WO2011105205A1 - 紫外線酸化装置及びそれを用いた超純水製造装置、並びに紫外線酸化方法及び超純水製造方法 - Google Patents
紫外線酸化装置及びそれを用いた超純水製造装置、並びに紫外線酸化方法及び超純水製造方法 Download PDFInfo
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- WO2011105205A1 WO2011105205A1 PCT/JP2011/052562 JP2011052562W WO2011105205A1 WO 2011105205 A1 WO2011105205 A1 WO 2011105205A1 JP 2011052562 W JP2011052562 W JP 2011052562W WO 2011105205 A1 WO2011105205 A1 WO 2011105205A1
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- ultraviolet
- water
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- ultrapure water
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- 239000012498 ultrapure water Substances 0.000 title claims abstract description 46
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Images
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B01D61/08—Apparatus therefor
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
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- 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
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3224—Units using UV-light guiding optical fibers
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- 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
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3227—Units with two or more lamps
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- 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
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/328—Having flow diverters (baffles)
Definitions
- the present invention relates to an ultraviolet oxidation apparatus that oxidizes and decomposes organic substances contained in water to be treated using ultraviolet rays, an ultrapure water production apparatus using the same, an ultraviolet oxidation method, and an ultrapure water production method.
- Patent Document 1 hydrogen peroxide and ozone are added to a liquid such as ultrapure water, and in the presence of a photocatalyst such as an anatase type, ultraviolet irradiation is performed with an ultraviolet lamp or the like, and A method for decomposing a TOC component in a liquid is described, and Patent Document 2 discloses that air bubbling is generated in the vicinity of an ultraviolet lamp in an apparatus that combines an ultraviolet lamp and an ultraviolet treatment tank having an inner wall holding a photocatalyst. Promotes oxidation of organic substances, and Patent Document 3 describes a combination of a bypass member and a photocatalytic filter in addition to an ultraviolet lamp.
- a photocatalyst such as an anatase type
- the method using hydrogen peroxide and ozone described in Patent Document 1 increases the running cost, and further requires removal of hydrogen peroxide and ozone on the downstream side of the ultraviolet irradiation device.
- the method of holding the photocatalyst on the inner wall of the ultraviolet treatment tank described in Patent Document 2 is not necessarily in contact with the TOC component to be treated and the photocatalyst, and the treated water is out of the ultraviolet treatment apparatus. Therefore, there is a problem that the decomposition efficiency of the TOC component by the photocatalyst may become extremely low.
- Patent Document 3 When the mounting angle is changed from 45 degrees to 135 degrees, it cannot be said that the ultraviolet light emitted perpendicularly to the ultraviolet lamp is effectively used. A.
- the present invention provides an ultraviolet oxidation apparatus capable of efficiently and safely decomposing organic substances present in water with low energy consumption and low cost, an ultrapure water production apparatus using the same, an ultraviolet oxidation method, and an ultrapure.
- An object is to provide a water production method.
- the present inventors have conducted extensive research, and as a result, accommodated an ultraviolet irradiation unit that accommodates an ultraviolet irradiation unit over the entire surface intersecting the flow direction of the water to be treated in the fluid tank.
- an ultraviolet irradiation unit that accommodates an ultraviolet irradiation unit over the entire surface intersecting the flow direction of the water to be treated in the fluid tank.
- the present invention includes a flow tank that allows the water to be treated to flow in one direction, a photocatalyst fiber that is disposed in the fluid tank so that the water to be treated can pass, an ultraviolet irradiation unit that can irradiate ultraviolet light, and the flow An ultraviolet oxidation apparatus provided over the entire surface intersecting the flow direction of the water to be treated in the tank, and comprising an ultraviolet irradiation unit accommodating unit that accommodates the ultraviolet irradiation unit, wherein the ultraviolet irradiation unit accommodating unit Is formed so that the water to be treated flows into the housing portion from the upstream side toward the ultraviolet irradiation portion accommodated from the upstream side, flows inside the housing portion and then flows out to the downstream side, and the ultraviolet rays from the ultraviolet irradiation portion are It is comprised from the raw material which can irradiate the said photocatalyst fiber.
