TW200936510A - Water purifying device and water purifying method - Google Patents

Abstract

A water purifying device and method for purifying water by efficiently decomposing unwanted organic substances present in water. The water purifying device comprises a water flowing tank through which water to be purified is made to flow in one direction, one or more platy nonwoven fabrics permeable to water, placed in the water flowing tank, and composed of fibers having a photocatalytic function, and an ultraviolet radiation irradiating means for irradiating the platy nonwoven fabrics with ultraviolet radiation. The device is characterized in that the ultraviolet irradiating means has a shape extending in the length direction and can radiates ultraviolet radiation having peak wavelengths in the range from 180 to 190 nm and in the range from 250 to 260 nm, and the platy nonwoven fabrics are parallel to the length direction of the ultraviolet irradiating means.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water purification apparatus and a water purification method which can purify water by efficiently decomposing unnecessary organic substances present in water. [Prior Art] In recent years, technological innovation in the field of electronics industry has been fast, and progress has been made in the miniaturization of the semiconductor industry. With the advancement of such technology,

For example, the water quality standard for ultrapure water used in semiconductor manufacturing has become very strict, and there is a need for a water purification apparatus that can efficiently decompose and purify unwanted micro-organisms contained in water. An apparatus for purifying an organic substance contained in water, for example, in the patent document, discloses a water purification apparatus which oxidizes and decomposes an organic substance which is present in water by irradiating ultraviolet rays with water. Further, Patent Document 2 discloses a water purification device in which ultraviolet rays having a peak wavelength of 254 nm are irradiated onto a photocatalyst carried by a non-woven fabric to generate a ruthenium H radical, thereby causing a lack of water. In the water purifying device, the non-woven fabric having the photocatalytic function is formed into a hollow truncated cone shape, and a wavelength line lamp having a decreasing value of 254 nm is disposed at the center portion. Japanese Patent Laid-Open Publication No. Hei 6-198279. Patent Document 2: Japanese Patent No. 3436267. [Summary of the Invention] Strong rfn, in order to decompose the organic matter in the water by irradiation with ultraviolet rays, "so most of them use high-intensity ultraviolet lamps - several ultraviolet and linear lamps. In the patent literature or the use number" It is obvious that in order to save the energy of 200936510', the output of the ultraviolet lamp is monitored and treated in the water. 2 Because the concentration should be changed, the problem is that the oxidative decomposition by irradiation still requires a large amount of energy. In Patent Document 2 , ', and the structure of efficiently generating 〇H radicals with a titanium oxide photocatalyst and making the OH radicals in good contact with the water towel (4) can achieve high cleavage efficiency. However, the problem is that Obtaining sufficient decomposition efficiency to meet today's high water quality standards. Seed water purification device and organic water that is not in the water. Therefore, the object of the present invention is to provide a method for efficiently decomposing the presence of water. In order to achieve the above object, the inventors of the present invention have diligently studied and found that a flat plate composed of fibers disposed parallel to a photocatalytic function is used. The ultraviolet non-woven fabric of the non-woven fabric is irradiated with ultraviolet rays having a peak wavelength of 180 to 190 nm and 250 to 26 nm at the flat non-woven fabric, and the organic matter existing in the water can be efficiently decomposed. A water purification device comprising: a flow channel for flowing water to be purified in one direction; and at least one of the fibers having photocatalyst function disposed in the flow channel and allowing the water to be purified to pass through And a UV-ray irradiation means for irradiating ultraviolet rays on the flat-shaped nonwoven fabric. The ultraviolet irradiation means is configured to have a shape extending in the longitudinal direction and can be irradiated at 180 to 190 nm and 250 to 260 nm. The peak, the length of the skin is 200936510, and the setting point is Jin, Huang, and gt; and the direction of the long side is parallel with the flat non-woven fabric. The invention is also a method for the birthing of a stalk. It is to make the water of the desired flow flow through the flat non-woven fabric composed of the fibers of the eight-photocatalyst function. And the right side of the i swimming ^ is extended in the direction of the long side and is set to be an ultraviolet irradiation means in parallel with the flat non-woven fabric, and the pair of flat non-woven fabrics are irradiated with (10) to (10) coffee and 25Q to fine coffee having a peak wavelength.