the polyester resin and the polyolefin resin of the present invention, the intermediate layer, and the back side resin layer contacting the water surface is a porous film having a density of 0.96 g / cm 3 or less.
본 발명에서 상기 표면 수지층은 폴리에스테르 수지 100 중량%에 대하여 폴리올레핀계 수지, 바람직하게는 폴리에틸렌 수지, 더욱 바람직하게는 저밀도 폴리에틸렌 수지를 5~30 중량% 함유하여 이를 압축 성형 등의 방법으로 제조함으로써 얻어질 수 있다. In the present invention, the surface resin layer contains 5 to 30% by weight of a polyolefin resin, preferably a polyethylene resin, more preferably a low-density polyethylene resin, based on 100% by weight of the polyester resin, Can be obtained.
또한, 상기 표면 수지층에 다공성을 부여하기 위해 발포제를 소정량 함유시키고 용융 압출시 미세기공을 형성하게 하는 것이 바람직하다. 상기 발포제는 폴리에스테르 수지 100 중량%에 대하여 0.3~10 중량%가 첨가되는 것이 바람직하다. 즉, 첨가량이 0.3 중량% 미만이면 발포가 불충분하여 미세 기공의 형성이 부족하므로 필름 전체의 밀도를 높이는 문제가 있으며, 10 중량%를 초과하면 기공이 과도하게 형성되어 내열성, 수치 안정성 및 기계적 성질이 저하되고 공압출시 공정 안정성이 저하되는 문제가 있다. In order to impart porosity to the surface resin layer, it is preferable that a predetermined amount of the foaming agent is contained and fine pores are formed upon melt extrusion. The foaming agent is preferably added in an amount of 0.3 to 10% by weight based on 100% by weight of the polyester resin. That is, if the addition amount is less than 0.3% by weight, the foaming is insufficient and the formation of the micropores is insufficient. Thus, there is a problem of increasing the density of the entire film. When the addition amount exceeds 10% by weight, the pores are excessively formed, There is a problem that the stability of the pneumatic release process is lowered.
상기 발포제로는 통상의 발포제라면 어떠한 것이라도 사용할 수 있으나, 프레온 12와 같은 염화불화탄화수소 화합물, 메틸렌클로라이드와 같은 염화탄화수소 화합물, 프로판, 부탄 등의 지방족 탄화수소 화합물 등의 휘발성 발포제; 아조디카본 아미드, 디아조아미노벤젠 등의 아조계 화합물, 벤젠 1,3-디설포히드라지드와 같은 설포히드라지드 화합물, N,N'-디니트로소-N,N'-디메틸테레프탈아미드와 같은 니트로소 화합물, 테레프탈아미드와 같은 아미드 화합물 등의 분해형 발포제를 사용할 수 있다.As the foaming agent, any conventional foaming agent may be used, but volatile foaming agents such as chlorinated hydrocarbon compounds such as Freon 12, chlorinated hydrocarbon compounds such as methylene chloride, and aliphatic hydrocarbon compounds such as propane and butane; Azo compounds such as azodicarbonamide and diazoaminobenzene, sulfohydrazide compounds such as benzene 1,3-disulfohydrazide, and N, N'-dinitroso-N, N'-dimethyl terephthalamide A decomposition type foaming agent such as an amide compound such as nitroso compound and terephthalamide can be used.
다음으로 상기 표면 수지층에 적층되면서 수면과 접하는 이면 수지층 사이에 개재되는 중간층은 폴레에스테르 수지에 상기 발포제를 수지 100 중량%에 대하여 0.3~10 중량%가 첨가하여 공압출함으로써 중간층을 형성할 수 있다.Next, the intermediate layer interposed between the surface resin layers which are laminated on the surface resin layer and which is in contact with the water surface is formed by co-extruding the foaming agent into the polyester resin in an amount of 0.3 to 10% by weight based on 100% by weight of the resin, have.
이면 수지층 역시 중간층과 동일한 방법으로 형성할 수 있다.The resin layer can be formed in the same manner as the intermediate layer.