- the ultraviolet irradiation unit accommodating portion includes an inner tube that accommodates the ultraviolet irradiation unit and an outer tube that covers the inner tube.
- the radial interval is preferably 1 to 10 mm.
- the inner tube and the outer tube are made of a material that transmits ultraviolet rays having wavelengths of 180 to 190 nm and 250 to 260 nm. It is preferably configured to be able to irradiate ultraviolet rays having peak wavelengths at ⁇ 190 nm and 250-260 nm, respectively.
- the ultraviolet irradiation section is formed in a long shape
- the photocatalytic fiber is formed in a flat plate shape
- the longitudinal direction of the ultraviolet irradiation section and the planar direction of the photocatalytic fiber are It is preferable that they are set to be parallel.
- the present invention also provides a reverse osmosis membrane device for removing impurities in the water to be treated and an ionic component in the water to be treated, which is installed downstream of the reverse osmosis membrane device and from which impurities have been removed by the reverse osmosis membrane device.
- An ion exchange device installed downstream of the ion exchange device, the ultraviolet oxidation device for decomposing organic components in the water to be treated whose ion components have been removed by the ion exchange device, and installed downstream of the ultraviolet oxidation device, A mixed bed type ion exchange apparatus that removes ion components generated in the water to be treated by decomposition of organic components by the ultraviolet oxidation apparatus, and a process after the reverse osmosis membrane apparatus installed downstream of the mixed bed type ion exchange apparatus. And an ultrafiltration device for removing particulate matter generated in the water to be treated.
- the ultrapure water production apparatus may further include a deaeration device that is installed upstream of the ultrafiltration device and removes gas in the water to be treated. It is preferable to be installed between the osmosis membrane device and the ion exchange device and between the ion exchange device and the ultrafiltration device.
- a deaeration device By providing a deaeration device, it is possible to reduce dissolved oxygen, which is a problem in ultrapure water used in the semiconductor industry and the like. Further, by further providing a deaeration device on the upstream side of the ion exchange device, it is possible to remove carbon dioxide and other gases existing in the water, thereby extending the life of the ion exchange device. It is possible to reduce dissolved oxygen, which is a problem in ultrapure water used in the above.
- the present invention provides a photocatalyst fiber through which water to be treated can pass, an ultraviolet ray irradiation part capable of irradiating ultraviolet rays, an ultraviolet ray irradiation part accommodating part that accommodates the ultraviolet ray irradiation part and allows the treated water to flow inside.
- the present invention provides an impurity removal step for removing impurities in the water to be treated, a first ion component removal step for removing ion components in the water to be treated treated by the impurity removal step, and the ultraviolet oxidation method.
- An organic substance component decomposing step for decomposing an organic component in the for-treatment water treated by the first ionic component removing step, and a second ionic component removing step for removing an ionic component generated in the for-treatment water by the organic substance component decomposing step
- a particulate matter removing step of removing particulate matter generated in the water to be treated after the impurity removing step is removing impurities in the water to be treated.
- an ultraviolet oxidation apparatus capable of efficiently and safely decomposing organic substances present in water with low energy consumption and low cost, an ultrapure water production apparatus using the same, and ultraviolet oxidation A method and an ultrapure water production method can be provided.
- FIG. 2 is a cross-sectional view taken along line A-A ′ of FIG. 1. It is a perspective view of the photocatalyst cartridge used for the ultraviolet-ray oxidation apparatus concerning this embodiment. It is a partial cutaway perspective view of a double tube in a state where an ultraviolet irradiation lamp of the ultraviolet oxidation apparatus according to the present embodiment is removed and a portion around the double tube. It is a front view of the ultraviolet-ray oxidation apparatus used for the Example. It is a conceptual diagram of the conventional ultraviolet-ray oxidation apparatus. It is a conceptual diagram of the ultrapure water manufacturing apparatus of this invention.
- the ultraviolet oxidation apparatus As shown in FIGS. 1 and 2, the ultraviolet oxidation apparatus according to the present embodiment is arranged so that the water to be treated flows in one direction and the water to be treated that flows in the fluid tank 10 can pass therethrough.