紫外线 ^ As described above, by the present invention, it is possible to provide a water purification device and a water purification method which can purify water by efficiently decomposing organic substances present in water. [Embodiment] The summer embodiment of the water purification device of the present invention will be described in detail with reference to the drawings. Fig. 2 is a conceptual perspective view of the water purification device of the first embodiment. The water purification device 10 of the first embodiment has: The water is flowed into the flow channel 11 by the flow inlet 41 formed in the bottom surface toward the flow outlet 42 formed in the top surface, and the surface thereof is disposed to intersect perpendicularly with respect to the flow direction of the water to be purified. The three photocatalysts 平行2〇 parallel to each other and the ultraviolet lamp 3〇 disposed between the photocatalysts g20. The outer casing member constituting the outer surface of the ultraviolet lamp 30 is formed in a columnar shape, and is made of a material that can transmit not only 250 to 260 nm but also a peak wavelength of 180 to 190 nm. The material of the outer casing member can be, for example, synthesized. quartz. A typical low-pressure mercury lamp has two wavelengths of 185 ηηη and 254 nm. However, since the raw material glass of the usual outer casing member does not transmit the short-wavelength ultraviolet rays of the light of 200936510, only the wavelength of 254 nm is irradiated. In the water purifying apparatus of the present embodiment, the ultraviolet lamp 3 is irradiated at 18 〇 to 19 〇 nm and 250 to 26 〇 nm with a peak wavelength by using a special raw material as a raw material of the outer casing member. The composition of ultraviolet light. The ultraviolet ray irradiated by the ultraviolet lamp % has a peak wavelength at 180 to 19 Å (preferably 185 nm) and a peak wavelength at 250 to 260 nm (preferably 254 nm). Each of the ultraviolet lamps 30 is provided in two "between two photocatalysts", and four of them are provided in total, and are arranged in parallel, and the axial direction thereof is parallel to the photocatalyst. Further, in the first embodiment, the outer casing member of the ultraviolet irradiation lamp 3G is formed in a columnar shape. However, the outer casing member is not limited thereto, and may have a shape extending in the longitudinal direction. The number of the ultraviolet irradiation lamps 30 is determined depending on the required water quality or the amount of unnecessary organic matter contained in the treated water. As shown in Fig. 2, each of the photocatalysts S20 is composed of a flat non-woven fabric pair 22, and a flat non-woven fabric 2 bundles are privately held from the non-ferrous steel. Therefore, by using the net 22 as Support: 'The flat non-woven fabric 2 which can easily replace the photocatalytic function is replaced by a multi-stage photocatalyst £2G by using a frame or the like to facilitate attachment and detachment. In the third embodiment, the extension can be "+ ten-plate non-woven fabric. 21 is 3, - depending on the water quality required, etc. Further, in the first embodiment, a flat non-woven fabric is used. The solid groove 1 to 50 is used as the light contact 20, but it is also possible that the (four) segment is in the embodiment, and each of the flat non-woven fabrics 21 is used. In the direction in which the first direction intersects perpendicularly, i π ¥ . , the surface is placed in a straight line with the flow of water J, but the ground is passed through each flat non-woven fabric 21: the water is efficient 1 J It can also be tilted. Flat 200936510 The slab-shaped non-woven fabric 2 is preferably disposed such that its surface is perpendicularly intersected with the flow direction of water. It may also be inclined 10 forward and backward with respect to the flow direction. (preferably 5° front and rear) settings. In the water purifying apparatus of the first embodiment, the average 々 ultraviolet ray intensity on the flat non-woven fabric is preferably, more preferably, 2 to 8 mW/cm 2 , and the ultraviolet ray intensity of the surface of the right flat woven fabric is 1 to 1 〇 mW. /Gm2, it is possible to efficiently carry out water at two ultraviolet components. To achieve such a standard, 'the distance between the ultraviolet ray irradiation means and the flat non-woven t can be set to an appropriate range. Here, the average ultraviolet ray intensity measures the intensity of the ultraviolet rays from a plurality of portions from the central portion to the end portion of the non-woven fabric surface, and these values can be regarded as an average ultraviolet ray intensity on average. The treated water containing the unnecessary organic matter is purified. First, the treated water flows into the inlet 41 of the water purification device 104. The inflowing treated water is discharged through the flow port 11 or 16 and then discharged from the outlet 42. The flat non-woven fabric 21-fiber-root-root structure has a structure in which a gap of 1 degree is dispersed, so that the contact area with the photocatalyst is very large when the water passes, and therefore, the flat-shaped residual cloth 21 with the first catalyst function can be used. The free radicals