WO2012036231A1 - 光触媒能を有するガラス - Google Patents
光触媒能を有するガラス Download PDFInfo
- Publication number
- WO2012036231A1 WO2012036231A1 PCT/JP2011/071078 JP2011071078W WO2012036231A1 WO 2012036231 A1 WO2012036231 A1 WO 2012036231A1 JP 2011071078 W JP2011071078 W JP 2011071078W WO 2012036231 A1 WO2012036231 A1 WO 2012036231A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- sample
- acid
- hydrofluoric acid
- photocatalytic activity
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 58
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 51
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 32
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 239000005388 borosilicate glass Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 abstract description 27
- 239000003365 glass fiber Substances 0.000 abstract description 16
- 239000011941 photocatalyst Substances 0.000 abstract description 15
- 239000010453 quartz Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000005357 flat glass Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000005416 organic matter Substances 0.000 abstract description 2
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 238000005562 fading Methods 0.000 description 32
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 31
- 229960000907 methylthioninium chloride Drugs 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 25
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 superoxide anions Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000011481 absorbance measurement Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 208000008842 sick building syndrome Diseases 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000003921 oil Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2003—Glass or glassy material
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B01J35/39—
-
- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0428—Rendering the filter material hydrophobic
Definitions
- the present invention relates to a photocatalyst material that is sensitive to light over a wide wavelength region, decomposes harmful organic substances, and effectively renders them harmless, and a filter that uses the photocatalyst material as an application thereof.
- titanium dioxide has the highest stability and exhibits almost no biotoxicity, so it is widely used as a photocatalyst for various chemical reactions and environmental purification.
- this photocatalyst electrons in the full band are excited to the conduction band by irradiation of near-ultraviolet light near 400 nm, and charge separation occurs, and hydroxyl radicals and superoxide anions are generated at the generated charge sites. and, these powerful oxidizing action, decomposing environmental contaminants such as organic halogen compounds and NO x.
- HEPA filters High Efficiency made of glass fiber are used for air supply to sites where semiconductor manufacturing equipment, medical equipment such as operating rooms, pharmaceutical manufacturing equipment, and food manufacturing equipment are installed, or for exhaust equipment of nuclear facilities. Particurate (Air Filter) is used.
- the HEPA filter is “an air filter that has a particle collection rate of 99.97% or more with respect to particles with a rated air volume of 0.3 ⁇ m and an initial loss of 245 Pa or less”. It is.
- the filter portion of the HEPA filter is generally configured by filling glass fibers having a diameter of 1 to 10 ⁇ m or less with a gap of several tens of ⁇ m at a filling rate of about 10%.
- various liquid or gaseous organic substances are present in addition to the particles having a particle size of 0.3 ⁇ m or more, which are to be collected by the HEPA filter, and these cannot be removed even by the HEPA filter.
- particles that cannot be removed by the HEPA filter are harmful to the air supply destination, they are rendered harmless by using other means, but the air supply / exhaust facilities become complicated and expensive.
- glass fibers such as HEPA filters
- silicon dioxide is a stable substance, has low chemical activity, and cannot be expected to have a catalytic ability to detoxify harmful substances.
- a photocatalytic ability obtained by treating fine particles of artificial quartz crystal, which is a crystal of pure silicon dioxide (SiO 2 ), which is an inexpensive and stable material, instead of titanium dioxide with hydrofluoric acid (HF) is WO 2005/089941 JP-A-2006-511175, JP-A-2007-098205, JP-A-2007-098206, and JP-A-2007-307430.
- Japanese Unexamined Patent Application Publication No. 2007-098205 discloses a photocatalytic material in which natural quartz or artificial quartz is supported on granular inorganic or organic matter.
- a photocatalytic material obtained by halogenating with hydrofluoric acid, hydrochloric acid, or hydrobromic acid using plate-like, granular, powdery, block-like, or fiber-like quartz (silicon dioxide) glass is disclosed in JP-A-2004-290747. And Japanese Patent Application Laid-Open No. 2004-290748.