- a photocatalyst cartridge 12 made of fibers having a photocatalytic function, an ultraviolet irradiation lamp 14 capable of irradiating ultraviolet rays to the flowing water to be treated in the fluid tank 10, and a surface intersecting with the flow direction of the water to be treated in the fluid tank 10
- An ultraviolet irradiation lamp accommodating member 16 that accommodates the ultraviolet irradiation lamp 14 is provided over the entire area.
- the fluid tank 10 flows the water to be treated from the inlet 10A formed on the upstream side surface (left side surface in FIGS. 1 and 2) to the outlet 10B formed on the downstream side (right side in FIG. 1) on the upper surface. It is configured.
- each photocatalyst cartridge 12 is installed in the flow tank 10 in a state in which five photocatalyst cartridges 12 are juxtaposed along the flow direction over the entire area perpendicular to the flow direction of the water to be treated.
- each photocatalyst cartridge 12 includes a flat nonwoven fabric 12A and a pair of wire meshes 12B and 12B.
- the flat nonwoven fabric 12A is sandwiched between a pair of stainless steel wire meshes 12B and 12B.
- the wire mesh 12B, 12B as a support material and making it into a cartridge shape, the flat nonwoven fabric 12A having a deteriorated photocatalytic function can be easily replaced.
- each photocatalyst cartridge 12 is installed so that its surface intersects perpendicularly to the flow direction of water. However, it is sufficient that the flowing water passes through the flat nonwoven fabric 12A efficiently, for example, in the flow direction. On the other hand, it may be installed at an angle of around 10 °, preferably around 5 °.
- the ultraviolet irradiation lamp 14 is formed in a columnar shape, and a cylindrical cover member (not shown) is provided on the outer surface thereof.
- the cover member is made of a material that transmits not only 250 to 260 nm but also a peak wavelength of 180 to 190 nm, for example, synthetic quartz.
- a general low-pressure mercury lamp originally has two wavelengths of 185 nm and 254 nm. However, since glass, which is a material of a normal cover member, does not transmit short-wave ultraviolet light, it irradiates only a wavelength of 254 nm.
- the ultraviolet lamp 11 is configured to irradiate ultraviolet rays having peak wavelengths of 180 to 190 nm and 250 to 260 nm by making the material of the cover member special as described above.
- the ultraviolet rays irradiated from the ultraviolet lamp 11 have a peak wavelength at 180 to 190 nm, preferably 185 nm, and a peak wavelength at 250 to 260 nm, preferably 254 nm.
- the ultraviolet irradiation lamp accommodating member 16 is provided from the bottom surface to the upper surface in the fluid tank 10, and includes a double pipe 18 that accommodates the cylindrical ultraviolet radiation lamp 14 and a cover between the double pipe 18 and the fluid tank 10. It is comprised from a pair of partition plates 20 and 20 provided over the whole area of the surface which cross
- the double tube 18 is formed in a cylindrical shape composed of an outer tube 18A and an inner tube 18B as shown in FIGS.
- the distance between the outer tube 18A and the inner tube 18B in the radial direction is preferably 10 mm or less, and particularly preferably 3 to 8 mm.
- An inflow port 18C penetrating into a region between the outer tube 18A and the inner tube 18B is formed below the partition plate 20 of the outer tube 18A of the double tube 18 on the upstream side.
- an outlet 18D penetrating into a region between the outer tube 18A and the inner tube 18B is formed above the downstream side.
- the water to be treated flowing in the fluid tank 10 always flows from the inlet 18C on the upstream side of the double pipe 18 toward the ultraviolet irradiation lamp 14. It flows out of the outlet 18D downstream through the region between the outer pipe 18A and the inner pipe B.
- the ultraviolet lamps 14 are provided so as to be positioned at the center thereof, and a total of four ultraviolet oxidizers according to this embodiment are arranged. As described above, the ultraviolet lamps 14 are arranged between the photocatalyst cartridges 12, so that ultraviolet rays can be irradiated on both surfaces of the flat nonwoven fabric 21 provided in the photocatalyst cartridge 12. The ultraviolet lamps 20 are arranged in parallel so that their axial directions are parallel to the photocatalyst cartridge 12.
- the cover member of the ultraviolet lamp 14 is formed in a cylindrical shape, but is not limited thereto, and may be any shape that extends in the longitudinal direction.