are efficiently generated, and the organic matter which is not decomposed is decomposed. Further, if it is not completely decomposed, it is decomposed by a radical or the like to an organic acid which is a decomposition intermediate product, and therefore can be discharged by the outflow port 42. The treated water is removed by ions. The temple is usually used in a water purification device using titanium dioxide photocatalyst. The ultraviolet light system uses a black light fluorescent lamp or a wave light of a wavelength 351. The reason is that the titanium dioxide photocatalyst is only 387 nm or less 200936510. It can be excited, and the products of the lamps are easily obtained. The water purifying device of the present invention utilizes ultraviolet rays which have not been used in the past, and is formed by photocatalyst. The water-purifying device of the present invention has a flat-shaped non-woven fabric having a photocatalytic function, and is disposed in parallel with the flat-shaped non-woven fabric and irradiated with 18 〇 to 19, such as m. With an ultraviolet ray irradiation means having a peak wavelength of 250 to 260 nm, the light irradiation efficiency to the photocatalyst and the contact efficiency with the fluid can be maintained, and the ultraviolet ray of 180 to 190 nm is not interrupted by the photocatalyst. Irradiating the flat non-woven fabric with ultraviolet light of 250 to 26 〇 nm to excite the photocatalyst to decompose the organic substance by the generated OH radical, thereby directly decomposing the organic substance in the water by the ultraviolet ray, thereby maintaining a high decomposition effect. The flat non-woven fabric 21 Preferably, it is a composite oxide of an oxide phase mainly composed of a cerium oxide component (hereinafter referred to as a first phase) and a metal oxide phase containing Ti (hereinafter referred to as a second phase), that is, a cerium oxide group. The composite oxide fiber is composed of the first phase of the oxide phase mainly composed of the ceria component, which may be amorphous or crystalline, and may also contain dioxable The metal element or metal oxide which forms a solid solution or a eutectic compound, and the metal element (A) which can form a solid solution with cerium oxide, for example, titanium, etc., can form a metal of a co-melting point compound with dioxo The element (8) may, for example, be a smear, a samarium, a bell, a nano, a samarium, a crane, a boron, a zinc, a nickel, a manganese, a magnesium, or an iron. The first phase forms an internal phase of the cerium oxide-based composite oxide fiber. The shoulder and shoulder negative mechanical properties play an important role. Compared with the ceria-based composite oxygen 200936510 compound fiber, the first phase is preferably present in a ratio of 4〇 to 98% by weight, and in order to fully exert the function of the desired second phase, The high mechanical properties are exhibited, and the ratio of the presence of the first phase is preferably in the range of 5 Torr to 95% by weight.

On the other hand, the second phase contains a metal oxide phase of Ti and plays an important role in functioning as a photocatalyst. The metal constituting the metal oxide can be exemplified by Ti. The metal oxide thereof may be a monomer or a eutectic compound thereof or a substituted solid solution formed of a specific element. The second phase forms a surface layer of the ceria-based composite oxide fiber, and the ratio of the second phase of the ceria-based composite oxide fiber varies depending on the kind of the metal oxide, but is preferably 2 to 6 G% by weight. It is more preferable to control the thickness to be 5 to 50% by weight in order to fully exert its function and simultaneously exhibit high strength. The proportion of the metal oxide contained in the second phase of the second phase increases obliquely toward the surface of the cerium oxide composite oxide fiber, and the inclination of the composition can clearly indicate the thickness of the confirmed region, preferably controlled from the surface layer. Open * $ ~ 鸠 please range 'but can also reach about 1/3 of the fiber diameter. Further, the "presence ratio" of the i-th phase and the second phase means that the metal oxide constituting the 帛1 phase and the metal oxide of the second phase are oxidized with respect to the metal oxide constituting the second phase and the metal constituting the second = The weight % of the whole material (i.e., the entire dioxin-cut composite oxide fiber). The flat non-woven fabric 21 composed of 7 cerium oxide-based composite oxide fibers can be obtained by the following production method. (Smelting and Visiting Wire Method) The water-oxygen-cut composite oxide fiber can be obtained by the following steps 1 to 4, and f ', P will have a main chain represented by the following 1: 11 200936510 Polycarbosilane having a skeleton and a number average molecular weight of 200 to 10000, a modified polycarbosilane modified with an organometallic compound, or a mixture of a denatured polycarbane and an organometallic compound, is subjected to 'melt spinning After the insolubilization treatment, it is fired in the air or in oxygen, whereby the cerium oxide-based composite oxide fiber can be produced.

