WO2021124983A1 - 殺菌作用による水質浄化機能を有する構造体 - Google Patents

殺菌作用による水質浄化機能を有する構造体 Download PDF

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WO2021124983A1
WO2021124983A1 PCT/JP2020/045644 JP2020045644W WO2021124983A1 WO 2021124983 A1 WO2021124983 A1 WO 2021124983A1 JP 2020045644 W JP2020045644 W JP 2020045644W WO 2021124983 A1 WO2021124983 A1 WO 2021124983A1
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water
bacteria
needle
calcium
acicular
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PCT/JP2020/045644
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English (en)
French (fr)
Japanese (ja)
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根岸　信彰
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国立研究開発法人産業技術総合研究所
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Publication of WO2021124983A1 publication Critical patent/WO2021124983A1/ja

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention relates to a structure that captures bacteria in water or exerts a bactericidal effect depending on its form, and its use.
  • Non-Patent Document 1 Black silicon has the strongest bactericidal action against Gram-negative bacteria, with dragonfly wings and cicada wings becoming weaker in that order.
  • Black silicon has nanopillars with a height of 500 nm
  • cicada and dragonfly wings have nanopillars with a height of 240 nm
  • the surface composition of black silicon is mainly silicon oxide, which is formed from chitin.
  • the composition of the surface of the wings of cicadas and dragonflies is lipid.
  • the mechanism by which bacteria are killed by these nanopillars is not described in Non-Patent Document 1, and the reason why black silicon has a stronger bactericidal action than the wings of dragonflies and cicadas is due to the difference in the shape of the nanopillars, or constitutes the nanopillars. It is unknown whether it is due to the chemical reason of the substance.
  • the needle-shaped structure has a bactericidal effect based on the mechano bactericidal effect, which is not limited to black silicon and the like.
  • a bactericidal effect based on the mechano bactericidal effect, which is not limited to black silicon and the like.
  • gecko skin Non-Patent Document 2
  • nanoglass and black diamond nanocone Non-Patent Document 3
  • titania nanowires organic polymers such as PMMA
  • gold nanostructures gold nanostructures
  • Patent Document 1 describes the application of an antibacterial surface having a surface structure that prevents the adhesion of bacteria to medical devices, household water supplies, and even marine structures.
  • Patent Document 2 discloses a method for synthesizing nanopillars by anodizing for the purpose of anti-mold performance on the surface of a water heater including a coffee maker, a lunch box, a heat exchanger, etc.
  • Patent Document 3 discloses a method for synthesizing nanopillars with polycarbonate. It is disclosed that a laminated film with a synthetic polymer film having nano-sized convex portions is used to impart bactericidal properties to the surfaces of various molded articles.
  • Non-Patent Documents 1 to 3 show that there are materials having various mechano-bactericidal effects, from natural materials to artificial ones, and these documents are intended to treat bacterial species existing in water. I haven't done anything. The reason is that suppressing the adhesion of bacteria to the surface of the skin and wings of animals including insects is a required function, and Patent Document 3 also describes the surface of a touch panel display such as a smartphone made of polycarbonate. It is described that a synthetic polymer film having a surface having a bactericidal action is attached to the touch panel installed in a hospital or a public place and can be touched by an unspecified number of people.
  • the present invention provides a structure having a surface structure that can sterilize water simply by placing it in running water and that can be safely drunk water that is not contaminated with bacteria, and that the structure is placed in water. It is an object of the present invention to provide a method for sterilizing and purifying water simply by placing it on the water.
  • the present invention captures bacteria contained in drinking water or the like into micron-sized acicular crystals or acicular habits precipitated or carried on the surface thereof, and smaller nano-sized acicular crystals or acicular crystals. It relates to a structure having a solid surface that can be sterilized by habit. By passing water containing bacteria through the surface of the structure of the present invention, the bacteria are caught in the peculiar needle-like structure and do not flow downstream, and the needle-like structure forms a cell membrane that constitutes the bacteria. By destroying it, intracellular substances are eluted and the bacteria are killed.
  • the bacteria captured in the needle-like structure are photocatalytically decomposed by the active species generated from the photocatalyst by irradiation with an excitation light source. It is possible to mineralize the cells, and unlike filtration, it is possible to add a technique for avoiding the adverse effects of dead bacteria accumulating.
