CN1938829A - Ozone water supply method and ozone water supply device - Google Patents
Ozone water supply method and ozone water supply device Download PDFInfo
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- CN1938829A CN1938829A CNA2005800100348A CN200580010034A CN1938829A CN 1938829 A CN1938829 A CN 1938829A CN A2005800100348 A CNA2005800100348 A CN A2005800100348A CN 200580010034 A CN200580010034 A CN 200580010034A CN 1938829 A CN1938829 A CN 1938829A
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- ozone
- ozone water
- water
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- dissolved
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 544
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000007246 mechanism Effects 0.000 claims abstract description 55
- 239000000126 substance Substances 0.000 claims abstract description 45
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 44
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 41
- 230000002829 reductive effect Effects 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 30
- 230000005855 radiation Effects 0.000 claims description 26
- 230000033228 biological regulation Effects 0.000 claims description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 12
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000012776 electronic material Substances 0.000 abstract description 5
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- 238000012546 transfer Methods 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 2
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- 238000012360 testing method Methods 0.000 description 16
- 230000014509 gene expression Effects 0.000 description 15
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- 230000009467 reduction Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 ozone ion Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
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- 239000003595 mist Substances 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/005—Details of cleaning machines or methods involving the use or presence of liquid or steam the liquid being ozonated
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/23—O3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Physical Water Treatments (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
A method for supplying ozone water is characterized in that ozone water containing an ozone decomposition inhibitor is transferred to a point of use (7), and the concentration of the ozone water is reduced to a predetermined ozone concentration by a concentration adjusting mechanism in the vicinity of the point of use. An ozone water supply device is characterized by comprising an ozone dissolving device (4) for dissolving ozone gas in pure water to prepare ozone water; a mechanism for supplying an ozonolysis inhibiting substance to the pure water or the ozonized water; an ozone water transfer pipe (6) for transferring the ozone water prepared by the ozone dissolving device to a point of use; and a concentration adjusting mechanism (8) which is arranged near the using point and reduces the ozone water transferred through the ozone water transfer pipe to a predetermined ozone concentration. The apparatus can stably supply ozone water having a predetermined ozone concentration to a point of use in a wet cleaning process, a surface treatment process, or the like of an electronic material such as a semiconductor or a liquid crystal.
Description
Technical field
The present invention relates to method of ozone water supply and ozone water supply apparatus.More particularly, the present invention relates to can be in the wet-cleaned operation of the electronic material of semiconductor, liquid crystal etc., surface treatment procedure etc., and stably the Ozone Water with the ozone concentration of regulation feeds to method of ozone water supply and the ozone water supply apparatus that uses point.
Background technology
From semiconductor with silicon substrate, liquid crystal with glass substrate, photomask electronic material surface with quartz base plate etc., remove organic substance, metal etc. for guaranteeing Products Quality and qualification rate, be very important.The Ozone Water that is dissolved with ozone in pure water is used for the low concentration of dissolved ozone concentration for number mg/L degree, simultaneously, bring into play extremely strong oxidizing force, be used in operation and the surface oxidation that makes silicon substrate equably of removing the pollution that the impurity be attached to the lip-deep organic substance of electronic material, metal etc. causes, the operation that forms oxidation film layer.In this occasion,, be very main so its concentration is managed because the concentration of the Ozone Water of being supplied with impacts the cleaning force of substrate surface, the control of oxide thickness etc.
As the ozone that is dissolved in the water have itself decompose very violent, the problem that the dissolved ozone concentration of Ozone Water reduces easily.Even long distance ground passes under the situation of Ozone Water, reduction amount as the ozone concentration in passing on is little, certain concentration of ozone water can be fed to the ozone water supply apparatus that uses point, people propose to have following ozone water supply apparatus, it comprises is dissolved in the pure water ozone, forms the Ozone Water dissolver of Ozone Water; Pass on the ozone water supply pipe of the Ozone Water that forms, in this device, be provided with and make carbon dioxide or organic compound be dissolved in interpolation mechanism (patent documentation 1) in pure water or the Ozone Water.As the feedway of the ozone dissolving water with same effect, people propose to have the feedway of ozone dissolving water, and it comprises ozone is dissolved in ozone dissolver in the dissolved water; Dissolved water is supplied with the feed pipe of dissolver; Ozone is dissolved water send pipe from what dissolver was sent, in this device, to the optional position of sending the pipe chemical agent feedway is being set from feed pipe, this chemical agent feedway adds the ozone decomposing inhibitor of selecting more than a kind or 2 kinds (patent documentation 2) from the group that nitrous acid, nitrite, carbonic acid, carbonate, bicarbonate, sulfurous acid, sulphite, bisulfites and hydrazine are formed.
In addition, as when ozone water supply is used the position, can supply with the density adjusting method of Ozone Water of the Ozone Water of desired concn easily, people propose to have the method for adjustment of following consistency of ozone water, in the method, dissolved ozone too much, the length by the water flowing path, heat, ultrasonic wave, ultraviolet ray or turbulent flow handle, promote the decomposition of ozone, adjust the concentration (patent documentation 3) of Ozone Water.As the ozone concentration method of adjustment that can supply with required dissolved ozone concentration of ozone water easily, people propose to have the method for adjustment of following ozone concentration, wherein, make the water and the glass contact that contain ozone, form the water that comprises ozone (patent documentation 4) of desired concn.
But, in the past the method for ozone water supply and ozone water supply apparatus, have following problem, that is, be difficult to supply with stable concentration of ozone water, in addition, also be very difficult to it is controlled at the dissolved ozone concentration of regulation using point.
Patent documentation 1:JP spy opens 2000-37695 document (the 2nd page);
Patent documentation 2:JP spy opens 2002-18454 document (the 2nd page);
Patent documentation 3:JP spy opens 2000-180433 document (the 2nd～3 page);
Patent documentation 4:JP spy opens 2000-334468 document (the 2nd page);
The object of the present invention is to provide can be in the wet-cleaned operation of the electronic material of semiconductor, liquid crystal etc., surface treatment procedure etc., and stably the Ozone Water with the ozone concentration of regulation feeds to method of ozone water supply and the ozone water supply apparatus that uses point.
Summary of the invention
In order to solve above-mentioned problem, the inventor furthers investigate, consequently find, the high Ozone Water of concentration that will have ozone decomposition inhibiting substances is transferred to the use point, is using point, this water is reduced to the ozone concentration of regulation by the concentration adjusting mechanism, thus, can according to this viewpoint, finish the present invention stably with the ozone water supply use point of regulation ozone concentration.