- Japanese Patent Application Laid-Open No. 2007-098206 discloses a photocatalyst material in which granular silicon dioxide such as natural silica, artificial silica, fused silica, silica sol or the like is used and its fine particles are halogenated with hydrofluoric acid.
- This document also shows a photocatalytic material in which natural silica, artificial silica, fused silica, silica sol or the like is supported on a granular inorganic or organic substance.
- Japanese Unexamined Patent Application Publication No. 2007-098205 discloses a photocatalyst material obtained by using natural quartz or artificial quartz and halogenating fine particles thereof with hydrofluoric acid. This document shows that a photocatalytic material is supported on a granular inorganic substance or organic substance.
- Japanese Unexamined Patent Application Publication No. 2007-098206 discloses a photocatalytic material in which granular silicon dioxide such as natural silica, artificial silica, fused silica, silica sol or the like is used, and the fine particles are halogenated with hydrofluoric acid. This document also shows that this photocatalytic material is supported on a granular inorganic substance or organic substance.
- Japanese Unexamined Patent Publication No. 2007-307430 discloses a photocatalytic material in which fine particles of artificial quartz are supported on granular inorganic or organic substances.
- an object is to obtain an inexpensive photocatalytic material.
- an object is to obtain a photocatalyst having a form other than fine particles.
- an object is to obtain a photocatalyst capable of using light other than ultraviolet rays.
- an object is to obtain a filter having photocatalytic activity.
- an object is to obtain a supply / exhaust device using a filter having photocatalytic activity.
- the inventors have found that photocatalytic activity can be obtained even with a material obtained by treating a silicon dioxide-containing material such as soda-lime glass, alkali-free glass, or borosilicate glass with hydrofluoric acid.
- a silicon dioxide-containing material such as soda-lime glass, alkali-free glass, or borosilicate glass with hydrofluoric acid.
- photocatalytic ability can be obtained with a hydrofluoric acid-treated material of silicon dioxide-containing materials such as soda-lime glass, alkali-free glass, and borosilicate glass.
- a photocatalytic ability can be obtained with a material obtained by treating a silicon dioxide-containing material such as soda-lime glass, alkali-free glass, or borosilicate glass with a hydrohalic acid.
- a silicon dioxide-containing material such as soda-lime glass, alkali-free glass, or borosilicate glass with a hydrohalic acid.
- the inventors have found that a plate or fibrous material other than fine particles made of a silicon dioxide-containing material that has not been treated with hydrohalic acid has photocatalytic activity.
- the inventors have discovered that a material obtained by treating soda-lime glass used for window glass with hydrofluoric acid has photocatalytic activity.
- a soda-lime glass material is provided as a photocatalyst treated with hydrohalic acid.
- Photocatalytic material that is soda-lime glass treated with hydrohalic acid.
- Photocatalytic material that is glass fiber treated with hydrohalic acid.
- Filter with photocatalytic ability made of glass fiber treated with hydrohalic acid.
- a glass having photocatalytic activity which is obtained by treating a glass containing components other than silicon dioxide with hydrohalic acid.
- a supply / exhaust device configured manually using a filter formed of a fibrous body obtained by treating glass containing a silicon dioxide component with hydrohalic acid.
- soda-lime glass treated with hydrohalic acid decomposes organic pollutants when irradiated with light.
- a filter having photocatalytic activity can be obtained by forming glass fiber treated with hydrohalic acid into a woven or non-woven fabric.
- a soda-lime glass plate treated with hydrohalic acid decomposes organic substances when irradiated with ultraviolet light or visible light.
- this hydrohalic acid-treated soda lime glass exhibits catalytic ability even when the glass plate surface is smooth and transparent.
- the photocatalytic activity was measured by measuring the basic matters by the methylene blue amber color test, and by measuring the practical photocatalytic activity by the degradation test of acetaldehyde, one of the causative substances of sick house syndrome.