상기 중간층과 이면 수지층의 차이점은 수지에 혼합되는 광촉매에 있다. 즉, 본 발명에서는 수면 부유형 투명 필름으로서, 오염수와 접촉면적이 넓으면서도 태양광에 의해 광촉매 반응이 효율적으로 일어나며, 넓은 표면적을 통해 필름의 밀도를 낮추면서도 광촉매 반응 효율을 높일 수 있는 적층 구조를 얻는 것을 과제로 한다.The difference between the intermediate layer and the backside resin layer is that the photocatalyst is mixed with the resin. That is, in the present invention, as a water-borne type transparent film, a photocatalytic reaction can be efficiently performed by sunlight while having a large contact area with contaminated water, and a laminated structure capable of increasing the photocatalytic reaction efficiency while lowering the density of the film through a large surface area Is obtained.
이러한 과제를 해결하기 위하여, 상기 중간층은 광촉매가 담지된 메조포러스 실리카 입자를 함유하는 수지로 이루어지며, 상기 이면 수지층은 광촉매가 담지된 매크로포러스 실리카 입자를 함유하는 수지로 이루어지는 것이 바람직하다.In order to solve such a problem, it is preferable that the intermediate layer is made of a resin containing mesoporous silica particles carrying a photocatalyst, and the backside resin layer is made of a resin containing macroporous silica particles carrying a photocatalyst.
매크로포러스 물질은 일반적으로 기공의 직경이 50nm 이상인 다공성 물질로 정의되며, 메조포러스 물질은 기공의 직경이 2~50nm인 다공성 물질로 정의된다. 따라서 기공의 크기에 따라 담지되는 광촉매 입자의 크기나 분포가 달라지게 되며 담지량에 따른 광촉매의 표면적도 달라지게 된다.The macroporous material is generally defined as a porous material having a pore diameter of 50 nm or more, and the mesoporous material is defined as a porous material having a pore diameter of 2 to 50 nm. Therefore, the size and distribution of the photocatalyst particles to be supported depend on the pore size, and the surface area of the photocatalyst varies depending on the amount of the pore.
즉, 수면과 접촉하는 이면 수지층에는 매크로포러스 실리카 입자를 혼합함으로써 수지층의 밀도를 상대적으로 낮게 할 수 있고, 물과 광촉매의 접촉면적을 크게할 수 있다.That is, the density of the resin layer can be relatively lowered by mixing the macroporous silica particles in the back resin layer in contact with the water surface, and the contact area between water and the photocatalyst can be increased.
매크로포러스 실리카 입자는 실리카 마이크로비드를 소성하는 통상의 제조방법으로 얻어질 수 있다. 본 발명에서는 상기 매크로포러스 실리카 입자의 투과도(water permiability)가 1.5kg/㎠의 질소압에서 측정할 때 1.4(ml/㎠)·(min)-1·(kg/㎠)-1 이상이고, 비드의 평균 직경이 0.05~0.10㎛이며, 압밀화 지수가 0.60 이하 것이 바람직하다.The macroporous silica particles can be obtained by a conventional production method of calcining silica microbeads. The present invention, 1.4 (ml / ㎠) · ( min) -1 · (kg / ㎠) -1 or more when the transmittance of the macroporous silica particles (permiability water) is measured at a nitrogen pressure of 1.5kg / ㎠, beads Of 0.05 to 0.10 mu m and a consolidation index of 0.60 or less.
이러한 특성을 가짐으로써 본 발명의 매크로포러스 실리카 입자는 10~20 wt%의 광촉매를 담지할 수 있게 된다.By having such characteristics, the macroporous silica particles of the present invention can support 10 to 20 wt% of the photocatalyst.
또한, 메조포러스 실리카 입자는 공중합체를 주형으로 하여 테트라에틸오르소실리케이트 등의 실리케이트를 혼합하고 수열합성하는 통상의 제조방법으로 제조할 수 있다. 상기 메조포러스 실리카 입자는 1~10 wt%의 광촉매를 담지할 수 있게 된다. 예를 들어, 산화티탄 광촉매를 사용할 경우, 광촉매의 담지는 실리케이크와 티타늄 이소프로폭사이드, 사염화티탄 등의 티타늄 원료를 혼합하고, 이를 수열합성함으로써 간단히 제조할 수 있다.Further, the mesoporous silica particles can be produced by a usual production method in which the copolymer is used as a template and a silicate such as tetraethylorthosilicate is mixed and hydrothermally synthesized. The mesoporous silica particles can support 1 to 10 wt% of the photocatalyst. For example, when a titanium oxide photocatalyst is used, the photocatalyst can be easily supported by mixing the silica cake with a titanium raw material such as titanium isopropoxide or titanium tetrachloride, and hydrothermally synthesizing the titanium raw material.