That is, the present invention relates to following scheme:
(1) relate to a kind of method of ozone water supply, wherein, the Ozone Water that will have ozone decomposition inhibiting substances is transferred to the use point, near the use point, by the concentration adjusting mechanism, the concentration of this water is reduced to the ozone concentration of regulation.
(2) relate to above-mentioned (1) described method of ozone water supply, wherein, ozone decompose inhibiting substances for from the group that water-soluble organic compounds, inorganic acid or its salt and hydrazine constitute, select more than a kind or 2 kinds.
(3) relate to above-mentioned (2) described method of ozone water supply, inorganic acid or its salt are hydrochloric acid, sulfuric acid, carbonic acid, carbonate, bicarbonate, nitrous acid, nitrite, sulfurous acid, sulphite or bisulfites.
(4) relate to above-mentioned (1) described method of ozone water supply, wherein, the concentration adjusting mechanism carries out the decomposition of dissolved ozone.
(5) relate to above-mentioned (4) described method of ozone water supply, wherein, the decomposition of dissolved ozone by takes place from ultrasonic wave radiation, ultraviolet radiation, turbulent flow, stir, heat, alkali adds and hydrogen peroxide adds the mode of selecting the group of formation more than a kind or 2 kinds and carries out.
(6) relate to (1) described method of ozone water supply, wherein, the concentration adjusting mechanism carries out the dilution of Ozone Water.
(7) relate to any one described method of ozone water supply in above-mentioned (1)～(6), wherein, Ozone Water is carried out to the gas-liquid mixed state that passes in Ozone Water and ozone gas coexistence that uses point.
(8) relate to a kind of ozone water supply apparatus, this ozone water supply apparatus comprises ozone dissolver, and this ozone dissolver is dissolved in ozone gas in the pure water, the modulation Ozone Water; Ozone is decomposed inhibiting substances supply to mechanism in above-mentioned pure water or the above-mentioned Ozone Water; Ozone Water is passed on pipe arrangement, and this Ozone Water is passed on pipe arrangement and will be transferred to the use point by the Ozone Water of above-mentioned ozone dissolver modulation; Concentration adjusting mechanism, this concentration adjusting mechanism are arranged at and use near the point, will pass on Ozone Water that pipe arrangement passes on by Ozone Water and be reduced to the ozone concentration of regulation.
(9) relate to above-mentioned (8) described ozone water supply apparatus, wherein, ozone decompose inhibiting substances for from the group that water-soluble organic compounds, inorganic acid or its salt and hydrazine constitute, select more than a kind or 2 kinds.
(10) relate to above-mentioned (9) described ozone water supply apparatus, wherein, inorganic acid or its salt are hydrochloric acid, sulfuric acid, carbonic acid, carbonate, bicarbonate, nitrous acid, nitrite, sulfurous acid, sulphite or bisulfites.
(11) relate to above-mentioned (8) described ozone water supply apparatus, wherein, the concentration adjusting mechanism carries out the decomposition of dissolved ozone.
(12) relate to above-mentioned (11) described ozone water supply apparatus, wherein, the decomposition of dissolved ozone by takes place from ultrasonic wave radiation, ultraviolet radiation, turbulent flow, stir, heat, alkali adds and hydrogen peroxide adds the mode of selecting the group of formation more than a kind or 2 kinds and carries out.
(13) relate to above-mentioned (8) described ozone water supply apparatus, wherein, the concentration adjusting mechanism carries out the dilution of Ozone Water.
(14) relate to any one described method of ozone water supply in above-mentioned (8)～(13), it is characterized in that Ozone Water carries out to the gas-liquid mixed state that passes in Ozone Water and ozone gas coexistence that uses point.
Description of drawings
Fig. 1 is the working procedure systems figure of a form of ozone water supply apparatus of the present invention;
Fig. 2 is the key diagram with concentration adjusting mechanism of Cooper-Hewitt lamp;
Fig. 3 is the curve chart of the relation of output of expression Cooper-Hewitt lamp and dissolved ozone concentration;
Fig. 4 is the key diagram with concentration adjusting mechanism of heater and cooler;
Fig. 5 is the curve chart of the relation of output of expression Cooper-Hewitt lamp and dissolved ozone concentration.
Embodiment
In method of ozone water supply of the present invention, the Ozone Water that will have ozone decomposition inhibiting substances is transferred to the use point, by the concentration adjusting mechanism ozone concentration of regulation is reduced near using point.Ozone water supply apparatus of the present invention has ozone dissolver, and this ozone dissolver is dissolved in ozone gas in the pure water, the modulation Ozone Water; Ozone is decomposed inhibiting substances supply to mechanism in above-mentioned pure water or the above-mentioned Ozone Water; Ozone Water is passed on pipe arrangement, and this Ozone Water is passed on pipe arrangement and will be transferred to the use point by the Ozone Water of above-mentioned ozone dissolver modulation; Concentration adjusting mechanism, this concentration adjusting mechanism are arranged at and use near the point, will pass on Ozone Water that pipe arrangement passes on by Ozone Water and be reduced to the ozone concentration of regulation.
Fig. 1 is the working procedure systems figure of a form of ozone water supply apparatus of the present invention.To silent discharge type ozone generator 3, supply with the mist of oxygen and micro-nitrogen from oxygen container 1 and nitrogen gas container 2, make the gas that contains ozone, in ozone dissolver 4, ozone is dissolved in the pure water of degasification in advance and makes Ozone Water.Device shown in this figure has, and decomposes the mechanism 5 of inhibiting substances to above-mentioned pure water or above-mentioned ozone water supply ozone; To be transferred to the Ozone Water of using point by the Ozone Water of ozone dissolver manufacturing and pass on pipe arrangement 6; Be located at and use near the point 7, make and pass on Ozone Water that pipe arrangement passes on by Ozone Water and be reduced to the concentration adjusting mechanism 8 of the dissolved ozone concentration of regulation.In the device of this form,, be recovered as the water that does not contain ozone having used the untapped Ozone Water of point to flow to fill the ozonolysed tower 9 of active carbon etc.
In the present invention, has ozone decomposition inhibiting substances in the Ozone Water by making, can under the situation that the dissolved ozone concentration that does not make the Ozone Water by the ozone dissolver manufacturing significantly reduces, Ozone Water be transferred to the use point, even therefore near using point, ozone concentration is reduced, also can use point to keep necessary dissolved ozone concentration by the concentration adjusting mechanism.In the present invention, after in pure water, adding ozone decomposition inhibiting substances, make the ozone dissolving, can be used as Ozone Water, or decompose inhibiting substances, also can be used as Ozone Water with ozone decomposition inhibiting substances by in Ozone Water, adding ozone with ozone decomposition inhibiting substances.Dissolved ozone concentration with Ozone Water of ozone decomposition inhibiting substances cans be compared at the high 1-100mg/L of ozone concentration that uses the some regulation most.