  • the present invention relates to the following structures (1) to (8).
  • (1) Nano-sized to micron-sized acicular crystals and acicular crystal habits of inorganic compound ceramics that are insoluble in aqueous solution and do not contain elements that are toxic to the living body are precipitated or supported on the solid surface of the base material.
  • the calcium-containing compound is calcium carbonate, apatite, or calcium silicate.
  • the present invention also relates to the following (9) water sterilization and purification method.
  • (9) A method for sterilizing and purifying water, which comprises placing the structure according to any one of (1) to (8) above in water.
  • the acicular crystals and acicular habits that form part of the structure of the present invention are naturally placed on the solid surface of the base material by passing an aqueous solution of a calcium-containing compound on the base material and repeating drying. Since it is precipitated or supported, it is easy to manufacture. Further, acicular crystals and acicular habits damaged by water flow can be easily recovered and repaired by exposing them to mineral components in water by passing natural water containing calcium ions. Since the needle-like crystals and needle-like crystal habits precipitated or supported in the structure of the present invention are crystals composed of calcium carbonate, apatite, and calcium silicate, they are dissolved in water when pure water is passed through them.
  • the body will gradually lose weight in a weakly acidic environment due to the influence of calcium carbonate, but the place where the structure of the present invention is expected to be used is especially in developing countries, and the purpose is to purify drinking water.
  • the water to be treated is often groundwater such as spring water, and usually contains mineral components.
  • water contains components such as calcium bicarbonate, it has the effect of recovering needle-like crystal habits damaged by water flow, so it can be said that it has a self-repairing function, like a filtration device. It is fundamentally different from the one that loses its function due to continuous use.
  • a major problem with purifying drinking water in developing countries is that access to safe water is too expensive, but purifying drinking water with the structures of the invention maintains bactericidal activity through continued use.
  • a photocatalytic material is used on the solid surface of the base material, bacteria captured by needle-like crystal habits can be mineralized by photocatalytic action.
  • (b) Magnification 5000 times An electron micrograph of calcite crystals grown on ceramics, which is the same calcium carbonate as aragonite. Magnification 1000 times.
  • the structure of the present invention has nano-sized to micron-sized acicular crystals and acicular crystal habits precipitated or supported on the solid surface of the base material.
  • the base material of the structure may be any material, shape, and size as long as it is insoluble in water and does not contain elements that are toxic to the living body. ..
  • the solid surface of the base material may be a material that is not only insoluble in water and does not contain elements that are toxic to the living body, but also has a needle-like structure on the surface.
  • the base material and its solid surface may be the same material or different materials, but a base material on which acicular crystals or acicular crystal habits made of inorganic oxide ceramic are precipitated or supported on the solid surface. However, it is convenient to use an inorganic oxide ceramic.
  • “Sterilization” in the present invention means reducing the effective number of proliferative microorganisms existing in water.
  • the term “bacteria” or “microorganisms” refers to organisms such as bacteria, fungi, and protozoans whose presence cannot be discerned with the naked eye and whose size is smaller than the size that can be observed with a microscope or the like. Not included.
  • the "nano-sized to micron-sized acicular to micron-sized acicular crystals and acicular habits of inorganic compound ceramics that are insoluble in aqueous solutions and do not contain elements that are toxic to the living body" of the present invention are preferably calcium-containing compounds.
  • the needle-like crystal habit composed of calcium carbonate is aragonite, and it is known that aragonite has no ecotoxicity (see Non-Patent Document 13).
  • the nano-sized to micron-sized have a length of about several tens of nm to about ten-odd ⁇ m, and the size of bacteria including fungi is about ten-odd ⁇ m at most, so these are captured. Or it may be long enough to be stabbed and physically destroyed. Further, it is described in Non-Patent Document 15 that the curvature of the tip of the needle has a size suitable for destroying the cell wall, and the aragonite needle-like crystal habit is almost the same as this.
  • the structure of the present invention can be produced by repeatedly passing water and drying the mixed aqueous solution on the solid surface of the base material to form aragonite having acicular crystal habit on the solid surface.
  • the saturated concentration of the aqueous calcium bicarbonate solution is desirable, but lower concentrations can also be used.