- the number of the ultraviolet lamps 14 is determined according to the required water quality, the amount of unnecessary organic substances contained in the treated water, and the like.
- the double tube 18 is formed in a cylindrical shape, but may be any shape as long as the ultraviolet lamp 14 can be disposed at the center.
- the flat nonwoven fabric 12A used in the ultraviolet oxidation apparatus is a composite oxide phase of an oxide phase (first phase) mainly composed of a silica component and a metal oxide phase (second phase) containing titanium. And a photocatalytic fiber in which the proportion of titanium in the metal oxide constituting the second phase increases in a gradient toward the surface layer of the fiber.
- the surface of the photocatalytic fiber may be platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), gold (Au), silver (Ag), copper (Cu), iron (Fe), if necessary.
- One or more of nickel (Ni), zinc (Zn), gallium (Ga), germanium (Ge), indium (In), and tin (Sn) may be supported.
- the supporting method is not particularly limited, but light having an energy equal to or higher than the energy corresponding to the band gap of the metal oxide constituting the second phase while contacting the liquid containing the supported metal ions and the photocatalytic fiber. Can be carried by irradiation.
- the first phase is an oxide phase mainly composed of a silica component, and may be amorphous or crystalline, and may be a metal element or metal oxide capable of forming a solid solution or a eutectic compound with silica. It may contain.
- the metal element (A) that can form a solid solution with silica include titanium.
- the metal element (B) of the metal oxide that can form a solid solution with silica include aluminum, zirconium, yttrium, lithium, sodium, barium, calcium, boron, zinc, nickel, manganese, magnesium, and iron. It is done.
- the first phase forms the internal phase of the silica-based composite oxide fiber and plays an important role in bearing the mechanical properties.
- the ratio of the first phase to the entire silica-based composite oxide fiber is preferably 40 to 98% by weight, so that the target second phase function can be sufficiently expressed and also high mechanical properties can be expressed. For this purpose, it is more preferable to control the ratio of the first phase within the range of 50 to 95% by weight.
- the second phase is a metal oxide phase containing titanium and plays an important role in developing the photocatalytic function.
- An example of the metal constituting the metal oxide is titanium.
- the metal oxide may be a simple substance, or may be a co-melting compound or a substance in which a substitutional solid solution is formed by a specific element, but is preferably titania.
- the second phase forms the surface layer of the silica-based composite oxide fiber, and the proportion of the second phase of the silica-based composite oxide fiber varies depending on the type of metal oxide, but is 2 to 60% by weight. Preferably, it is more preferably controlled within the range of 5 to 50% by weight in order to sufficiently exhibit its function and to simultaneously exhibit high strength.
- the crystal grain size of the metal oxide containing titanium in the second phase is preferably 15 nm or less, and particularly preferably 10 nm or less.
- the proportion of titanium in the metal oxide contained in the second phase increases in a gradient toward the surface of the silica-based composite oxide fiber, and the thickness of the region where the composition gradient is clearly recognized is the surface layer. From 5 to 500 nm, but may be about 1/3 of the fiber diameter.
- the “existence ratio” of the first phase and the second phase refers to the first phase with respect to the metal oxide constituting the first phase and the entire metal oxide constituting the second phase, that is, the entire silica-based composite oxide fiber. % By weight and the second phase metal oxide.
- the average ultraviolet intensity on the flat nonwoven fabric is preferably 1 to 10 mW / cm 2, and more preferably 2 to 8 mW / cm 2.
- the ultraviolet intensity on the surface of the flat nonwoven fabric is 1 to 10 mW / cm 2
- water treatment with two ultraviolet components can be performed with high efficiency.
- the distance between the ultraviolet irradiation means and the flat nonwoven fabric may be set to an appropriate range.
- the average ultraviolet intensity can be obtained by measuring the ultraviolet intensity at a plurality of locations from the center to the end of the nonwoven fabric surface, and averaging these values.
- the photocatalytic fiber having the inclined structure as described above can be produced by a known method, for example, based on the method described in WO2009 / 63737.
- the water to be treated is poured from the inlet 10A of the fluid tank 10.