상기 메조포러스 실리카는 표면적이 800 내지 1,000 ㎡/g이고, 세공 직경이 4 내지 10 nm인 것이 광촉매의 담지 및 수질 정화 효율에 있어서 가장 적합하다.The mesoporous silica having a surface area of 800 to 1,000 m < 2 > / g and a pore diameter of 4 to 10 nm is most suitable for supporting the photocatalyst and for purifying the water.
본 발명에 사용되는 광촉매는 태양광에 의하여 광촉매 활성을 나타낼 수 있는 광촉매라면 어떠한 것이라도 사용할 수 있다. 예를 들어, 아나타제형 이산화티탄, 산화아연, 황화카드뮴, 산화텅스텐 등을 들 수 있는데, 아나타제형 이산화티탄을 사용하는 것이 바람직하다. 상기 광촉매를 메조포러스 및 매크로포러스 실리카 입자에 담지하는 방법은 사염화티탄, 티탄이소프로폭사이드 등의 원료를 실리카 입자와 가열 혼합하고 소성하는 통상의 증발법을 이용할 수 있고, 또는 메조포러스 또는 매크로포러스 실리카 입자의 제조시 티타늄 원료를 혼합함으로써 제조할 수도 있다.The photocatalyst used in the present invention can be any photocatalyst capable of exhibiting photocatalytic activity by sunlight. For example, anatase type titanium dioxide, zinc oxide, cadmium sulfide, tungsten oxide and the like can be mentioned, and it is preferable to use anatase type titanium dioxide. The method of carrying the photocatalyst on the mesoporous and macroporous silica particles can be carried out by a conventional evaporation method in which raw materials such as titanium tetrachloride and titanium isopropoxide are heated and mixed with the silica particles and fired, Or may be produced by mixing a titanium raw material in the production of silica particles.
통상적인 광촉매는 자외선 조사에 의해 광촉매 반응을 일으키므로 태양광의 대부분을 차지하는 가시광을 이용할 수 없는 문제가 있다. 따라서 상기 광촉매의 표면에 조촉매를 담지함으로써 가시광에서도 촉매활성을 나타내도록 할 수 있다.Conventional photocatalyst causes a photocatalytic reaction by ultraviolet irradiation, and thus there is a problem that visible light occupying most of the sunlight can not be used. Therefore, by supporting the co-catalyst on the surface of the photocatalyst, the catalytic activity can be exhibited even in the visible light.
이러한 조촉매로는 백금, 로듐, 팔라듐, 루비듐 등의 귀금속이나 은, 금, 니켈 등을 사용할 수 있다. 상기 조촉매의 담지도 통상의 증발건고법을 통해 수행할 수 있다.
Examples of such a promoter include noble metals such as platinum, rhodium, palladium, and rubidium, and silver, gold, and nickel. Carrying of the promoter can also be carried out by a conventional evaporation-drying method.
본 발명의 필름은 상기 표면 수지층을 구성하는 폴리에스테르 수지, 상기 중간층을 형성하는 메조포러스 실리카 입자가 혼합된 폴리에스테르 수지, 및 상기 이면 수지층을 형성하는 매크로포러스 실리카 입자가 혼합된 폴리에스테르 수지를 공압출하고 이를 2축 연신함으로써 형성할 수 있다. 이때 필름의 연신배율은 1축 방향으로 3~5배, 2축 방향으로 3~5배 연신하는 것이 바람직하다. 또한, 연신공정 후 200~250℃로 열처리하는 것이 바람직하다.