R

I - (Si-CH2^- R ❹ (wherein R represents a hydrogen atom, a lower alkyl group or a phenyl group.) The first step is the production of a raw material for producing a cerium oxide-based composite oxide fiber. A step of using a denatured polycarbamide having a number average molecular weight of 1 〇〇〇 to 5 Å. The basic method for producing a modified polycarbohydrane is very similar to that of Japanese Patent Laid-Open Publication No. SHO 56-741-26, but It is necessary to pay close attention to and control the bonding state of the functional groups described therein, which will be briefly described below. The denatured polycarbosilane of the starting material is mainly composed of the main chain skeleton having the above-mentioned formula i and having a number average molecular weight of 2 Polycarbonate of 〇〇~1〇〇〇〇, and organometallic compound with basic structure M (0R,) n4 MR, 'm (M is a metal element, 111 and 11 are integers greater than 1) In the case of producing a ceria-based composite oxide fiber having a slanted structure, it is necessary to select a reaction condition in which only a part of the organometallic 4 chelate t is bonded to the polycarbene. Therefore, it is necessary. 28 (rc or less (preferably 25〇12 20 The temperature of 0936510 °c or less is reacted in an inert gas. Under the reaction conditions, the organometallic compound is bonded by a monofunctional polymer even if it reacts with polycarbodecane (ie, the bond is a pendant). It does not cause a large increase in molecular weight. A part of the denatured polycarbon which is bonded to the organometallic compound plays an important role in enhancing the compatibility of the polycarbonate with the organometallic compound. When a plurality of functional groups having two or more functional groups are bonded, it is confirmed that the crosslinked structure of the polycarbane is formed and the molecular weight is significantly increased at the same time. In the case of the ®, an imminent heat and melt viscosity are generated in the reaction. On the other hand, when the unreacted organometallic compound remains under the reaction of only the 1-functional group, the decrease in the melt viscosity is observed conversely. When the ceria-based composite oxide fiber having a slanted structure is produced, The best condition is to use an organic metallization in a state in which the unreacted organometallic compound remains. The coexistence of the organometallic compound to the extent of the product or the 2 to 3 polymer is used as the starting material, but even if only the polycarbene is denatured, when it contains a very low molecular weight denatured polysulfide component, it can also be used as a starting point. In the second step, the denatured polycarbane obtained in the second step, or a mixture of the denatured polycarbosilane and the low molecular weight organometallic compound (hereinafter, also referred to as a precursor) is melted to produce a spinning dope. And filtering it to remove microgels, impurities are harmful substances during spinning, and spinning them by a spinning device for spinning fibers generally used. The temperature of the spinning dope at the time of spinning is based on the raw materials. The softening temperature of the denatured polycarbane varies, but is preferably 50 to 200. (: The temperature range. In the above-mentioned spinning device, it is also possible to use 13 200936510 to set the discharge amount of the thirst heating nozzle in the lower part of the nozzle. And set in spinning, 3. Also, the fiber diameter can be adjusted by changing the speed. The second step of the winding of the lower speed winding is carried out. In addition to the above melt-spun denatured polycarbane or the denatured poly', the mixture obtained in the first step is dissolved in, for example, benzene, two low 77. The amount of organometallic denatured polycarbocarbonic calcined with low molecular weight I-toluene or other meltable ...._ ^ solvent of organometallic compound to prepare mash. 'Thickness to remove microgel, impurities equal to twirling Harmful substance, material spinning _ %Specially used for the spinning of the green stock solution, the wire is used in the dry spinning method, and the fiber is required. And 4, controlling the winding speed, in the spinning step, when the steaming is required, the spinning drum can be installed in the spinning device, and the environmental atmosphere in the cylinder is Λ l, +. The silk garment can be seen as a mixed atmosphere of at least the sorghum in the above-mentioned solvent, or as a sputum, as a gas, an inert gas, a hot air, a hot inert gas, a vapor, an ammonia gas, a hydrocarbon gas, and the like. The ambient atmosphere of the organic hydrazine compound gas whereby the curing of the fibers in the spin pack can be controlled.

In the third step, the spun fiber obtained in the second step is preheated under tension or no tension in an oxidizing atmosphere, and the spun fiber is infusible. The purpose of this step is to prevent the fibers from melting during the next step of firing and not for the purpose of subsequent fibers. The treatment temperature and the treatment time are not particularly limited, but are generally selected from the range of 50 to 40 (the range of TC, several hours to 3 hours), and may contain moisture in an oxidizing atmosphere. Nitrogen oxides, ozone, etc., which increase the oxidizing power of the spun fiber, can also actively change the partial pressure of oxygen 200936510. However, the softening temperature of the spun fiber is also lower than 5 according to the ratio of the low molecular weight contained in the raw material. (In the case of TC, in this case, it is important to apply the treatment for promoting the oxidation of the surface of the fiber at a temperature lower than the above-mentioned treatment temperature.] It is considered that the raw material is included in the second step and the third step. The low molecular weight material will bleed out toward the surface of the fiber to form the underlying layer of the desired tilt.