  • Non-Patent Document 4 It is possible to accelerate the growth rate of aragonite by using a photocatalytic material on the solid surface and continuing to irradiate light with an excitation wavelength that activates the photocatalyst. This utilizes the calcium carbonate precipitation mechanism associated with the photocatalytic decomposition reaction of bicarbonate ions described in Non-Patent Document 4.
  • Cationic species other than calcium such as sodium, potassium, and magnesium, also become carbonates by photocatalytic action, but these carbonates are water-soluble, and by shifting to an equilibrium state between carbonate ions and bicarbonate ions, these Not only does salt precipitation not occur, but the concentration of bicarbonate ions does not change before and after the photocatalytic reaction. Only in the presence of calcium ions does the bicarbonate ion concentration decrease before and after the reaction.
  • the crystal forming the needle-like crystal habit consisting of calcium silicate, in the wollastonite group, Nekoilite, Okenite, Xonolite, Jennite , Hillebramdiote, Tobermorite, the gyro light group, Gyrolite, Truscottite, at [nu-C 2 S Group , Afwillite, and others, such as Trickium silicate hydrate and ⁇ -calcium silicate hydrate are known. Any of these needle-like crystal habits can be formed on the solid surface by the same procedure as the method for precipitating aragonite using water containing calcium ions and water-soluble silica.
  • the main components in natural water usually contain not only calcium but also water-soluble silica (dissolved silica, metasilicic acid). If the acicular structure is formed of calcium silicate instead of calcium carbonate, it is possible to self-repair the acicular structure damaged in the process of utilization by passing water in which calcium ions and dissolved silica coexist. .. As a mechanism, it is known that calcium silicate hydrate is formed by slowly reacting calcium ions in water with dissolved silica over time, and it is considered that this mechanism exerts self-repairing ability.
  • the acicular structure of calcium silicate does not form in a short time at normal temperature and pressure, but it is possible to pre-form calcium silicate crystals on the solid surface by using the autoclave method. This makes it possible to deposit calcium silicate on the surface of the photocatalyst and apply the self-repair as described above. Details of the method for synthesizing calcium silicate and the mechanism of precipitation are described in Non-Patent Documents 5 to 7.
  • apatite which is said to have excellent biocompatibility among calcium-containing compounds, becomes acicular crystals.
  • apatite a part of apatite (apatite), which is said to have excellent biocompatibility among calcium-containing compounds, becomes acicular crystals.
  • apatite has a self-healing function in natural water, but it is possible to immobilize acicular apatite crystals on the surface of titanium oxide photocatalyst by hydrothermal synthesis to give mechano-bactericidal effect. It is considered possible as well as calcium.
  • hydroxyapatite (hydroxyapatite) is famous for its high biocompatibility, and it is considered that it will not cause any harmful effects even if it is taken into the human body. Therefore, it is a material that constitutes a needle-like structure. As promising.
  • This synthesis method is a hydrothermal synthesis method described in Non-Patent Documents 8 to 10, and it is possible to generate needle-shaped apatite on a solid surface such as a titanium oxide photocatalyst material.
  • a photocatalyst material for the purpose of acting as a block layer between a photocatalyst and a biological tissue is also synthesized by precipitating apatite having biocompatibility on a solid surface such as titanium oxide.
  • apatite having biocompatibility on a solid surface such as titanium oxide.
  • this technique is not intended to have a mechano-bactericidal effect at all, it is considered possible to have a mechano-bactericidal effect instead of biocompatibility if apatite is formed into needle-like crystals.
  • the liquid phase synthesis methods shown in Patent Documents 4 to 6 and Non-Patent Documents 11 and 12 have also been studied. According to this method, apatite can be precipitated on the solid surface in a milder environment than the above-mentioned hydrothermal synthesis method.
  • the structure of the present invention for sterilizing and purifying water, it is only necessary to place it in running water, and it is necessary to capture and strain bacteria in which nano-sized to micron-sized needle-shaped crystal habits have flowed on the solid surface. take.
  • the cell membrane of the bacterium is damaged by the needle-like crystal habit and sterilized, so that water can be sterilized and purified.
  • bacteria can be captured and sterilized more efficiently by stirring or shaking the water.