- the treated water poured in is discharged from the outlet 10 ⁇ / b> B through the fluid tank 10. Since the flat nonwoven fabric 12A has a structure in which each fiber has a certain amount of voids and is dispersed, the contact area with the photocatalyst is very large when water passes through. For this reason, radicals are efficiently generated by the flat nonwoven fabric 12A having a photocatalytic function, and unnecessary organic substances are decomposed.
- Radiation can be generated more efficiently by irradiating both the front and back surfaces of the flat nonwoven fabric 12A made of photocatalytic fibers with ultraviolet rays.
- ultraviolet rays of 185 nm are effectively irradiated to the whole amount of treated water, and unnecessary organic matter Is efficiently decomposed.
- the ultraviolet lamp is a black light fluorescent lamp having a wavelength of 351 nm or a sterilizing lamp having a wavelength of 254 nm. This is because titania photocatalysts can be excited at wavelengths of 387 nm or less, and these lamps are easily available as products.
- high decomposition efficiency can be obtained by using ultraviolet rays that have not been used in the past and making the photocatalyst have a predetermined arrangement structure.
- a flat nonwoven fabric made of photocatalytic fibers and ultraviolet rays having peak wavelengths at 180 to 190 nm and 250 to 260 nm, which are installed in parallel with the flat nonwoven fabric. Since the ultraviolet irradiation means for irradiating is provided, ultraviolet light of 180 to 190 nm is not blocked by the photocatalyst while maintaining the light irradiation efficiency to the photocatalyst and the contact efficiency with the processing fluid.
- the entire amount of water to be treated is forced to circulate in the vicinity of the ultraviolet lamp by using a quartz double tube, the entire amount of water to be treated is effectively irradiated with ultraviolet rays of 180 to 190 nm. For this reason, it is possible to excite the photocatalyst by irradiating the flat nonwoven fabric with ultraviolet rays of 250 to 260 nm, decompose organic substances with generated OH radicals, and directly decompose organic substances in water with ultraviolet rays of 180 to 190 nm. As a result, the decomposition efficiency is increased as compared with the conventional ultraviolet oxidation apparatus. By incorporating the ultraviolet oxidation apparatus according to the present embodiment into an ultrapure water production line or the like, it becomes possible to obtain high quality ultrapure water while greatly reducing power consumption costs.
- the ultrapure water production apparatus according to the present embodiment can be constructed by incorporating the ultraviolet oxidation apparatus according to the present embodiment into an ultrapure water production line or the like. That is, the ultrapure water production apparatus according to the present embodiment is installed downstream of the reverse osmosis membrane device 40 and the reverse osmosis membrane device 40 for removing impurities in the water to be treated, as shown in FIG.
- An ultraviolet oxidizer 46 that is installed and decomposes organic matter components in the water to be treated whose ion components have been removed by the ion exchange device 42, and is disposed downstream of the ultraviolet oxidizer 46, and is treated by the decomposition of the organic matter components by the ultraviolet oxidizer 46.
- a mixed bed type ion exchange device 48 that removes ion components generated in water and a downstream of the mixed bed type ion exchange device 48, for the treatment after the reverse osmosis membrane device 40.
- a ultrafilter 50 to remove particulate matter generated in the water to be treated I.
- the water to be treated is reverse osmosis membrane device 40 ⁇ ion exchange device 42 ⁇ tank 44 ⁇ ultraviolet oxidation device 46 ⁇ mixed bed ion exchange device 48 ⁇ ultrafiltration device 50.
- TOC total organic carbon content
- part of the water to be treated is returned to the tank 44 after the treatment by the ultrafiltration device 50, and the tank 44 ⁇ ultraviolet oxidizer 46 ⁇ mixed bed.
- Circulation processing of the type ion exchange device 48 ⁇ ultrafiltration device 50 ⁇ tank 44 is also performed.
- the ultrapure water production apparatus when the water to be treated is treated by the reverse osmosis membrane device 40, impurities such as ion components and salts contained therein are removed, and the ion exchange device 42 When treated, the ionic components in the water to be treated are removed, and when treated by the ultraviolet oxidizer 46, the organic matter components in the water to be treated are decomposed and treated by the mixed bed ion exchange device 48.
- the ultrafiltration device 50 particulate matter generated in the water to be treated during the flow is removed, and the TOC (total organic carbon content) is sufficiently reduced. Ultra pure water can be obtained.