The film of the present invention is obtained by mixing a polyester resin constituting the surface resin layer, a polyester resin mixed with mesoporous silica particles forming the intermediate layer, and a polyester resin mixed with macroporous silica particles forming the above- And then biaxially stretching the same. At this time, the stretching magnification of the film is preferably 3 to 5 times in the uniaxial direction and 3 to 5 times in the biaxial direction. After the stretching step, it is preferable to perform heat treatment at 200 to 250 ° C.
본 발명의 필름은 수면 부유형 투명 필름이므로, 양식장, 수족관, 저수조 등 물을 저장하는 장소에 자연광에 노출되도록 적당한 면적으로 절단하여 1개월 정도 띄워두는 것만으로 수질 정화의 효과를 달성할 수 있다. 또한, 제품의 수명이 다 하면 수면 위에 떠있는 상태의 필름을 걷어내기만 하면 되므로 수거도 용이한 장점이 있다.
Since the film of the present invention is a waterproof type transparent film, it is possible to achieve the effect of purifying the water by simply cutting it to an appropriate area so as to be exposed to natural light at a place where water is stored, such as a farm, aquarium or water tank, and floating it for about one month. In addition, when the life of the product is over, it is easy to collect the film because it is only necessary to remove the film floating on the water surface.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 하기 실시예에 의하여 본 발명의 내용이 한정되는 것은 아니다.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.
광촉매 담지 매크로포러스 실리카 입자의 제조Preparation of Photocatalyst-bearing Macrophous Silica Particles
100g의 실리카 마이크로스피어(평균입도 68nm)를 도가니에 담고 800℃에서 1시간 소성한 후, 이를 분쇄하여 평균입경이 15㎛인 매크로포러스 실리카 입자를 얻었다.100 g of silica microspheres (average particle size of 68 nm) were placed in a crucible and calcined at 800 DEG C for 1 hour, followed by pulverization to obtain macroporous silica particles having an average particle size of 15 mu m.
상기 매크로포러스 실리카 입자를 에탄올 용액이 담긴 증발접시에 담고 매크로포러스 실리카의 중량에 대하여 이산화티탄 기준으로 10 wt%가 되도록 티타늄이소프로폭사이드(TTIP)을 부가한 후 증발건고하고, 이를 450℃에서 2시간 소성하여 광촉매를 담지하였다.The macroporous silica particles were placed in an evaporation dish containing an ethanol solution, and titanium isopropoxide (TTIP) was added thereto in an amount of 10 wt% based on the weight of the macro-porous silica, followed by evaporation to dryness. And calcined for 2 hours to carry the photocatalyst.
소성이 끝난 매크로포러스 실리카 입자를 다시 에탄올 용액이 담긴 증발접시에 담고 이산화티탄 기준으로 2 wt%의 은이 담지되도록 질산은을 부가하고 증발건고한 후, 이를 300℃에서 1시간 소성하여 조촉매를 담지하였다.
The fired macroporous silica particles were again placed in an evaporation dish containing an ethanol solution. Silver nitrate was added so that 2 wt% of silver was supported on the basis of titanium dioxide, evaporated to dryness, and fired at 300 ° C for 1 hour to carry the cocatalyst .
광촉매 담지 메조포러스 실리카 입자의 제조Preparation of photocatalyst-bearing mesoporous silica particles
트리블록 공중합체인 P-123(EO20PO70EO20)을 1.6M의 염산 수용액에 녹인 후 테트라에틸오르소실리케이트(TEOS) 0.1M을 부가하고 30분간 혼합하였다.P-123 (EO20PO70EO20) as a triblock copolymer was dissolved in a 1.6 M hydrochloric acid aqueous solution, 0.1 M tetraethylorthosilicate (TEOS) was added, and the mixture was mixed for 30 minutes.
상기 용액에 티타늄 이소프로폭사이드(TTIP)의 이소프로판올 용액을 투입하고 30분간 교반하였다. 이때, TEOS와 TTIP의 Si/Ti 몰비는 30:1이었다.To this solution was added isopropanol solution of titanium isopropoxide (TTIP) and stirred for 30 minutes. At this time, the Si / Ti molar ratio of TEOS to TTIP was 30: 1.