Among the present invention, the amount that the ozone in the Ozone Water decomposes inhibiting substances is preferably 0.1-500mg/L, more preferably 1-400mg/L, more preferably 10-300mg/L.Ozone decomposes the amount of inhibiting substances less than 0.1mg/L, then can not demonstrate fully ozone and decompose and suppress effect, decomposes the danger of carrying out rapidly at the ozone that has in the Ozone Water in using the passing on of point.The amount that ozone decomposes inhibiting substances surpasses 500mg/L, and then having ozone decomposition inhibiting substances becomes the impurity that is cleaned thing, thereby produces dysgenic danger.By the interpolation of ozone decomposition inhibiting substances, the concrete mechanism of inhibition ozone decomposition is not conspicuous, is because ozone decomposes the hydroxyl reaction of inhibiting substances and the decomposition of promotion dissolved ozone but infer, thereby stops the chain reaction that ozone decomposes.
In the present invention, ozone decompose that inhibiting substances preferably selects from the group that water-soluble organic compounds, inorganic acid or its salt and hydrazine constitute more than a kind or 2 kinds.As the water-soluble organic compounds that uses among the present invention, enumerated such as, the alcohols of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol etc.; The glycols of the ketone of acetone, methyl ethyl ketone, methyl isopropyl Ketone etc., ethylene glycol, propylene glycol etc.; The alkanol amine of monoethanolamine, diethanol amine etc.; The aromatic compound of the aliphatic acid of acetic acid, propionic acid etc., benzylalcohol, phenol, hydroquinones, benzoic acid, M-phthalic acid etc. etc.In these compositions, because the alcohols of isopropyl alcohol etc. when the cleaning of silicon wafer, glass substrate etc., do not have being cleaned the danger that thing causes adverse effect, so preferably adopt the alcohols of this isopropyl alcohol etc.Water-soluble organic compounds can be used as the cleanser of the hydroxyl of capturing the decomposition that promotes ozone, and that suppresses ozone itself decomposes the rapid decline of ozone concentration.
As inorganic acid of the present invention or its salt, can enumerate such as, hydrochloric acid, sulfuric acid, carbonic acid, carbonate, bicarbonate, nitrous acid, nitrite, sulfurous acid, sulphite, bisulfites, fluoric acid etc.In these, owing to carbonic acid can use the back to volatilize as carbon dioxide in Ozone Water, so preferably adopt carbonic acid.Inorganic acid or its salt can be used as the aqueous solution and make an addition in pure water or the Ozone Water, also can add according to the mode of the gas of carbon dioxide, sulphurous acid gas etc., also can be by to HCO
3The anion exchange resin of-shape carries out the mode of water flowing and adds.By adding acid, make the pH value in 2～6 scope, can reduce the amount of the hydroxyl of the decomposition that promotes ozone, suppress decomposing of ozone itself, prevent the rapid decline of ozone concentration.In addition, the anion of the carbonic acid ion of formation salt, nitrite ion etc. also has the effect that reduces hydroxyl, prevents the rapid decline of ion concentration.
In the present invention, as the ion concentration adjusting mechanism, can enumerate the decomposition of the dissolved ozone in the Ozone Water, the dilution of Ozone Water etc.The method of the dissolved ozone in the ozone decomposition water has no particular limits, such as, can enumerate that ultrasonic irradiation, ultraviolet irradiation, turbulent flow take place, stir, heat, alkali interpolation, hydrogen peroxide interpolation etc.The dissolved ozone concentration of the Ozone Water by the adjustment of concentration adjusting mechanism is preferably in more than the 5mg/L.If the dissolved ozone ion concentration less than 5mg/L, then has when using the use of point, the cleaning performance of Ozone Water, inadequate danger such as surface treatment effect.
In the present invention, hyperacoustic radiation of Ozone Water by such as, mechanically with the water flowing path ways of connecting of ultrasonic oscillator and Ozone Water, can be to the Ozone Water radiate supersonic wave.By to the Ozone Water radiate supersonic wave, in Ozone Water, produce the ultrasonic wave hole, produce hydroxyl, promote the decomposition of ozone.Best, the frequency of ultrasonic of institute's radiation is in the scope of 10kHz～3MHz.Owing to have the danger that produces fine particle etc. at hyperacoustic oscillating portion, preferably with the combination of filters use.By the selection of hyperacoustic amplitude, frequency, output etc., be adjustable to the ozone concentration of regulation.
In the present invention, for the radiation of ultraviolet ray to Ozone Water, such as, in the water flowing path of Ozone Water, ultraviolet radiation device is set, can be to Ozone Water radiation ultraviolet ray.Be used for the light source that ultraviolet radiation adopts and have no particular limits, such as exemplifying out Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, xenon lamp, deuterium lamp, metal halide lamp etc.By changing the kind of lamp, can change the ultraviolet wavelength of institute's radiation.In these lamps, preferably adopt the high Cooper-Hewitt lamp of ultraviolet radiation efficient that has dominant wavelength at 253.7nm.In the pipe of the ultraviolet radiation portion of water flowing path, the unit that the material by the ultraviolet (uv) transmission of quartz glass, transparent polytetrafluoroethylene etc. forms is set, thus, can be effectively to Ozone Water radiation ultraviolet ray.Ultraviolet amount of radiation can be by adjusting lamp the mode of output control.Perhaps, the mode on surface that also can be by blocking lamp is controlled.By ultraviolet radiation, produce hydroxyl, promote decomposing of ozone itself.For ultraviolet radiation,, do not produce Ozone Water yet and pollute, so preferably adopt this mode because the concentration adjusting mechanism is operated easily.
In the present invention, the adjustment of the output of ultra-violet lamp can be undertaken by the adjustment of lamp primary side magnitude of voltage, primary side current value, secondary side magnitude of voltage, secondary side current value etc.In the occasion of the ultraviolet lamp employing of radiation Cooper-Hewitt lamp, best, lamp secondary side power consumption is in the scope of 0.5～15W.Occasion in the scope of secondary side power consumption at 0.5～15W of Cooper-Hewitt lamp, between lamp secondary side power consumption and ozone decomposition amount, the good mild curved line relation of reproducibility is set up, and can easily Ozone Water be adjusted to the ozone concentration of regulation.As the ultraviolet lamp of radiation, in the occasion of using high-pressure mercury-vapor lamp, preferably lamp secondary side power consumption is 5～1,500W.At the secondary side power consumption of high-pressure mercury-vapor lamp 5～1, the occasion in the scope of 500W, between lamp secondary side power consumption and ozone decomposition amount, reproducibility is good, mild curved line relation is set up, and can easily Ozone Water be adjusted to the ozone concentration of regulation.Best, the inverse of the residence time of the Ozone Water in the container of the ultraviolet lamp of radiation, that is, space velocity (SV) is at 100～5000h
-1Scope in.