- the methylene blue fading test was performed as follows. After washing and drying the sample, it is put into a methylene blue aqueous solution, irradiated with ultraviolet light with a wavelength of 300 to 400 nm from the black light for 24 hours, and the fading rate of the methylene blue aqueous solution is measured from the change in absorbance with respect to the light with a wavelength of 664 nm before and after that. did.
- a methylene blue aqueous solution having a concentration of 0.01 mmol / L in which 495 mL of purified water was added to 5 mL of methylene blue aqueous solution added to 0.0374 g of methylene blue trihydrate (MW 374) to make 100 mL was used.
- the fading rate is measured by placing a sample in 20 mL of methylene blue reagent in a polystyrene container, irradiating with ultraviolet light having a wavelength of 300 to 400 nm from a black light in a dark room for 24 hours, and light having a wavelength of 664 nm before and after irradiation. The change in absorbance of the methylene blue reagent for was measured.
- the fading rate (%) of the methylene blue reagent was calculated from the Lambert Bale equation shown below to obtain the decomposition rate of the methylene blue reagent of the sample.
- 100 ⁇ Abs (24h) / Abs (0h) ⁇ 100 Fade rate (%)
- Abs (24h) is the absorbance after irradiation for 24 hours
- Abs (0h) is the absorbance before irradiation.
- the adsorption rate (%) of methylene blue to the sample was measured in the dark for 24 hours, and the difference between the fading rate and the adsorption rate (%), which is considered to be true catalytic ability. was calculated.
- acetaldehyde decomposition test method The acetaldehyde decomposition test was conducted as follows. After cleaning and drying the sample, place it in an acetaldehyde atmosphere with a concentration of 5.0 ppm and a gas flow rate of 1.0 L / min, and irradiate ultraviolet light with a wavelength of 300 to 400 nm from the black light, The amount of decomposition and the amount of carbon dioxide generated per unit time due to the decomposition of acetaldehyde were measured.
- Example 1 As Example 1, an example in which soda-lime glass particles are used as a photocatalyst will be described.
- Sample 1 the basic composition content omit components of less than 1% SiO 2 is 71.9%, CaO is 7.8%, Al 2 O 3 is 1.7%, MgO 4.0 Glass fiber made of commonly used soda-lime glass having a Na 2 O content of 13.3% is immersed in a hydrofluoric acid aqueous solution having a concentration of 10% for 5 minutes, washed and dried to obtain a particle size of 0. It is crushed to 2 mm.
- the glass sample thus obtained was immersed in an aqueous methylene blue solution, and the fading rate of methylene blue before and after irradiation or standing was measured for those irradiated with visible light for 70 hours or left standing in the dark for 70 hours.
- the soda-lime glass of Sample 1 is effective in a methylene blue amber without being treated with hydrofluoric acid, and more effective when treated with hydrofluoric acid.
- Sample 2 is composed of 55.0% SiO 2 , 23.0% CaO, 14.2% Al 2 O 3 and B 2 O 3 in which the basic composition is less than 1%.
- the alkali-free glass is 6.2%.
- the alkali-free glass of Sample 2 is effective in the color of methylene blue without being treated with hydrofluoric acid, and more effective when treated with hydrofluoric acid.
- Sample 3 is composed of 33.0% SiO 2 , 6.8% CaO, 1.3% Al 2 O 3 and B 2 O 3 with a basic composition of less than 1%.
- Borosilicate glass with 37.4%, MgO 5.5%, Na 2 O 16.0%.
- the borosilicate glass of Sample 3 is effective in the fading rate of methylene blue without being treated with hydrofluoric acid, and more effective when treated with hydrofluoric acid.
- Measurement of the fading rate with glass fiber is performed by putting 1 g of hydrofluoric acid-treated glass fiber in 100 mL of methylene blue reagent in a quartz glass container, irradiating visible light from a fluorescent lamp for 24 hours, and the wavelength before and after irradiation. The absorbance of the methylene blue reagent for light at 664 nm was measured.