상기 용액을 수열합성기에 투입하고 12시간 수열합성하여 메조포러스 실리카를 제조하였다.The solution was introduced into a hydrothermal synthesizer and hydrothermally synthesized for 12 hours to prepare mesoporous silica.
상기 메조포러스 실리카 입자를 에탄올 용액이 담긴 증발접시에 담고 이산화티탄의 중량을 기준으로 1 wt%의 은이 담지되도록 질산은 용액을 부가한후 열을 가하면서 증발건고하고, 이를 300℃에서 1시간 소성하여 조촉매를 담지하였다.
The mesoporous silica particles were placed in an evaporation dish containing an ethanol solution, and a silver nitrate solution was added so that 1 wt% of silver was supported on the basis of the weight of titanium dioxide. Then, the mesoporous silica particles were evaporated to dryness while heating, Thereby carrying a promoter.
필름의 제조Production of film
폴리에스테르 수지에 용융지수 4.0g/min의 랜덤폴리에틸렌 수지를 80:20의 중량비로 혼합하고 상용화제, 윤활제, 발포제를 혼합하고 컴파운딩하여 제1 폴리에스테르 수지를 제조하였다.A random polyester resin having a melt index of 4.0 g / min was mixed in a weight ratio of 80:20 to a polyester resin, and a compatibilizing agent, a lubricant and a foaming agent were mixed and compounded to prepare a first polyester resin.
폴리에스테르 수지 100 중량%에 대하여 광촉매 담지 메조포러스 실리카 입자를 5 중량% 첨가하고 컴파운딩하여 제2 폴리에스테르 수지를 제조하였다.5% by weight of photocatalyst-carrying mesoporous silica particles was added to 100% by weight of the polyester resin, and compounding was carried out to prepare a second polyester resin.
다음으로 폴리에스테르 수지 100 중량%에 대하여 광촉매 담지 매크로포러스 실리카 입자를 10 중량% 첨가하고 컴파운딩하여 제3 폴리에스테르 수지를 제조하였다.Next, 10 wt% of photocatalyst-bearing macroporous silica particles was added to 100 wt% of the polyester resin, and compounding was conducted to produce a third polyester resin.
상기 제1 내지 제3 폴리에스테르 수지를℃ 건조한 후, 압출기와 피드블럭이 장착된 T-다이를 사용하여 제2 폴리에스테르 수지를 중간층인 제1 층으로 하여 압출하고, 이와 동시에 제1 및 제3 폴리에스테르 수지를 각각 표면 수지층과 이면 수지층이 되도록 하여 각 측의 두께비가 20:35:45가 되도록 공압출하여 필름을 제조하였다. After the first to third polyester resins are dried at a temperature of 캜, a second polyester resin is extruded as a first layer as an intermediate layer by using a T-die equipped with an extruder and a feed block, and at the same time, The polyester resin was made into a surface resin layer and a back resin layer, respectively, and co-extruded so that the thickness ratio on each side was 20:35:45.
이어서 상기 필름을 180℃에서 종방향으로 4배 연신하고, 220℃에서 열처리하고, 다시 220℃에서 횡방향으로 4배 연신하고, 230℃에서 열처리함으로써 두께 100㎛의 수면 부유형 투명 필름을 제조하였다. 제조된 수면 부유형 투명 필름의 밀도는 0.85g/㎤이었다.
Subsequently, the film was stretched four times in the longitudinal direction at 180 ° C, heat-treated at 220 ° C, stretched four times in the transverse direction at 220 ° C, and heat-treated at 230 ° C to prepare a water- . The density of the produced waterproof type transparent film was 0.85 g / cm3.
[비교예 1][Comparative Example 1]
폴리에스테르 수지 100 중량%에 대하여 광촉매 담지 메조포러스 실리카 입자를 10 중량% 첨가하고 컴파운딩하여 제3 폴리에스테르 수지를 제조한 것 외에는 실시예 1과 동일한 방법으로 수면 부유형 투명 필름을 제조하였다. 제조된 수면 부유형 투명 필름의 밀도는 0.91g/㎤이었다.