In the present invention, take place for turbulent flow, such as, on the water flowing path of Ozone Water, turbulent current generating device is set, can make the mobile generation turbulent flow of Ozone Water.The turbulator that is adopted has no particular limits, such as, can list static mixer with drive part, mechanical oscillation formula ultrasonic wave, be assembled with the pipe-line mixer of turbine and stator etc.In these devices, because the easy maintenance management of static mixer does not have foreign matter to sneak into and the danger of Ozone Water pollution, so preferably adopt this static mixer.By making the mobile generation turbulent flow of Ozone Water, transfer energy in the ozone of dissolving, promote the decomposition of ozone.
In the present invention, for stirring, such as, by on the water flowing path, rabbling mechanism being set, can stir Ozone Water.As the rabbling mechanism of water flowing path, can enumerate, such as, the electromagnetic stirrer of the stirring vane of paddle sheet, turbine blade, camber blades etc., electromagnetic agitation formula, state type mixer etc.In them, because the state type mixer does not have the dust because of producing, with the danger of Ozone Water pollution, so preferably adopt this state type mixer.By Ozone Water is stirred, give the ozone that is dissolved with energy delivery, promote the decomposition of ozone.
In the present invention, for heating of Ozone Water, can by such as, on the water flowing path of Ozone Water, heat exchanger etc. is set, Ozone Water is heated.There is not foreign matter to sneak into and danger that Ozone Water is polluted owing to be arranged at heat exchanger on the water flowing path, so preferably adopt this heat exchanger.By Ozone Water is heated, provide energy to the ozone that is dissolved, promote to decompose.Best, by being arranged at cooler on the water flowing path etc., will be by heating, its dissolved ozone concentration is reduced to the concentration of ozone water cooling of regulation to the temperature of using the desired regulation of point.In the gentle cooling of adding of Ozone Water, can adopt recovery heat exchanger, improve the heat efficiency.
In the present invention, by in Ozone Water, adding alkali, can promote the decomposition of ozone.The alkali that makes an addition in the Ozone Water has no particular limits, such as, can enumerate ammonia, NaOH, potassium hydroxide, calcium hydroxide etc.In them, because ammonia volatilization and retained foreign body not, so preferably adopt ammonia.If by adding alkali, the pH value rises, Ozone Water is an alkalescence, and then the ozone instability promotes to decompose.
In the present invention, by in Ozone Water, adding hydrogen peroxide, can promote the decomposition of ozone.Hydrogen peroxide produces hydroxyl in water, hydroxyl decomposes ozone.
In the present invention, because between reduction amount to the dissolved ozone concentration of the Ozone Water of the intensity of the intensity of the ultraviolet amount of radiation of Ozone Water, hyperacoustic amount of radiation, the turbulent flow that produced, stirring and time, the ascending temperature of heating, alkali addition or hydrogen peroxide addition, decomposition, the relation of clear and definite amount is set up with good reproducibility, so can the dissolved ozone concentration of Ozone Water be adjusted to setting by obtaining the relation of this amount in advance.
In the present invention, use near the concentration adjusting mechanism of the Ozone Water of point to dilute to Ozone Water.Best, the dilution employing of Ozone Water and the identical pure water of purity of the employed pure water of manufacturing of this Ozone Water.The concentration that causes for the decomposition that prevents ozone reduces, and pure water that also can be by acidity, has added organic compound, particularly organic acid pure water, dilutes.With the Ozone Water dilution, form dissolved ozone concentration of ozone water with regulation, thus, can under the situation that does not have waste, fully utilize to be dissolved in the ozone that is transferred in the Ozone Water of using point.
In the present invention, Ozone Water is to using passing on of point to carry out at the gas-liquid mixed state of Ozone Water and ozone gas coexistence.The gas-liquid mixed state of Ozone Water and ozone gas coexistence can form by following mode, this mode is: such as, pure water is pressed in the injector, the pure water that has been pressed into is ejected into the center of venturi (ベ Application チ ユ リ one) nozzle, by reduction, suck the gas that contains ozone at its peripheral pressure that produces.The ozone that is in the gas that contains ozone that sucks in the injector is dissolved in the pure water, produce Ozone Water, and the remaining gas that contains ozone is the gas-liquid mixed state of Ozone Water and ozone gas, in the stream enlarging section, follow reducing of flow velocity, pressure increases, and is discharged to Ozone Water and passes in the pipe arrangement.In the Ozone Water that is in the gas-liquid mixed state with ozone gas, in being transferred to the ozone water supply pipe during, dissolve in ozone, replenish the ozone that disappears because of decomposition, thus, can prevent the reduction of dissolved ozone concentration.Preferably the pressure of the gas-liquid mixture fluid of the Ozone Water of the outlet of injector and ozone gas is higher than atmospheric pressure, is preferably in more than the 200kPa.Because the pressure of the gas-liquid mixture fluid of Ozone Water and ozone gas is higher than atmospheric pressure, can realize the passing on of long distance of Ozone Water.Particularly, the rapid concentration reduction inhibitory action of the ozone that the existence that best ozone decomposes inhibiting substances causes is kept effect with the ozone concentration that Ozone Water, ozone gas coexisting state cause and is matched, and can pass under the state of keeping ozone concentration with higher degree.
According to the inventive method and device, because can be at the gas-liquid mixed state of Ozone Water and ozone gas coexistence, be transferred to long distance the use point, before using point, adjust to the concentration of regulation, so can freely supply with concentration of ozone water necessary separately in a plurality of use points from an Ozone Water manufacturing installation.In the occasion of passing on the gas-liquid mixed state, best, remove residual gas by using the preceding gas-liquid separator of point, then, reduce ozone concentration by the concentration adjusting mechanism.When being that concentration is adjusted, ozone decomposes and the oxygen that forms is in the occasion of hypersaturated state, also can after the concentration adjusting mechanism gas-liquid separator be set.That is, gas-liquid separator can be arranged at prime, back level or prime and the two place of back level of the concentration adjusting mechanism of ozone.
Embodiment
Enumerate embodiment below, the present invention is more specifically described, still, the present invention is not limited to embodiment fully.