- the fading rate (%) of the methylene blue reagent was calculated from the Lambert Bale equation described above to obtain the decomposition rate of the methylene blue reagent of the sample.
- Sample 4 is a typical soda-lime glass fibers are glass fibers, the basic composition content omit components below 1% SiO 2 is 71.9%, CaO is 7.8%, Al A glass fiber made of commonly used soda-lime glass having 2 O 3 of 1.7%, MgO of 4.0% and Na 2 O of 13.3% has a concentration of 0.05%, 0.1%, It was immersed in 0.5% and 1% hydrofluoric acid aqueous solutions for 5 minutes, washed and dried.
- ⁇ Glass plate> A photocatalyst using plate-like glass instead of granular or fiber will be described.
- Example 5 an example using the above-described soda-lime glass plate will be described.
- a 1 mm thick soda-lime glass plate was cut into 30 ⁇ 30 mm 2 , immersed in a hydrofluoric acid solution, subjected to immersion treatment while changing its concentration and treatment time, then washed and dried to obtain a test piece.
- the discoloration rate (%), the adsorption rate (%), and the difference (%) are shown below for samples 5 to 14 which are test pieces processed by changing the hydrofluoric acid solution concentration and the treatment time.
- Sample 5 was immersed in hydrofluoric acid having a concentration of 5% for 5 minutes.
- the fading rate of Sample 5 was 15%, the adsorption rate was 15%, and the difference was 0%.
- Sample 6 was immersed in hydrofluoric acid having a concentration of 10% for 5 minutes. Sample 6 had a fading rate of 14%, an adsorption rate of 15%, and the difference was -1%.
- Sample 7 was immersed in hydrofluoric acid having a concentration of 1% for 5 minutes.
- the discoloration rate of Sample 7 was 16%, the adsorption rate was 15%, and the difference was 1%.
- Sample 8 was immersed in hydrofluoric acid having a concentration of 10% for 10 minutes. Sample 8 had a fading rate of 21%, an adsorption rate of 16%, and a difference of 5%.
- Sample 9 was immersed in hydrofluoric acid having a concentration of 20% for 5 minutes. Sample 9 had a fading rate of 19%, an adsorption rate of 14%, and a difference of 5%.
- Sample 8 having a fading rate of 21% and an adsorption rate of 16% and Sample 9 having a fading rate of 19% and an adsorption rate of 14% are useful. It was determined that there was. Further, in order to confirm the treatment conditions, Samples 10 to 14 were prepared with the hydrofluoric acid concentration kept constant at 20% and the immersion treatment time varied, and the same measurement was performed.
- Sample 10 was immersed in hydrofluoric acid for 15 minutes. Sample 10 had a fading rate of 22%, an adsorption rate of 11%, and a difference of 11%.
- Sample 11 was immersed in hydrofluoric acid for 15 minutes.
- the discoloration rate of sample 11 was 13%, the adsorption rate was 5%, and the difference was 8%.
- Sample 12 was immersed in hydrofluoric acid for 15 minutes in the same manner as Sample 7.
- the sample 12 had a fading rate of 13%, which was the same as the sample 7, but the adsorption rate was as large as 11%, and the difference was 2%.
- Sample 13 was immersed in hydrofluoric acid for 20 minutes. Sample 13 had a fading rate of 15%, an adsorption rate of 8%, and a difference of 7%.
- sample 13 showed the water repellency estimated to be a lotus effect as a matter of special mention.
- Sample 14 was immersed in hydrofluoric acid for 30 minutes. Although the fading rate of the sample 14 was as small as 2%, the difference was 2% because the adsorption rate was 0%.
- Sample 15 had a fading rate of 22%, an adsorption rate of 11%, and a difference of 11%.
- Sample 16 had a fading rate of 13%, an adsorption rate of 5%, and a difference of 8%.