A water surface type transparent film was prepared in the same manner as in Example 1, except that 10 wt% of photocatalyst-carrying mesoporous silica particles was added to 100 wt% of the polyester resin and compounding was conducted to produce a third polyester resin. The density of the produced waterproof type transparent film was 0.91 g / cm 3.
[시험예 1][Test Example 1]
실시예 1 및 비교예 1에서 제조된 투명 필름을 가로×세로가 1×1m가 되도록 절단하여 양식장 물 500L가 담긴 수조 위에 부유하도록 둔 후 시간에 따른 화학적 산소요구량(COD), 용존 총질소(T-N), 용전 총인(T-P) 저감정도를 측정하였다. 아래 표 1에 그 결과를 나타내었다.
The transparent film prepared in Example 1 and Comparative Example 1 was cut to have a size of 1 x 1 m and allowed to float on a water tank containing 500 L of aquaculture, and then the chemical oxygen demand (COD), dissolved total nitrogen (TN ), And the TP reduction (TP). The results are shown in Table 1 below.
125
125
10.81
10.81
2.65
2.65
상기 시험결과를 살펴보면, 투명 필름을 설치하지 않은 수조에 비해 실시예 1, 비교예 1에서 모두 COD, T-N, T-P가 감소하는 결과를 얻었으나, As a result of the test, COD, T-N, and T-P were decreased in Example 1 and Comparative Example 1, respectively,
본 발명의 광촉매가 담지된 메조포러스 실리카 입자를 함유하는 수지로 이루어진 중간층, 광촉매가 담지된 매크로포러스 실리카 입자를 함유하는 수지로 이루어진 이면 수지층이 적층된 투명 필름에서 수질 정화의 향상된 효과가 얻어지는 점을 확인하였다.An intermediate layer made of a resin containing the photocatalyst-bearing mesoporous silica particles of the present invention, and an improved effect of water purification in a transparent film laminated with a backside resin layer made of a resin containing macroporous silica particles carrying photocatalyst Respectively.
Claims (4)
상기 중간층은 광촉매가 담지된 메조포러스 실리카 입자를 함유하는 수지로 이루어지며,
상기 이면 수지층은 광촉매가 담지된 매크로포러스 실리카 입자를 함유하는 것을 특징으로 하는 수질정화용 수면 부유형 투명 필름.A waterproof type transparent film laminated with a surface resin layer comprising a polyester resin and a polyolefin resin, an intermediate layer, and a back side resin layer contacting the water surface,
Wherein the intermediate layer is made of a resin containing mesoporous silica particles carrying a photocatalyst,
Wherein the backside resin layer contains macroporous silica particles on which a photocatalyst is supported.
상기 매크로포러스 실리카 입자는 실리카 마이크로비드에 의해 형성되며, 2차 입자의 평균입경이 5~20㎛인 것을 특징으로 하는 수질정화용 수면 부유형 투명 필름.The method according to claim 1,
Wherein the macroporous silica particles are formed by silica microbeads, and the secondary particles have an average particle diameter of 5 to 20 占 퐉.
상기 메조포러스 실리카는 블록공중합체를 주형으로 하여 제조되며, 평균입경이 1~10㎛ 것을 특징으로 하는 수질정화용 수면 부유형 투명 필름.The method according to claim 1,
Wherein the mesoporous silica is prepared using a block copolymer as a template and has an average particle size of 1 to 10 占 퐉.
상기 광촉매는 1~5wt%의 조촉매가 담지된 것을 특징으로 하는 수질정화용 수면 부유형 투명 필름.The method according to claim 1,
Wherein the photocatalyst is supported by 1 to 5 wt% of a promoter.
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| JPH09174046A (en) * | 1995-12-28 | 1997-07-08 | Takenaka Komuten Co Ltd | Water purifying apparatus |
| JPH10235346A (en) * | 1997-02-24 | 1998-09-08 | Sanenerugii Kk | Sheet material for water treatment and its production |
| JP2005040769A (en) * | 2003-07-25 | 2005-02-17 | Yukio Hirose | Water-quality enhancement structure and water-quality enhancement method using it |
| JP3117334U (en) * | 2005-10-03 | 2006-01-05 | 株式会社上田敷物工場 | Water purification tool |
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