In the fourth step, the fiber which has not been melted after the third step is fired in an oxidizing atmosphere at a temperature of 5 〇〇 18 〇〇〇 于 under tension or no tension, and the desired fiber is obtained. The cerium oxide-based composite oxide fiber is composed of an oxide phase (second phase) mainly composed of a cerium oxide component and

The composite oxide phase of the metal oxide phase (second phase) of Ti is formed, and the Ti content ratio of the metal oxide constituting the second phase increases obliquely toward the surface layer. In this step, the organic component contained in the infusible fiber is substantially oxidized, but depending on the conditions selected, carbon or carbide remains in the fiber. In such a state, it can be used directly when it does not hinder the desired function, and if it is hindered, it can be further oxidized. At this time, you must select the temperature and processing time that will not cause problems for the desired tilt composition and crystal structure. After the photocatalyst-functional cerium oxide-based composite ytterbium-based fiber obtained as a short fiber is formed into a short fiber, a needle-shaped fabric (Needle Punch) or the like is formed to form a flat-shaped nonwoven fabric 21. (Smelting and blowing, spinning, and squeezing, and other methods, the method of blowing) The cerium oxide-based composite oxide 15 200936510 = the flat-shaped non-woven fabric composed of the ray-forming method Melting the melter's melter's melted from the spinning nozzle while spraying heated nitrogen gas around the spinning nozzle for spinning' to capture the spun fiber at the receptacle disposed below the spinning nozzle This forms a non-woven fabric. Then, the nonwoven fabric is not melted and then fired in an oxidizing atmosphere, whereby it can be produced. The direct gift of the nozzle is usually the use of melons. The nitrogen gas speed is about 30~30〇m/s, and the faster the speed, the finer the fiber. The heating temperature of nitrogen is not particularly limited as long as the desired spun fiber is obtained, but it is usually sprayed and heated to 5 Torr. . Nitrogen around. In the past, in the case of the melt-spray spinning method, the air is used in the gas-jet system, but the gas must be used when spinning the precursor. Spinning can be performed more stably by using gas as the gas to be ejected. _ When the receptacle disposed at the lower portion of the spinning nozzle captures the spun fiber, it is preferred to use a respirable receiver and to perform spinning by sucking the side under the receptacle. By inhaling the 'fibers' can be effectively entangled to obtain a high-strength nonwoven fabric. The suction speed is preferably in the range of about 2 to 1 〇 m/s. By performing the same non-woven treatment and baking as the above-described melt spinning, the non-woven fabric can be used as a flat-shaped nonwoven fabric 21 of the cerium oxide-based composite oxide fiber by the above-described melt-blowing spinning method. The produced cerium oxide-based composite oxide fiber 'when the average fiber diameter is preferably Μ "m, more preferably 2 to 6 /zm), it can be made into a fiber made by melt spinning. Fine. Thereby, the surface area of the fiber can also be increased to increase the catalytic activity. Further, the flat-shaped nonwoven fabric produced by the melt-blowing spinning method is made of a needle-made method of a short fiber having a length of about 40 to 50 mm which is produced by melt spinning, and the fiber is longer than the nonwoven fabric. As a result, the non-woven fabric has a tensile strength of -above), and when processed into a filter or the like, it has a :: 撊 processability. The weight or thickness of the flat non-woven fabric is not particularly limited. (4) (4) The weight is 50 to 500 g/m 2 , and the thickness is preferably 〇 5 to 2 〇. ^ Can be adjusted by layering non-woven as needed. When the thickness is thinner than 0.5 mm, the amount of the medium is too small to obtain a sufficient water purification effect. When it is 20mm ❿::LI plate-like non-woven fabric will become impedance, the pressure loss will increase, and it is difficult to handle the water. The shape of the flat non-woven fabric is not particularly limited, and it may be formed into a circular or square shape in accordance with the shape of a flow groove into which the flat non-woven fabric is inserted, or may be formed into a corrugated plate shape. According to the method for producing the flat-shaped nonwoven fabric 21 as described above, it is possible to: a bridge formed of photocatalyst fibers having a structure of a photocatalyst such as titanium dioxide, which is bridging and brittle with each other on the surface of one fiber; Weaving 21. Further, the photocatalyst fiber does not have the problem that the photocatalyst component of the fiber surface does not fall off by the conventional coating method. The flat non-woven fabric 21 composed of the fibers is a fiber-root one, and has a structure in which the voids are dispersed. Therefore, the contact area between the treatment fluid and the photocatalyst becomes very large. In general, in order to sufficiently induce photocatalyst chyme, it is necessary to increase the efficiency of light irradiation to the photocatalyst and the contact