- Sample 17 had a fading rate of 13%, an adsorption rate of 11%, and a difference of 2%.
- the fading rate of sample 18 was 8%, the adsorption rate was 6%, and the difference was 2%.
- the fading rate of sample 19 was 8%, the adsorption rate was 8%, and the difference was 0%.
- Sample 20 used in the acetaldehyde decomposition test is soda-lime glass generally used in the same manner as in Examples 1 to 15, and the basic composition in which components with a content of less than 1% are omitted is SiO 2. Is 71.9%, CaO is 7.8%, Al 2 O 3 is 1.7%, MgO is 4.0%, and Na 2 O is 13.3%.
- Sample 20 is a soda lime glass having a thickness of 1 mm that has been dipped in hydrofluoric acid having a concentration of 20% for 15 minutes in the same manner as Samples 10 to 12, then washed with water and dried, and cut into 50 ⁇ 100 mm 2. .
- the amount of acetaldehyde decomposed per unit time by the sample 20 was 0.98 ⁇ mol / hour, the amount of carbon dioxide produced per unit time was 1.38 ⁇ mol / hour, the acetaldehyde removal rate was 7.11%, The conversion is 5%. From this result, the soda lime glass of the sample 20 has a catalytic ability practical for acetaldehyde.
- the sample 21 having the same conditions as the soda lime glass of the sample 20 was used, and the ultraviolet light from the fluorescent lamp was removed by the ultraviolet cut filter, and the wavelength was 400 to 710 nm.
- the soda lime glass of the sample 20 has a catalytic ability practical for acetaldehyde.
- the soda-lime glass treated with hydrohalic acid exhibits a photocatalytic ability to decompose organic substances when irradiated with light.
- a filter having photocatalytic activity can be obtained by using woven or non-woven fabric of soda-lime glass fiber treated with hydrohalic acid.
- a supply / exhaust device using a filter made of glass fiber treated with hydrohalic acid is useful in facilities where organic substances are required to be removed.
- the soda lime plate glass treated with hydrohalic acid according to the invention of this application exhibits a photocatalytic ability to decompose organic substances when irradiated with light, while being smooth and transparent.
- This plate glass can be used for window glass, the surface on the side in contact with the atmosphere decomposes and removes organic pollutants in the atmosphere, and the indoor side removes acetaldehyde, the causative agent of sick house syndrome, oil smoke at the kitchen, cigarette smoke, etc. It can be disassembled and removed, and is useful as a building window material.