- the ultrapure water production apparatus In the conventional ultrapure water production system, urea remains in the obtained ultrapure water unless a special apparatus for removing urea is provided.
- the ultrapure water production apparatus according to the present invention is the present invention.
- a known pretreatment apparatus for removing organic matters, hardness components (Ca component, Mg component), particulate matter, etc. remaining in the water to be treated is provided as necessary. Then, the water to be treated that has been treated by the pretreatment device may be introduced into the reverse osmosis membrane device 40.
- a known pretreatment device for example, when clean water is used as water to be treated, there is a device that performs treatment such as activated carbon ⁇ water softener ⁇ filter.
- the ultrapure water production apparatus may be provided with at least one deaeration device between the ion exchange device 42 and the ultrafiltration device 50 as necessary. Thereby, it is possible to reduce dissolved oxygen, which is a problem in ultrapure water used in the semiconductor industry and the like.
- the ultrapure water production apparatus according to the present embodiment may further include at least one deaeration device between the reverse osmosis membrane device 40 and the ion exchange device 42 as necessary. As a result, carbon dioxide and other gases existing in water can be removed, the life of the ion exchange device can be extended, and dissolved oxygen, which is a problem in ultrapure water used in the semiconductor industry, etc. Reduction can be achieved.
- the mixture of the modified polycarbosilane and the low molecular weight organometallic compound was dissolved in toluene, the mixture was charged into a melt blow spinning apparatus, the interior was sufficiently purged with nitrogen, and the temperature was raised to distill off the toluene. Spinning was performed. The spun nonwoven fabric was heated to 150 ° C stepwise in air and infusible, and then fired in air at 1200 ° C for 1 hour to obtain titania / silica fibers as photocatalyst fibers.
- the photocatalyst fiber obtained in Production Example 1 had a first phase content of 80% by weight and a second phase content of 20% by weight. The abundance ratio was determined by fluorescent X-ray analysis. The titania crystal particles contained in the second phase were 8 nm. The particle diameter was determined by TEM (transmission electron microscope observation). From the surface of the photocatalyst fiber, the existing ratio of titanium metal oxide was inclined at a depth of 300 nm. The inclination depth was determined by Auger electron spectroscopy.
- Example 1 The titania / silica fiber obtained in Production Example 1 was used as a flat nonwoven fabric to form a photocatalyst cartridge including the same, and an ultraviolet oxidation apparatus shown in FIG. 5 was produced.
- the output of the ultraviolet lamp was 60 W, and 24 lamps were used.
- the wavelength of the ultraviolet lamp emits both 254 nm and 185 nm.
- the distance between the ultraviolet lamp and the flat nonwoven fabric was 90 mm, and the average ultraviolet intensity on the flat nonwoven fabric surface was 2 mW / cm 2.
- Ultrapure water was obtained by processing with a filtration device.
- the TOC of the obtained ultrapure water was about 20 ppb.
- the treatment speed was adjusted so that the finally obtained TOC of ultrapure water was about 0.5 ppb. In this case, the processing speed was 16.1 m 3 / h, and the energy consumed by the ultraviolet oxidation apparatus was 0.13 kWh / m 3.
- Example 2 the ultrapure water production apparatus shown in FIG. 7 was produced using the ultraviolet oxidation apparatus obtained in Example 1.
- the reverse osmosis membrane device the AG type manufactured by GE is used, as the ion exchange device, the continuous electric regenerative ion exchange device (XL type) manufactured by SnowPure is used, and as the mixed bed type ion exchange device, Shinei is used.
- a cartridge polisher (RT type) manufactured by Chemical Industry Co., Ltd. was used, and an NTU type manufactured by Nitto Denko Corporation was used as the ultrafiltration device.
- Shinei Chemical Industry Co., Ltd. activated carbon filter (RT type), water softener (RT type), and Shinryo Aqua Air Co., Ltd. filter (BL type) were used as known pretreatment devices.
- the raw water is treated as clean water, treated with a known pre-treatment device, added with 100 ppb of urea, and treated with the ultrapure water production device according to Example 2, the residual amount of urea is 1 ppb or less and the TOC is reduced. Ultrapure water of 1 ppb or less could be obtained.