efficiency with the treatment fluid. Next, the second embodiment of the water purification apparatus of the present invention will be described in detail using the drawings. L. Fig. 3 is a conceptual view of a water purification device according to a second embodiment of the present invention. The water purification device 5 of the embodiment is configured to flow the water to be purified 17 200936510 from left to right and to circulate the water to be purified. The two points of the circulation mechanism are different from the first embodiment. The light touch 2G and the ultraviolet light 3 are the same as those in the first embodiment. In the water purifying apparatus 5 of the second embodiment, the flow cell 52 has an opening at the upper side, and an outflow port 54 is formed on the bottom surface of the downstream side (the right side of Fig. 3 t). The circulation mechanism is formed in a long cylindrical shape, and includes a flow person portion 56 having a plurality of flow holes A formed in a row in the longitudinal direction, and a circulation groove 58 for accumulating the water flowing out of the flow outlet The circulation path μ and the circulation path of the water flowing into the 4 56 can be made to flow into the circulation path (9). Between the crucibles 56, the water of the circulation tank 58 is caused to flow to the pump p of the inflow portion 56 through the circulation path; and the inflow portion 56 is disposed on the upstream side of the flow tank 52 (on the left side of FIG. 3) and the circulation groove 58 is provided. Provided below the outflow port 54, the water to be purified flows from the left side to the right side in the flow cell 52, and the outflowing water can be passed back to the flow cell 52 through the circulation groove 58, the sowing ring path 6 and the inflow portion 56. . In the water purification apparatus 5 of the second embodiment, three photocatalysts are arranged in parallel so as to intersect the flow direction of the flow cell 52 perpendicularly. Between each of the photocatalyst media 20, two ultraviolet irradiation lamps 3 are arranged such that the longitudinal direction of the ultraviolet irradiation lamp 3 is parallel to the surface of the flat non-woven fabric 21. On the more downstream side of the flow cell 52, two baffles 62 having different degrees are disposed on the downstream side of the photocatalyst g 2G, thereby preventing the treatment water from flowing into the outflow port 54. In the first embodiment and the second embodiment, the flat non-woven fabric 21 is preferably used as described above. However, as long as the water to be purified can pass through and has the function of light-touching 18 200936510, a well-known person can be used. Photocatalyst fibers composed of oxidized or titanium oxide-cerium oxide fibers may also be used. For example, the one described in Japanese Laid-Open Patent Publication No. H-347417 can be used. EXAMPLES Hereinafter, examples of the water purifying apparatus of the present invention will be described. (Production Example 1) First, a titanium dioxide/cerium oxide fiber which is a flat nonwoven fabric used in the examples was produced. Namely, 2.5 liters of anhydrous toluene and 400 g of metallic sodium were placed in a 5-liter three-necked flask, and heated to a boiling point of toluene under a nitrogen gas stream, and dimethyl dioxane 丨 liter was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was heated under reflux for 10 hours to form a precipitate. The precipitate was filtered, washed with decyl alcohol, and washed with water to obtain a white powder of polydimethyl decane (42 g). 250 g of polydioxyl decane was charged into a three-necked flask equipped with a water-cooled reflux apparatus, and further heated at 420 ° C for 30 hours under a nitrogen gas stream to obtain a polycarbane having an average molecular weight of 1,200.

16 g of fluorene xylene and 64 g of titanium tetrabutoxide were added to 16 g of polycarbocarbonate, and preheated at ι ° C for 1 hour, and then slowly heated to 15 (TC to distill off the hydrazine, and directly proceeded in this state. The reaction was carried out for 5 hours, and the temperature was further raised to 25 (TC reaction for 5 hours to synthesize a denatured polycarbane. The denatured polycarbane was used to actively coexist a low molecular weight organometallic compound, and 5 g of tetrabutoxytitanium was added to obtain denaturation. a mixture of a polycarbodecane and a low molecular weight organometallic compound. The mixture of the denatured polycarbosilane and the low molecular weight organometallic compound is dissolved in toluene, and then charged into a spinning device made of glass, and the inside is fully replaced by nitrogen. The temperature was increased, and the toluene was distilled off and then melt-spun at 8 (rc). The spun fiber was heated in the air to a temperature of 5 Torr to be melted, and then fired in air at 1200 ° C. In the hour, the titanium dioxide/cerium dioxide fiber was obtained. (Example 1) Using the titanium dioxide/cerium oxide fiber obtained in Production Example 1, a photocatalyst containing a flat non-woven fabric as shown in Fig. 2 was prepared and placed in the figure. The water purification device shown in the figure. The ultraviolet lamp used is G]L16KZF (output .15 W). The outer casing member is made of synthetic quartz. The output is 15W, and the ultraviolet lamp is used in four. The wavelength of the ultraviolet lamp is emitted. 