Abstract
Description
この光触媒は400nm付近の近紫外光の照射によって充満帯にある電子が伝導帯に励起されることにより電荷分離を生じ、このようにして生じた電荷サイトで、水酸ラジカルやスーパーオキシドアニオンが発生し、これらの強力な酸化作用で、有機ハロゲン化合物やNOxのような環境汚染物質を分解する。
HEPAフィルタのフィルタ部分は一般的に直径1~10μm以下のガラス繊維を数10μmの空隙をもたせて10%程度の充填率で充填して構成されている。
HEPAフィルタによって除去することができない粒子等が給気先にとって有害物である場合には他の手段を併用して無害化しているが、給排気設備が複雑になり、高価になる。
ガラス繊維は二酸化珪素を主成分としているが、二酸化珪素は安定な物質であり、化学的活性は低く、有害物質を無害化する触媒能を期待することはできない。
この文献には、天然シリカ,人工シリカ,溶融石英,シリカゾル等を粒状の無機物あるいは有機物に担持させた光触媒材料も示されている。
この文献には、光触媒材料を粒状の無機物あるいは有機物に担持させることが示されている。
この文献には、この光触媒材料を粒状の無機物あるいは有機物に担持させることも示されている。
その上、このハロゲン化水素酸処理したソーダ石灰ガラスはガラス板表面が平滑透明な状態でも触媒能を発揮する。
メチレンブルー褪色試験は次のようにして行った。
試料を洗浄・乾燥後、メチレンブルー水溶液に入れ、ブラックライトからの波長が300~400nmの紫外光を24時間照射し、その前後の波長664nmの光に対する吸光度の変化から、メチレンブルー水溶液の褪色率を計測した。
100-Abs(24h)/Abs(0h)×100=褪色率(%)
ここで、Abs(24h)は、24時間照射後の吸光率、
Abs(0h)は、照射前の吸光率である。
アセトアルデヒド分解試験は次のようにして行った。
試料を洗浄・乾燥後、濃度を5.0ppm、ガス流量を1.0L/分としたアセトアルデヒド雰囲気に置き、ブラックライトからの波長が300~400nmの紫外光を照射し、単位時間当たりのアセトアルデヒドの分解量及びアセトアルデヒドの分解により発生する単位時間当たりの二酸化炭素の発生量を計測した。
実施例1として、ソーダ石灰ガラス粒を光触媒として用いる例を説明する。
試料1は、含有量が1%未満の成分を省略した基本的な組成がSiO2が71.9%,CaOが7.8%,Al2O3が1.7%,MgOが4.0%,Na2Oが13.3%である一般に使用されているソーダ石灰ガラスからなるガラス繊維を濃度10%のフッ化水素酸水溶液に5分間浸漬処理し、洗浄・乾燥させて粒径0.2mmに粉砕したものである。
なお、フッ化水素酸処理をしていない場合は22%であった。
試料2は、含有量が1%未満の成分を省略した基本的な組成がSiO2が55.0%,CaOが23.0%,Al2O3が14.2%,B2O3が6.2%である無アルカリガラスである。
なお、フッ化水素酸処理をしていない場合は16%であった。
試料3は、含有量が1%未満の成分を省略した基本的な組成がSiO2が33.0%,CaOが6.8%,Al2O3が1.3%,B2O3が37.4%,MgOが5.5%,Na2Oが16.0%であるホウケイ酸ガラスである。
なお、フッ化水素酸処理をしていない場合は16%であった。
粒状のガラスに代えて繊維状のガラスを用いた光触媒について説明する。
ガラス繊維による褪色率の測定は、石英ガラス製容器中のメチレンブルー試薬100mLにフッ化水素酸処理したガラス繊維1gを入れ、蛍光灯からの可視光を24時間照射し、照射前と照射後の波長664nmの光についてのメチレンブルー試薬の吸光度を測定した。
なお、同じソーダ石灰ガラス繊維でフッ化水素酸に浸漬処理していない場合のメチレンブルー褪色率は7%である。
粒状あるいは繊維状に代えて板状のガラスを用いた光触媒を説明する。
実施例5として、前述したソーダ石灰ガラス板を用いた例について説明する。
以下、フッ化水素酸溶液濃度及び処理時間を変化させて処理した試験片である試料5~試料14に関して、褪色率(%)、吸着率(%)及び差(%)を以下に示す。
試料5の褪色率は15%、吸着率は15%、その差は0%であった。
試料6の褪色率は14%、吸着率は15%、その差は-1%であった。
試料7の褪色率は16%、吸着率は15%、その差は1%であった。
試料8の褪色率は21%、吸着率は16%、その差は5%であった。
試料9の褪色率は19%、吸着率は14%、その差は5%であった。
さらに処理条件を確認すすために、フッ化水素酸濃度を20%と一定にし、浸漬処理時間を変えた試料10~試料14を用意し、同様な計測を行った。
試料10の褪色率は22%、吸着率は11%、その差は11%であった。
試料11の褪色率は13%、吸着率は5%、その差は8%であった。
この試料12は褪色率は13%と試料7と同じであるが、吸着率が11%と大きく、その差は2%であった。
試料13の褪色率は15%、吸着率は8%、その差は7%であった。
試料14の褪色率は2%と小さいが、吸着率は0%であるため、その差は2%であった。
フッ化水素酸処理した青板ガラスの触媒能と比較するために、二酸化チタンをソーダ石灰ガラス基板上に塗布してアナターゼ型二酸化チタンとした比較試料の褪色率は29%、吸着率は25%、その差は4%であった。