- the treated water was treated with a known coagulation filtration device, a two-bed three-column ion exchange device, a reverse osmosis membrane device, and a deaeration device, and then treated with this ultraviolet oxidizer.
- ultrapure water was obtained by treatment with a known ion adsorption device and ultrafiltration device.
- the treatment speed was adjusted so that the finally obtained TOC of ultrapure water was about 0.5 ppb.
- the processing speed was 4.7 m3 / h
- the energy consumption of the ultraviolet oxidation apparatus was 0.47 kWh / m3.
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Abstract
Description
5リットルの三口フラスコに無水トルエン2.5リットルと金属ナトリウム400gとを入れ窒素ガス気流下でトルエンの沸点まで加熱し、ジメチルジクロロシラン1リットルを1時間かけて滴下した。滴下終了後、10時間加熱還流し沈殿物を生成させた。この沈殿を濾過し、まずメタノールで洗浄した後、水で洗浄して、白色粉末のポリジメチルシラン420gを得た。ポリジメチルシラン250gを、水冷還流器を備えた三口フラスコ中に仕込み、窒素気流下、420℃で30時間加熱反応させて数平均分子量が1200のポリカルボシランを得た。
製造例1により得られたチタニア/シリカ繊維を平板状不織布とし、それを備える光触媒カートリッジとし、図5に示される紫外線酸化装置を作製した。紫外線ランプの出力は60Wであり、24本を使用した。紫外線ランプの波長は254nmと185nmの両方を放射する。紫外線ランプと平板状不織布の距離は90mmとし、平板状不織布表面の平均紫外線強度は2mW/cm2であった。上水を公知の凝集濾過装置、2床3塔型イオン交換装置、逆浸透膜装置で処理した後、この紫外線酸化装置で処理し、続けて公知の脱気装置、イオン吸着装置、及び限外濾過装置で処理することにより超純水を得た。得られた超純水のTOCは20ppb程度あった。処理速度は、最終的に得られる超純水のTOCが0.5ppb程度になるように調整した。この場合の処理速度は16.1m3/h、紫外線酸化装置に係る消費エネルギーは0.13kWh/m3であった。
次に、実施例1により得られた紫外線酸化装置を用いて、図7に示される超純水製造装置を作製した。逆浸透膜装置としては、GE社製のAG型を用い、イオン交換装置としては、SnowPure社製の連続電気再生式イオン交換装置(XL型)を用い、混床式イオン交換装置としては、伸栄化学産業(株)製のカートリッジポリッシャー(RT型)を用い、限外濾過装置としては、日東電工(株)製のNTU型を用いた。また、公知の前処理装置として、伸栄化学産業(株)製の活性炭濾過器(RT型)、軟水器(RT型)、及び新菱アクアエア(株)製のフィルター(BL型)を用いた。
特開平10-151450の実施例に記載の方法を参考に、直径250mm、長さ1500mmのステンレス製の筒に、254nmと194nmと184nmの各波長を放射する65Wの低圧紫外線ランプ24本を内蔵した紫外線酸化装置を作成した。光触媒は、アナターゼ型チタニアを透光性アルミナ板材に担持したものを紫外線酸化装置の内部に挿入した。紫外線酸化装置の内容積に対する光触媒の重量は80ppmとした。紫外線酸化装置以外は、実施例1と同様に、上水を公知の凝集濾過装置、2床3塔型イオン交換装置、逆浸透膜装置、脱気装置で処理した後、この紫外線酸化装置で処理し、続けて公知のイオン吸着装置および限外濾過装置で処理することにより超純水を得た。処理速度は、最終的に得られる超純水のTOCが0.5ppb程度になるように調整した。この場合の処理速度は4.7m3/hであり、紫外線酸化装置に係る消費エネルギーは0.47KWh/m3であった。