  • a method for producing a structure of the present invention mainly composed of a calcium compound having a needle-like morphology having a sterilizing function for aquatic bacteria and a method for sterilizing aquatic bacteria using this structure are specified. It is described in. Further, due to the mineralization of sterilized bacteria when a photocatalytic material is used on the solid surface of the structure of the present invention, the recovery action of the needle-shaped water mineral component damaged by running water, and the recovery of the needle-shaped morphology. The maintenance of the bactericidal function and the method for treating aquatic bacteria to which these functions are applied are also inventions incidental to the present invention.
  • a ceramic titanium oxide photocatalyst was used as the base material.
  • water was passed through the solid surface of the base material while irradiating it with light in mineral water having a high concentration of calcium bicarbonate in which a small amount of strontium ions were dissolved, needle-like crystals of aragonite began to precipitate on the ceramic titanium oxide photocatalyst. This is because bicarbonate ion is changed to carbonate ion by photocatalytic action, and calcium ion is present at the same time, so that it immediately precipitates as insoluble calcium carbonate.
  • the precipitated calcium carbonate When even a small amount of strontium ion is dissolved in mineral water, the precipitated calcium carbonate has a crystal structure of aragonite having acicular crystal habit (Fig. 1).
  • a pure calcium bicarbonate aqueous solution is used for the photocatalytic reaction, Calcium carbonate deposited on the surface of the photocatalyst becomes calcite without acicular crystal habit (Fig. 2).
  • Aragonite and calcite are polymorphs with the same elemental composition but different atomic arrangements, and can be easily distinguished from each other because they have different X-ray diffraction and laser Raman spectra (Fig. 3).
  • the needle-like crystal habit of aragonite on the surface of the photocatalyst has a length of several hundred nm to several tens of ⁇ m, as shown in the photograph of FIG.
  • Bacteria including fungi have a size of about ten and several ⁇ m at the maximum, and have a length of being physically destroyed and sterilized by being captured or stabbed by needle-like crystal habit. Since needle-like crystal habits are deposited in a very coarse state microscopically, when the solid surface is a titanium oxide photocatalyst, when the structure of the present invention is used for water purification, organic pollutants (solutes) can easily be photocatalysted. Reach the surface.
  • the hydroxide radical which is an active species generated on the surface of the photocatalyst, diffuses to a distance of several microns from the surface of the photocatalyst, which is the tip of the needle-like crystal habit.
  • calcium carbonate does not have absorption in the ultraviolet light region of the UV-A region required to excite the titanium oxide photocatalyst, organic pollutants that have reached the photocatalyst surface and bacteria captured by acicular crystal habits.
  • the tissue is immediately photocatalytically oxidatively degraded. That is, the aragonite precipitated on the surface of the photocatalyst hardly inhibits the photocatalytic ability of the solid surface.
  • Non-Patent Document 14 describes the mechanism by which aragonite grows around an organic substance including a fungus as a nucleus.
  • the process of sterilizing the cell membrane by being strained by aragonite needle-like habit or being damaged by needle-like habit is effective as a technique for treating bacteria contained in water, especially drinking water.
  • a material having a needle structure other than aragonite needle-like crystal habit, which has a bactericidal ability the material group described in the above background technique is known. When taken up, it is expected to exhibit physically negative physiological effects, such as tumor formation due to ecological stimulation.
  • the structure of the present invention uses a needle-like crystal habit composed of calcium carbonate, so that not only can an antibacterial material be synthesized inexpensively, but also damage to the needle-like structure due to water treatment with this structure is caused by actual environment water.
  • the needle-like structure is self-repaired by the passage of water.
  • the aragonite needle-like crystal habit that has flowed out due to breakage has the advantage that it dissolves immediately when taken into the human body and does not affect the living body.
  • FIG. 6 shows when 500 mL of water containing Escherichia coli (about 4000 cfu / mL) was passed through a glass tube filled with about 17 g of titanium oxide ceramics at 100 mL / min in the closed circulatory system shown in FIG. It shows the change in the number of E. coli. Titanium oxide photocatalytic ceramics were used for the solid surface, but the experiment was conducted under dark conditions so that the photocatalytic activity was not exhibited.
  • viable bacteria cover the surface of dio 2 only on the surface of TiO 2 (upper center and upper right), but in the aragonite-supporting system, the total number of bacteria is small, and the number of viable bacteria is small and the dead bacteria are relative. (Lower center and lower right).