In addition, in embodiment and comparative example, ozone generator " Sumitomo accurate industry (strain), silent discharge type ozone generator SG-01CHU " 3, ozone dissolver " ジ ヤ パ Application go ア テ Star Network ス (strain), ozone dissolving film assembly " 4, the carbon dioxide that employing has a working procedure systems figure shown in Figure 1 adds mechanism 5, Ozone Water and passes on pipe arrangement 6, the branched pipe that uses point 7 and the testing equipment (pilot plant) of ozone concentration adjusting mechanism 8.Ozone generating-device passes through oxygen container 1 and nitrogen gas container 2, respectively supplying high purity oxygen and high-purity nitrogen.Remaining Ozone Water is carried out water flowing to the ozonolysed tower 9 of filling activated carbon " chestnut field industry (strain), Network リ コ-Le WG160 ", ozone decomposed, then, with its discharging.Supply with oxygen 1L (standard state)/min and nitrogen 4mL (standard state)/min to ozone generator, the electric current of ozone generator is 0.6A, and the manufacturing ozone concentration is 200g/m
3The gas that contains ozone of (standard state).In ozone dissolver 4, supply with pure water 20L/min, with the ozone gas dissolving, with the concentration adjusting mechanism 8 of its supply apart from 10m.
Embodiment 1
The concentration adjusting mechanism adopts water flowing unit 11 to test, and this water flowing unit 11 comprises having and has the Cooper-Hewitt lamp " thousand generation field worker Trafficking (strain) GL-4, GL-10 and GL-40 " of stabilizer 10 that carries out the function of light modulation according to dominant wavelength 253.7nm shown in Figure 2.Adopt dissolved ozone meter 12, measure the dissolved ozone concentration of the Ozone Water of this water flowing unit outlet.
Ultra-pure water is supplied with testing equipment (pilot plant), from add the carbon dioxide bottle of mechanism as carbon dioxide, according to CO
2Concentration is the mode of 3mg/L, carbon dioxide is added being dissolved in the ultra-pure water, in ozone dissolver, ozone is dissolved in the carbon dioxide dissolving ultra-pure water, and modulation dissolved ozone concentration is the Ozone Water of 25.9mg/L.Under the situation of not lighting Cooper-Hewitt lamp, this Ozone Water is led in the unit, at this moment, the dissolved ozone concentration of Ozone Water is 25.9mg/L at unit inlet and exit, unit.Then, when lighting Cooper-Hewitt lamp with 1.5W output, the dissolved ozone concentration of unit outlet is 20.1mg/L.If improve the output of Cooper-Hewitt lamp gradually, when then the pass between the dissolved ozone concentration of output and unit outlet ties up to 2W, be 18.0mg/L, when 3.5W 13.7mg/L, when 5W 11.6mg/L, when 10W 8.0mg/L, when 15W 5.7mg/L.
Comparative example 1
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 25.9mg/L, operates according to the mode identical with embodiment 1.
Under the situation of not lighting Cooper-Hewitt lamp, this Ozone Water is led in the unit, at this moment, the dissolved ozone concentration of Ozone Water is 8.2mg/L in unit inlet and exit, unit.Then, when lighting Cooper-Hewitt lamp with 1.5W, the dissolved ozone concentration of unit outlet is 5.9mg/L.If improve the output of Cooper-Hewitt lamp gradually, when then the pass between the dissolved ozone concentration of output and unit outlet ties up to 2W, be 5.0mg/L, when 3.5W 4.1mg/L, when 5W 2.1mg/L, when 10W 2.6mg/L.
The results are shown among table 1 and Fig. 3 of embodiment 1 and comparative example 1.
Table 1
| Lamp output (W) | Dissolved ozone concentration (mg/L) | |
| Embodiment 1 | Comparative example 1 | |
| 0 | 25.9 | 8.2 |
| 1.5 | 20.1 | 5.9 |
| 2 | 18.0 | 5.0 |
| 3 | 15.0 | 5.0 |
| 3.5 | 13.7 | 4.1 |
| 4.5 | 12.6 | 2.3 |
| 5 | 11.6 | 2.1 |
| 5.5 | 10.7 | 3.2 |
| 7 | 9.5 | 3.0 |
| 8 | 8.8 | 2.0 |
| 10 | 8.0 | 2.6 |
| 13 | 6.7 | 1.6 |
| 15 | 5.7 | - |
| 17 | 5.0 | - |
As table 1 and shown in Figure 3, be in the ultra-pure water to have as ozone and decompose among the embodiment 1 of carbonic acid of inhibiting substances, the dissolved ozone concentration by the ozone dissolver modulation is that the dissolved ozone concentration of the Ozone Water of 25.9mg/L does not reduce, and is transferred to the use point.Know in addition, if improve the output of the Cooper-Hewitt lamp of water flowing unit, then ozone decomposes, dissolved ozone concentration reduces, pass between output and the dissolved ozone concentration is mild curve, thus, the output by the control Cooper-Hewitt lamp can stably obtain required dissolved ozone concentration of ozone water.Relative this situation, be not have in the ultra-pure water as ozone and decompose in the comparative example 1 of carbonic acid of inhibiting substances, the dissolved ozone concentration that is transferred to the Ozone Water of using point is reduced to 8.2mg/L, in the output of Cooper-Hewitt lamp and the relation between the dissolved ozone concentration, differs greatly.
The ozone concentration adjusting mechanism adopts heater 13 and cooler 14 shown in Figure 4 to test.Adopt dissolved ozone meter 12, measure the dissolved ozone concentration of the Ozone Water of cooler outlet.
According to the mode identical with embodiment 1, modulation CO
2Concentration is 3mg/L, and dissolved ozone concentration is the Ozone Water of 25.9mg/L.In heater, this Ozone Water is heated to 25 ℃, in cooler, under 25 ℃ state, make its outflow.The dissolved ozone concentration of the Ozone Water of cooler outlet is 14.1mg/L.The heating-up temperature of heater is 30 ℃, 40 ℃, 50 ℃, and when being cooled to 25 ℃ by cooler, the dissolved ozone concentration of the Ozone Water of cooler outlet is respectively 12.8mg/L, 10.0mg/L, 6.4mg/L.
Comparative example 2
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 25.9mg/L, operates according to the mode identical with embodiment 2.
In heater Ozone Water is heated to 25 ℃, in cooler, makes its outflow at 25 ℃ states, at this moment, the dissolved ozone concentration of the Ozone Water of cooler outlet is 6.0mg/L.Adopt heater with heating-up temperature to 30 ℃, 40 ℃, 50 ℃, when being cooled to 25 ℃ with cooler, the dissolved ozone concentration of the Ozone Water of cooler outlet is respectively 2.0mg/L, 0.6mg/L, 0.6mg/L.
The results are shown in Table 2 for embodiment 2 and comparative example 2.