254nnl and 丨85nm. The distance between the UV lamp and the photocatalyst is 5〇mm, and the average UV intensity of the flat non-woven surface is 2mW/cm2. ^The UV intensity is measured by the UVR-2 ultraviolet illuminometer manufactured by TOPCON. Nine parts were measured from the center of the flat non-woven surface to the end, and the average value was regarded as the average ultraviolet intensity. In terms of treated water, IpA (isopropyl alcohol) was dissolved in ultrapure water to make IPA of 1 〇 ppm. The aqueous solution of the IPA aqueous solution had a TOC (total organic carbon) of 6 ppm. 15 L of the IPA aqueous solution was subjected to a circulation treatment at a flow rate of 5 L/min for 2 hours using the water purification apparatus. The TOC of the water after the circulation treatment was measured, and the result was 0 · 1 Below ppm, the composition of the treated water was investigated. The result was that ip A was not detected, and only the oxidative decomposition products of IPA, namely acetic acid and formic acid, were detected. From this result, it can be seen that the water purification device can be fully lived. The organic matter decomposition ability of ultraviolet light can be added and the organic matter decomposition effect by photocatalyst can be added. (Comparative Example 1) 200936510 Ultraviolet lamp system uses GL16KSH (output: 15W) manufactured by Sankyo Electric Co., Ltd., and the outer casing member is ozone-free quartz which emits only 254 nm light. In the same manner as in Example 1, except that the IPA (isopropyl alcohol) was dissolved in ultrapure water and adjusted to 10 ppm of an IPA aqueous solution, the TOC of the IPA aqueous solution was prepared. The total organic carbon was 6 ppm. 15 L of the IPA aqueous solution was subjected to a circulation treatment at a flow rate of 5 L/min for 2 hours. The TOC of the water after the circulation treatment was measured and found to be 3.5 ppm. The composition of the treated water was investigated, and as a result, most (80%) of the IPA remained, and some oxidized decomposition products of IPA, namely acetic acid and formic acid, were detected. The reason why the decomposition efficiency is low as compared with the case of the first embodiment is presumed to be an organic decomposition effect by light having no light of 185 nm. (Comparative Example 2) A purification apparatus similar to that of Example 1 was produced except that the photocatalyst was not mounted. In the same manner as in Example 1, IPA (isopropyl alcohol) was dissolved in an IPA aqueous solution adjusted to 10 ppm of ultrapure water. The TOC (total organic carbon) of the IPA aqueous solution was 6 ppm. ® 15 L of IPA aqueous solution was circulated at a flow rate of 5 L/min for 2 hours. The TOC of the water after the circulation treatment was measured and found to be 2.5 ppm. As a result of investigating the composition of the treated water, the total amount of residual organic matter remained in the form of IPA, and acetic acid and citric acid which are oxidative decomposition products of IPA were not detected. The reason why the decomposition efficiency is low as compared with the case of the first embodiment is presumed to be that there is no decomposition effect of the photocatalyst. (Comparative Example 3) Using the titanium dioxide/cerium dioxide fiber obtained in Production Example 1, a crucible was produced. 21 200936510 Patent No. 3436267: A purification apparatus as shown in Fig. 2, which is formed into a circle

In the measurement, nine points were measured from the lower portion of the inner side surface (UV surface) to the upper portion, and the average value thereof was regarded as the average ultraviolet light intensity. In the same manner as in Example ◎, IPA (isopropyl alcohol) was dissolved in an IpA aqueous solution adjusted to 1 〇 ppm of ultrapure water. The TOC (total organic carbon) of the IPA aqueous solution was 6 ppm. 15 L of the IPA aqueous solution was circulated at a flow rate of 5 L/min for 2 hours. The TOC of the water after the circulation treatment was measured and found to be 2.0 ppm. The majority of the (85%) IPA remained in the results of the investigation of the composition of the treated water, and some of the oxidative decomposition products of IPA, namely acetic acid and formic acid, were detected. Compared with the case of the embodiment, the reason why the decomposition efficiency is low is presumed to be that the decomposition ability of the photocatalyst can be sufficiently obtained in the purification device, but the organic matter decomposition by the ultraviolet ray is blocked by the truncated cone-shaped photocatalyst. Reduced ability. Therefore, an ultraviolet lamp having two wavelengths of 254 nm and 185 nm is assembled only in the purification apparatus described in Japanese Patent No. 3,436,267, and sufficient purification efficiency cannot be obtained. (Comparative Example 4) A purification apparatus similar to that of Comparative Example 3 was produced except that the ultraviolet light was only emitted at 254 nm. In the same manner as in Example 1, Ipa (isopropyl alcohol) 22 200936510 