  • FIG. 5 The closed circulatory system shown in FIG. 5 was used. A glass tube (300 mm ⁇ ⁇ 10 mm ID) filled with TiO 2 ceramic or aragonite-supported TiO 2 ceramic was connected to the closed circulatory system, and an E. coli of about 5000 cfu / mL was used. 250 mL of water containing colli K-12 was circulated in the dark for 3 hours. The subsequent results of determining whether the bacteria are alive or dead on the surface of TiO 2 (observation with a phase-contrast microscope) are shown in FIG. In the system with only TiO 2 ceramic shown on the left of FIG.
  • the aragonite needle-like crystal habit-supporting TiO 2 ceramic photocatalyst showed 1.3 times the bacterial removal rate even under dark conditions as compared with the TiO 2 ceramic photocatalyst under UV irradiation. From this result, it can be seen that the needle-like crystal habit shows the processing ability based on the mechano-bactericidal effect regardless of the catalytic reaction. UV irradiation further triples the sterilization rate. This result indicates that the sterilizing effect is further synergistically enhanced by carrying aragonite as compared with photocatalytic sterilization using TiO 2 alone.
  • the bactericidal ability due to the photocatalytic effect can also be exhibited.
  • titanium oxide which is inexpensive, highly active, and harmless, as a photocatalytic material, it is possible to sterilize water with a photocatalyst when the daytime weather is good, and to sterilize using a needle-like structure in bad weather and at night. ..
  • a photocatalytic water treatment device using the structure of the present invention By introducing a photocatalytic water treatment device using the structure of the present invention into a regional village such as a developing country where safe water cannot be accessed, safe water can be supplied only by irradiating sunlight. Moreover, not only in developing countries, but also in Japan, when the supply of drinking water is stopped in the event of a disaster, it will be possible to purify river water, residual hot water from baths, etc. to a drinkable level.

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PCT/JP2020/045644 2019-12-17 2020-12-08 殺菌作用による水質浄化機能を有する構造体 WO2021124983A1 (ja)

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JP3598349B2 (ja) * 2002-06-05 2004-12-08 独立行政法人産業技術総合研究所 複合セラミックス材料の製造方法
JP2007296464A (ja) * 2006-04-28 2007-11-15 Onoda Chemical Industry Co Ltd フミン物質吸着剤とその製造方法
JP2007314359A (ja) * 2006-05-23 2007-12-06 National Institute For Materials Science 炭酸カルシウム・ゼオライト系化合物複合体とその製造方法およびそれを用いた物品
JP2010059005A (ja) * 2008-09-02 2010-03-18 Kanazawa Inst Of Technology 複合体および複合体の製造方法
KR101453923B1 (ko) * 2013-12-23 2014-10-24 한국해양대학교 산학협력단 전기화학적 프로세스를 통한 아라고나이트 결정구조의 탄산칼슘 막 제조방법
US20180362377A1 (en) * 2017-06-19 2018-12-20 Lg Electronics Inc. Hardness reduction filter

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KR20050010820A (ko) * 2002-06-05 2005-01-28 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 복합 세라믹스 재료의 제조방법
BRPI1009165A2 (pt) * 2010-12-20 2015-08-18 Inovamat Inovação Em Materiais Ltda Processo de nucleação e crescimento in situ de cristais nanométricos à base de silicato de cálcio em materiais cimentícios, cristais nanométricos à base de silicato de cálcio, uso dos cristais e uso de glicerina
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3598349B2 (ja) * 2002-06-05 2004-12-08 独立行政法人産業技術総合研究所 複合セラミックス材料の製造方法
JP2007296464A (ja) * 2006-04-28 2007-11-15 Onoda Chemical Industry Co Ltd フミン物質吸着剤とその製造方法
JP2007314359A (ja) * 2006-05-23 2007-12-06 National Institute For Materials Science 炭酸カルシウム・ゼオライト系化合物複合体とその製造方法およびそれを用いた物品
JP2010059005A (ja) * 2008-09-02 2010-03-18 Kanazawa Inst Of Technology 複合体および複合体の製造方法
KR101453923B1 (ko) * 2013-12-23 2014-10-24 한국해양대학교 산학협력단 전기화학적 프로세스를 통한 아라고나이트 결정구조의 탄산칼슘 막 제조방법
US20180362377A1 (en) * 2017-06-19 2018-12-20 Lg Electronics Inc. Hardness reduction filter

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