Table 2
| Heating-up temperature (℃) | Dissolved ozone concentration (mg/L) | |
| |
Comparative example 2 | |
| 25 | 14.1 | 6.0 |
| 30 | 12.8 | 2.0 |
| 36 | 11.2 | 1.0 |
| 40 | 10.0 | 0.6 |
| 43 | 9.1 | 1.0 |
| 45 | 8.0 | 1.0 |
| 50 | 6.4 | 0.6 |
As shown in table 2, in ultra-pure water, have as ozone and decompose among the embodiment 2 of carbonic acid of inhibiting substances, if improve the heating-up temperature of heater, then ozone decomposes, and dissolved ozone concentration reduces, relation between heating-up temperature and the dissolved ozone concentration is mild curve, like this, by the heating-up temperature of control heater, can stably obtain required dissolved ozone concentration.Relative this situation is not have in the ultra-pure water as ozone and decomposes in the comparative example 2 of carbonic acid of inhibiting substances, and by using heater heats, the dissolved ozone concentration of Ozone Water sharply reduces.
Adopt the water flowing unit as the ozone concentration adjusting mechanism, test, this water flowing unit comprises the Cooper-Hewitt lamp " thousand generation field worker Trafficking (strain) GL-4, GL-10 and GL-40 " that has the function of light modulation at dominant wavelength 253.7nm according to shown in Figure 2.
According to the mode identical with embodiment 1, modulation CO
2Concentration is 3mg/L, and dissolved ozone concentration is the Ozone Water of 25.9mg/L, according to space velocity (SV) 2000h
-1To carry out water flowing to the water flowing unit, the output of Cooper-Hewitt lamp becomes 40W from 1.6W.Pass between the dissolved ozone concentration of the Ozone Water of the output of Cooper-Hewitt lamp and unit outlet is 20.0mg/L when tying up to 1.6W, when 3.6W 13.9mg/L, when 5.6W 11.1mg/L, when 9.9W 8.1mg/L, when 15.0W 7.7mg/L, being 3.8mg/L when 20.0W, is 3.4mg/L when 31.8W, is 2.7mg/L when 40.0W.
The results are shown in Table 3 for embodiment 3.
As shown in table 3, be in the ultra-pure water, have as ozone and decompose among the embodiment 3 of carbonic acid of inhibiting substances, if improve the output of the Cooper-Hewitt lamp of water flowing unit, then ozone decomposes, and dissolved ozone concentration reduces, pass between output and the dissolved ozone concentration is mild curve, thus, the output by the control Cooper-Hewitt lamp can stably obtain required dissolved ozone concentration of ozone water.Particularly in the occasion of lamp output below 20W, the relation of lamp output and dissolved ozone concentration is stable.
Table 3
| Lamp output (W) | Dissolved ozone concentration (mg/L) |
| 1.6 | 20.0 |
| 2.0 | 18.0 |
| 3.0 | 15.0 |
| 3.6 | 13.9 |
| 4.4 | 12.7 |
| 5.1 | 11.8 |
| 5.6 | 11.1 |
| 7.1 | 9.6 |
| 8.1 | 8.9 |
| 9.9 | 8.1 |
| 13.1 | 6.8 |
| 15.0 | 7.7 |
| 17.2 | 5.0 |
| 20.0 | 3.8 |
| 23.8 | 2.0 |
| 27.9 | 3.0 |
| 31.8 | 3.4 |
| 36.0 | 4.0 |
| 40.0 | 2.7 |
The ozone concentration adjusting mechanism adopts the water flowing unit to test, and this water flowing unit comprises shown in Figure 2, is the Cooper-Hewitt lamp " thousand generation field worker Trafficking (strain) GL-4, GL-10 and GL-40 " that 253.7nm has dimming function in dominant wavelength.
Ultra-pure water is supplied with testing equipment (pilot plant), from add the carbon dioxide bottle of mechanism as carbon dioxide, according to CO
2Concentration is the mode of 3mg/L, carbon dioxide is added being dissolved in the ultra-pure water, in ozone dissolver, ozone is dissolved in the carbon dioxide dissolving ultra-pure water, and modulation dissolved ozone concentration is the Ozone Water of 36.5mg/L.According to space velocity (SV) 6000h
-1The water flowing unit is carried out water flowing, and the output of Cooper-Hewitt lamp becomes 17.0W from 1.5 W.Pass between the dissolved ozone concentration of the Ozone Water of the output of Cooper-Hewitt lamp and unit outlet is 20.0mg/L when tying up to 1.5W, is 13.9mg/L when 3.6W, is 10.9mg/L when 5.5W, is 8.3 mg/L when 9.8W, is 5.0mg/L when 17.0W.
Comparative example 3
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 36.5mg/L, operates according to the mode identical with embodiment 4.Pass between the dissolved ozone concentration of the Ozone Water of the output of Cooper-Hewitt lamp and unit outlet is 31.8mg/L when tying up to 1.5W, is 25.7mg/L when 3.6W, is 18.8mg/L when 5.5W, is 14.1mg/L when 9.8W, is 10.0mg/L when 17.0W.
The results are shown among table 4 and Fig. 5 of embodiment 4 and comparative example 3.
Table 4
| Lamp output (W) | Dissolved ozone concentration (mg/L) | |
| |
Comparative example 3 | |
| 1.5 | 20.0 | 31.8 |
| 2.0 | 18.1 | 25.0 |
| 3.0 | 15.1 | 27.4 |
| 3.6 | 13.9 | 25.7 |
| 4.4 | 12.8 | 20.0 |
| 5.0 | 12.0 | 17.9 |
| 5.5 | 10.9 | 18.8 |
| 7.0 | 9.7 | 19.0 |
| 8.0 | 9.0 | 13.4 |
| 9.8 | 8.3 | 14.1 |
| 12.9 | 7.0 | 12.0 |
| 14.9 | 5.6 | 9.1 |
| 17.0 | 5.0 | 10.0 |
As table 4 and shown in Figure 5, in ultra-pure water, have as ozone and decompose among the embodiment 4 of carbonic acid of inhibiting substances, if even be 6000h according to space velocity (SV)
-1Short situation of residence time of mode water flowing unit under, improve the output of the Cooper-Hewitt lamp of water flowing unit, then ozone decomposes, dissolved ozone concentration reduces, pass between output and the dissolved ozone concentration is mild curve, thus, the output by the control Cooper-Hewitt lamp can stably obtain required dissolved ozone concentration of ozone water.Relative this situation in ultra-pure water, does not have as ozone and decomposes in the comparative example 3 of carbonic acid of inhibiting substances, if be 6000h according to space velocity (SV)
-1Residence time of mode water flowing unit short, then the reduction amount of dissolved ozone concentration is little, the differing greatly of the relation between the output of Cooper-Hewitt lamp and the dissolved ozone concentration.