アセトアルデヒド分解試験で使用した試料20は実施例1~15の場合と同様に一般的に使用されているソーダ石灰ガラスであり、含有量が1%未満の成分を省略した基本的な組成はSiO2が71.9%,CaOが7.8%,Al2O3が1.7%,MgOが4.0%,Na2Oが13.3%である。
この結果から、試料20のソーダ石灰ガラスはアセトアルデヒドについて実用可能な触媒能を有している。
この結果から、試料20のソーダ石灰ガラスはアセトアルデヒドについて実用可能な触媒能を有している。
Claims (12)
- 二酸化珪素以外の成分を含むガラスをハロゲン化水素酸で処理したことを特徴とする、光触媒能を有するガラス。
- 前記ガラスがソーダ石灰ガラスであることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ガラスが無アルカリガラスであることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ガラスがホウケイ酸ガラスであることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ハロゲン化水素酸がフッ化水素酸であることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ハロゲン化水素酸が塩化水素酸であることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ハロゲン化水素酸が臭化水素酸であることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ガラスが粒状体であることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ガラスが繊維状体であることを特徴とする、請求項1の光触媒能を有するガラス。
- 前記ガラスが板状体であることを特徴とする、請求項1の光触媒能を有するガラス。
- 二酸化珪素を含むガラスをハロゲン化水素酸で処理した繊維状体により形成されたフィルタ。
- 二酸化珪素を含むガラスをハロゲン化水素酸で処理した繊維状体によって構成されたフィルタを用いた給・排気用装置。
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JP2012534049A JPWO2012036231A1 (ja) | 2010-09-15 | 2011-09-15 | 光触媒能を有するガラス |
SG2013018536A SG188983A1 (en) | 2010-09-15 | 2011-09-15 | Glass with photocatalytic function |
KR1020137007816A KR20130103731A (ko) | 2010-09-15 | 2011-09-15 | 광촉매 기능을 구비하는 유리 |
AU2011302987A AU2011302987A1 (en) | 2010-09-15 | 2011-09-15 | Glass with photocatalytic function |
US13/823,380 US20130336846A1 (en) | 2010-09-15 | 2011-09-15 | Glass having a photocatalytic function |
CN2011800479970A CN103167908A (zh) | 2010-09-15 | 2011-09-15 | 具有光催化能力的玻璃 |
EP11825231.1A EP2617492A4 (en) | 2010-09-15 | 2011-09-15 | GLASS WITH PHOTOCATALYTIC FUNCTION |
RU2013116900/04A RU2013116900A (ru) | 2010-09-15 | 2011-09-15 | Стекло, обладающее фотокаталитической активностью |
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CN104492500B (zh) * | 2014-12-10 | 2018-08-21 | 佛山市三水和美斯金铝业有限公司 | 蜂窝玻璃光触媒载体及其制备方法 |
KR101892812B1 (ko) * | 2016-09-13 | 2018-08-29 | 한국세라믹기술원 | 글라스 섬유 직조체/폴리머 투명 복합체 시트의 제조방법 |
TWI639466B (zh) * | 2018-02-09 | 2018-11-01 | 燕成祥 | Photocatalyst composition |
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SG188983A1 (en) | 2013-06-28 |
EP2617492A4 (en) | 2014-08-06 |
CN103167908A (zh) | 2013-06-19 |
AU2011302987A1 (en) | 2013-04-11 |
JPWO2012036231A1 (ja) | 2014-02-03 |
RU2013116900A (ru) | 2014-10-20 |
US20130336846A1 (en) | 2013-12-19 |
EP2617492A1 (en) | 2013-07-24 |
KR20130103731A (ko) | 2013-09-24 |
TW201217291A (en) | 2012-05-01 |
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