10A 流入口
10B 流出口
12 光触媒カートリッジ(光触媒繊維)
12A 平板状不織布
12B 金網
14 紫外線照射ランプ(紫外線照射部)
16 紫外線照射ランプ収容部材(紫外線照射部収容部)
18 二重管
18A 外管
18B 内管
18C 流入口
18D 流出口
20 仕切り板
40 逆浸透膜装置
42 イオン交換装置
44 タンク
46 紫外線酸化装置
48 混床式イオン交換装置
50 限外濾過装置
Claims (11)
- 被処理水を一方向に流動させる流動槽と、
被処理水が通過可能に前記流動槽内に配置された光触媒繊維と、
紫外線を照射可能な紫外線照射部と、
前記流動槽内の被処理水の流動方向に交差する面の全域に亘って設けられ、前記紫外線照射部を収容する紫外線照射部収容部とを備えた紫外線酸化装置であって、
前記紫外線照射部収容部は、上流側から収容された紫外線照射部に向かって被処理水を該収容部内に流入させ、前記収容部内を流動させた後に下流側に流出させるよう形成され、前記紫外線照射部からの紫外線が前記光触媒繊維に照射可能な素材から構成されていることを特徴とする紫外線酸化装置。 - 前記紫外線照射部収容部は、紫外線照射部を収容する内管と、該内管の覆う外管とを備えていること特徴とする請求項1記載の紫外線酸化装置。
- 前記内管と外管の径方向の間隔が1~10mmであることを特徴とする請求項2記載の紫外線酸化装置。
- 前記内管及び外管が、180~190nmと250~260nmの波長の紫外線を透過する素材から構成されていることを特徴とする請求項2又は3記載の紫外線酸化装置。
- 前記紫外線照射部は、180~190nmと250~260nmそれぞれにピーク波長を有する紫外線を照射可能に構成されていることを特徴とする請求項1乃至4いずれか記載の紫外線酸化装置。
- 前記紫外線照射部が長尺状に形成され、前記光触媒繊維が平板状に形成されており、前記紫外線照射部の長手方向と前記光触媒繊維の平面方向が平行になるように設定されていることを特徴とする請求項1乃至5いずれか記載の紫外線酸化装置。
- 被処理水中の不純物を除去する逆浸透膜装置と、
該逆浸透膜装置の下流に設置され、前記逆浸透膜装置によって不純物除去された被処理水中のイオン成分を除去するイオン交換装置と、
該イオン交換装置の下流に設置され、前記イオン交換装置によってイオン成分除去された被処理水中の有機物成分を分解する請求項1乃至6いずれか記載の紫外線酸化装置と、
該紫外線酸化装置の下流に設置され、前記紫外線酸化装置による有機物成分の分解によって被処理水中に生じたイオン成分を除去する混床式イオン交換装置と、
該混床式イオン交換装置の下流に設置され、前記逆浸透膜装置以降の処理によって被処理水中に生じた粒子状物を除去する限外濾過装置とを備えたこと
を特徴とする超純水製造装置。 - 前記限外濾過装置の上流側に設置され、被処理水中のガスを除去する脱気装置をさらに備えたことを特徴とする請求項7記載の超純水製造装置。
- 前記脱気装置は、少なくとも前記逆浸透膜装置とイオン交換装置の間及び前記イオン交換装置と前記限外濾過装置の間に設置されていることを特徴とする請求項8記載の超純水製造装置。
- 被処理水が通過可能な光触媒繊維と、紫外線を照射可能な紫外線照射部と、該紫外線照射部を収容し、被処理水が内部を流動可能な紫外線照射部収容部とを有する流動槽内を流動する被処理水中に含まれる有機物を酸化分解処理する紫外線酸化方法であって、
前記光触媒繊維に前記紫外線照射部から紫外線を照射させた状態で被処理水が前記光触媒繊維を通過する工程と、
被処理水に前記紫外線照射部から紫外線を照射させた状態で被処理水が前記紫外線照射部収容部内を流動する工程とを備えたこと
を特徴とする紫外線酸化方法。 - 被処理水中の不純物を除去する不純物除去工程と、
該不純物除去工程によって処理された被処理水中のイオン成分を除去する第1イオン成分除去工程と、
請求項10記載の紫外線酸化方法によって、前記第1イオン除去工程によって処理された被処理水中の有機物成分を分解する有機物成分分解工程と、
該有機物成分分解工程によって被処理水中に生じたイオン成分を除去する第2イオン成分除去工程と、
前記不純物除去工程以降に被処理水中に生じた粒子状物を除去する粒子状物除去工程とを備えたこと
を特徴とする超純水製造方法。
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