The ozone concentration adjusting mechanism adopts the water flowing unit to test, and ultrasonic oscillator " (strain) プ レ テ Star Network system, PT005JIA " is installed in this water flowing unit.
According to the mode identical with embodiment 1, modulation CO
2Concentration is 3mg/L, and dissolved ozone concentration is the Ozone Water of 25.9mg/L.This Ozone Water is led in the unit, be output as 30W, 40W when 50W or 60W, makes the supersonic oscillations of frequency 39kHz, and it is radiated Ozone Water.
The dissolved ozone concentration of the Ozone Water of water flowing unit outlet is 19mg/L when 30W, is 17mg/L when 40W, is 15mg/L when 50W, is 14mg/L when 60W.
Comparative example 4
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 25.9mg/L, according to the mode identical with embodiment 5, operates.
The dissolved ozone concentration of the Ozone Water of water flowing unit outlet is 5mg/L when being output as 30W, is 6mg/L when 40W, is 6mg/L when 50W, is 3mg/L when 60W.
The results are shown in Table 5 for embodiment 5 and comparative example 4.
Table 5
| Ultrasonic wave output (W) | Dissolved ozone concentration (mg/L) | |
| |
Comparative example 4 | |
| 30 | 19 | 5 |
| 40 | 17 | 6 |
| 50 | 15 | 6 |
| 60 | 14 | 3 |
As shown in table 5, be to have in the ultra-pure water as ozone and decompose among the embodiment 5 of carbonic acid of inhibiting substances, if improve the output of the ultrasonic oscillator of water flowing unit, then ozone decomposes, dissolved ozone concentration reduces, and the pass between output and the dissolved ozone concentration is mild curve, thus, output by the control ultrasonic oscillator can stably obtain required dissolved ozone concentration of ozone water.Relatively this situation is in the ultra-pure water, does not have as ozone to decompose in the comparative example 4 of carbonic acid of inhibiting substances, there is not certain relation between the output of ultrasonic oscillator and the dissolved ozone concentration, in addition, the decomposition of ozone is many, and the degree of the reduction of dissolved ozone concentration is big.
The ozone concentration adjusting mechanism adopts glass unit to test, and in this glass unit, has put into the rotor that stirs usefulness by magnetic stirrer " ア ズ ワ Application (strain), HS-3B ".
According to the mode identical with embodiment 1, modulation CO
2Concentration is 3mg/L, and dissolved ozone concentration is the Ozone Water of 25.9mg/L.This Ozone Water is led in the glass unit, according to 100rpm, 500rpm, the revolution of the rotor of 1000rpm or 1500rpm stirs.
Revolution at rotor is 100rpm, 500rpm, and 1000rpm, during 1500rpm, the dissolved ozone concentration of the Ozone Water of glass unit outlet is respectively 19mg/L, 15mg/L, 13mg/L, 12mg/L.
Comparative example 5
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 25.9mg/L, according to the mode identical with embodiment 6, operates.
Revolution at rotor is 100rpm, 500rpm, and 1000rpm, during 1500rpm, the dissolved ozone concentration of the Ozone Water of glass unit outlet is respectively 5mg/L, 7mg/L, 4mg/L, 5mg/L.
The results are shown in Table 6 for embodiment 6 and comparative example 5.
Table 6
| Revolution (rpm) | Dissolved ozone concentration (mg/L) | |
| |
Comparative example 5 | |
| 100 | 19 | 5 |
| 500 | 15 | 7 |
| 1000 | 13 | 4 |
| 1500 | 12 | 5 |
As shown in table 6, be in the ultra-pure water, have as ozone and decompose among the embodiment 6 of carbonic acid of inhibiting substances, if improve the revolution of rotor, then ozone decomposes, dissolved ozone concentration reduces, pass between rotation number and the dissolved ozone concentration is mild curve, thus, and by revolution by rotor, the intensity that control is stirred can stably obtain required dissolved ozone concentration of ozone water.Relative this situation is not have in the ultra-pure water as ozone and decomposes in the comparative example 4 of carbonic acid of inhibiting substances, does not have certain relation between the revolution of rotor and the dissolved ozone concentration, and in addition, the decomposition of ozone is many, and the degree of the reduction of dissolved ozone concentration is big.
Embodiment 7
The ozone concentration adjusting mechanism adds hydrogen peroxide to be tested.
Entrance side at the glass unit of the device identical with embodiment 6, the hydrogen peroxide inlet is set,, makes the rotor rotation according to the revolution of 100rpm by magnetic stirrer, stir, inject 1 weight % aquae hydrogenii dioxidi, the hydrogen peroxide water concentration in the Ozone Water is 5mg/L, 7mg/L, 15mg/L, 22mg/L, 32mg/L, 50mg/L.
Hydrogen peroxide water concentration in Ozone Water is 5mg/L, 7mg/L, and 15mg/L, 22mg/L, 32mg/L, during 50mg/L, the dissolved ozone concentration of the Ozone Water of glass unit outlet is respectively 18mg/L, 16mg/L, 8mg/L, 6mg/L, 5mg/L, 4mg/L.
Comparative example 6
Except do not add dissolved carbon dioxide gas in the ultra-pure water of supplying with testing equipment (pilot plant), modulation dissolved ozone concentration is beyond the Ozone Water of 25.9mg/L, operates according to the mode identical with embodiment 7.
Hydrogen peroxide water concentration in Ozone Water is 5mg/L, 7mg/L, and 15mg/L, 22mg/L, 32mg/L, during 50mg/L, the dissolved ozone concentration of the Ozone Water of glass unit outlet is respectively 5mg/L, 4mg/L, 5mg/L, 3mg/L, 4mg/L, 3mg/L.
The results are shown in Table 7 for embodiment 7 and comparative example 6.
Table 7
| Hydrogen peroxide (mg/L) | Dissolved ozone concentration (mg/L) | |
| Embodiment 7 | Comparative example 6 | |
| 5 | 18 | 5 |
| 7 | 16 | 4 |
| 15 | 8 | 5 |
| 22 | 6 | 3 |
| 32 | 5 | 4 |
| 50 | 4 | 3 |
As shown in table 7, be to have in the ultra-pure water as ozone and decompose among the embodiment 7 of carbonic acid of inhibiting substances, if improve the amount of the hydrogen peroxide that is added, then ozone decomposes, dissolved ozone concentration reduces, and the pass between the addition of hydrogen peroxide and the dissolved ozone concentration is mild curve, thus, addition by the control hydrogen peroxide can stably obtain required dissolved ozone concentration of ozone water.Relatively this situation is in the ultra-pure water, does not have as ozone to decompose in the comparative example 6 of carbonic acid of inhibiting substances, there is not certain relation between the addition of hydrogen peroxide and the dissolved ozone concentration, in addition, the decomposition of ozone is many, and the degree of the reduction of dissolved ozone concentration is big.
The inhibiting substances of decomposing ozone adopts isopropyl alcohol (being called " IPA " below) to test.
Except replacing the carbon dioxide of embodiment 1, be the mode of 50 μ g/L according to IPA concentration, IPA is added and beyond being dissolved in the ultra-pure water, according to the mode identical with embodiment 1, the output that changes Cooper-Hewitt lamp is tested.
Consequently, the dissolved ozone concentration of unit outlet is as shown in table 8.
Table 8
| Lamp output (W) | Dissolved ozone concentration (mg/L) |
| 0 | 26.4 |
| 1.5 | 20.5 |
| 3 | 15.3 |
| 4.5 | 12.9 |
| 5.5 | 10.9 |
| 7 | 9.7 |
| 8 | 9.0 |
| 10 | 8.2 |
| 13 | 6.8 |
| 17 | 5.1 |
Know according to this result, adopt under the situation of IPA, still can adjust ozone concentration corresponding to lamp (ultraviolet ray) output even decompose inhibiting substances at ozone.
Utilize possibility on the industry
According to method of ozone water supply of the present invention and device, can suppress the decomposition of ozone, the ozone that ozone concentration is high is transferred to the use point, near the use point, adopt the ozone concentration guiding mechanism, be reduced to the ozone concentration of regulation, to using point, supply with the Ozone Water of normal concentration stablely.
Label declaration
Label 1 expression oxygen container;
Point is used in label 7 expressions;
Label 9 expression ozonolysed towers;
Label 11 expression water flowing unit;
Claims (14)
1. a method of ozone water supply is characterized in that the Ozone Water that will have ozone decomposition inhibiting substances is transferred to the use point, near the use point, by the concentration adjusting mechanism, is reduced to the concentration of this water the ozone concentration of regulation.
2. method of ozone water supply according to claim 1, it is characterized in that ozone decompose inhibiting substances for from the group that water-soluble organic compounds, inorganic acid or its salt and hydrazine constitute, select more than a kind or 2 kinds.
3. method of ozone water supply according to claim 2 is characterized in that inorganic acid or its salt are hydrochloric acid, sulfuric acid, carbonic acid, carbonate, bicarbonate, nitrous acid, nitrite, sulfurous acid, sulphite or bisulfites.
4. method of ozone water supply according to claim 1 is characterized in that the concentration adjusting mechanism carries out the decomposition of dissolved ozone.
5. method of ozone water supply according to claim 4, the decomposition that it is characterized in that dissolved ozone by takes place from ultrasonic wave radiation, ultraviolet radiation, turbulent flow, stir, heat, alkali adds and hydrogen peroxide adds the mode of selecting the group of formation more than a kind or 2 kinds and carries out.
6. method of ozone water supply according to claim 1 is characterized in that the concentration adjusting mechanism carries out the dilution of Ozone Water.
7. according to each described method of ozone water supply in the claim 1～6, it is characterized in that Ozone Water carries out to the gas-liquid mixed state that passes in Ozone Water and ozone gas coexistence that uses point.
8. an ozone water supply apparatus is characterized in that this ozone water supply apparatus comprises ozone dissolver, and this ozone dissolver is dissolved in ozone gas in the pure water, the modulation Ozone Water; Ozone is decomposed inhibiting substances supply to mechanism in above-mentioned pure water or the above-mentioned Ozone Water; Ozone Water is passed on pipe arrangement, and this Ozone Water is passed on pipe arrangement and will be transferred to the use point by the Ozone Water of above-mentioned ozone dissolver modulation; Concentration adjusting mechanism, this concentration adjusting mechanism are arranged at and use near the point, will pass on Ozone Water that pipe arrangement passes on by Ozone Water and be reduced to the ozone concentration of regulation.
9. ozone water supply apparatus according to claim 8, it is characterized in that ozone decompose inhibiting substances for from the group that water-soluble organic compounds, inorganic acid or its salt and hydrazine constitute, select more than a kind or 2 kinds.
10. ozone water supply apparatus according to claim 9 is characterized in that inorganic acid or its salt are hydrochloric acid, sulfuric acid, carbonic acid, carbonate, bicarbonate, nitrous acid, nitrite, sulfurous acid, sulphite or bisulfites.
11. ozone water supply apparatus according to claim 8 is characterized in that the concentration adjusting mechanism carries out the decomposition of dissolved ozone.
12. ozone water supply apparatus according to claim 11, the decomposition that it is characterized in that dissolved ozone by takes place from ultrasonic wave radiation, ultraviolet radiation, turbulent flow, stir, heat, alkali adds and hydrogen peroxide adds the mode of selecting the group of formation more than a kind or 2 kinds and carries out.
13. ozone water supply apparatus according to claim 8 is characterized in that the concentration adjusting mechanism carries out the dilution of Ozone Water.
14. each described method of ozone water supply according to Claim 8～13 is characterized in that Ozone Water carries out to the gas-liquid mixed state that passes in Ozone Water and ozone gas coexistence that uses point.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP104505/2004 | 2004-03-31 | ||
| JP2004104505A JP4513122B2 (en) | 2004-03-31 | 2004-03-31 | Ozone water supply method and ozone water supply device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1938829A true CN1938829A (en) | 2007-03-28 |
Family
ID=35064065
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800100348A Pending CN1938829A (en) | 2004-03-31 | 2005-03-18 | Ozone water supply method and ozone water supply device |
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| Country | Link |
|---|---|
| JP (1) | JP4513122B2 (en) |
| CN (1) | CN1938829A (en) |
| TW (1) | TWI380954B (en) |
| WO (1) | WO2005096359A1 (en) |
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-
2004
- 2004-03-31 JP JP2004104505A patent/JP4513122B2/en not_active Expired - Fee Related
-
2005
- 2005-02-25 TW TW094105723A patent/TWI380954B/en not_active IP Right Cessation
- 2005-03-18 WO PCT/JP2005/005632 patent/WO2005096359A1/en active Application Filing
- 2005-03-18 CN CNA2005800100348A patent/CN1938829A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200533608A (en) | 2005-10-16 |
| TWI380954B (en) | 2013-01-01 |
| JP4513122B2 (en) | 2010-07-28 |
| JP2005294377A (en) | 2005-10-20 |
| WO2005096359A1 (en) | 2005-10-13 |
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