was dissolved in an IP A aqueous solution adjusted to 10 ppm of ultrapure water. The TOC (total organic carbon) of this IP A aqueous solution was 6 ppm. 15 L of the IPA aqueous solution was subjected to a circulation treatment at a flow rate of 5 L/min for 2 hours. The TOC of the water after the circulation treatment was measured and found to be 2.5 ppm. The composition of the treated water was investigated, and as a result, most (85%) of the IPA remained, and some of the oxidative decomposition products of IP A, namely acetic acid and citric acid, were detected. Compared with Comparative Example 3, the decomposition efficiency was somewhat reduced but not greatly different. Therefore, it can be seen that the device of Comparative Example 3 cannot effectively utilize light of 185 nm. (Examples 2 to 8) The same as in Example 1, except that the distance between the ultraviolet lamp and the photocatalyst was adjusted to the distance shown in Table 1, and the average ultraviolet light intensity of the surface of the nonwoven fabric was 0.5 to 15 mW/cm 2 . Cycling and measurement. The results of the average UV intensity of the photocatalyst surface and the TOC after the cycle treatment are shown in Table 1. It can be seen that with the ultraviolet intensity of the photocatalyst surface, the IPA decomposition effect is greatly different. That is, when the ultraviolet ray intensity is small, the decomposition effect of the photocatalyst cannot be sufficiently exerted, and if the distance between the ultraviolet ray lamp® and the photocatalyst enthalpy is too small in order to increase the ultraviolet ray intensity, since the ultraviolet ray is blocked by the photocatalyst enthalpy, the organic substance due to the ultraviolet ray is The decomposition ability is reduced. Table 1 Average UV Intensity UV Lamp and Non-woven Fabric Distance TOC (mW/cm2) (mm) (PPm) Example 2 0.5 80 2.2 Example 3 1 70 0.2 Example 4 2 50 <0.1 Example 5 5 40 < 0.1 Example 6 8 30 < 0.1 23 200936510 Example 7 10 20 0.3 Example 8 15 10 1.2 (Example 9) The titanium dioxide/cerium oxide fiber obtained in Production Example 1 was used to prepare as shown in Fig. 2 The photocatalyst having a flat non-woven fabric is provided in the water purifying device shown in FIG. The ultraviolet lamp used was a GL16KZL manufactured by Sankyo Electric Co., Ltd. (output: 15 W). The outer casing member was made of synthetic quartz. The output is 丨5W, and the UV lamp system uses 4 pieces. The wavelength of the external line lamp emits both 254n'm and 1 85nm. The distance between the UV lamp and the photocatalyst is £5 mm, and the average UV intensity of the flat non-woven surface is 2 mW/cm2. The ultraviolet ray intensity was measured using a UVR-2 ultraviolet illuminometer manufactured by TOPCON Co., Ltd., and nine points were measured from the center portion to the end portion of the flat nonwoven fabric surface, and the average value thereof was regarded as the average ultraviolet ray intensity. For the treatment of water, ιρA (isopropanol) was dissolved in ultrapure water to make an IPA aqueous solution of 1 〇 ppm. The TOC (total organic carbon) of the IPA aqueous solution was 6 ppm. 15 L of the IPA aqueous solution was subjected to a circulation treatment for 2 hours using the water purification apparatus at a flow rate of 5 L/min. The t〇c of the water after the circulation treatment was measured, and the result was 0.1 ppm or less. The composition of the treated water was investigated, and as a result, lpA was not detected, and only a small amount of IPA oxidative decomposition products, namely acetic acid and formic acid, were detected. From this result, it is known that the water purification device can fully utilize the organic matter decomposition ability of ultraviolet rays and can add an organic substance decomposition effect by a photocatalyst. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual perspective view of a water purification apparatus of a first embodiment. Figure 2' is an enlarged view of the photocatalyst. Fig. 3 is a conceptual cross-sectional view showing a water purification apparatus of a second embodiment. 24 200936510 [Description of main components] 10, 50 Water purification equipment 11, 52 Flow cell 20 Photocatalyst 匣 21 Flat non-woven fabric 22 Net 30 Ultraviolet light 41 Inlet 42, 54 Outlet 56 Inflow 58 Circulation groove 60 Circulation path 62 Board 25

Claims (1)

200936510 X. Patent application scope: 1 . A water purification device comprising: a flow tank for flowing water to be purified in one direction, at least one of which is disposed in the flow tank and allows the water to be purified to pass through A flat-plate non-woven fabric comprising a photocatalytic fiber and an ultraviolet ray irradiation means for irradiating ultraviolet ray on the flat woven fabric; wherein the ultraviolet ray irradiation means has a shape extending in a longitudinal direction and is illuminable Ultraviolet rays having a peak wavelength of from 180 to 190 nm and from 250 to 260 nm are disposed such that their longitudinal directions are parallel to the flat non-woven fabric. ❹ 2 The water purifying device according to claim 1, wherein the photocatalytic fiber is composed of an oxide phase (first phase) mainly composed of a cerium oxide component and a metal oxide phase containing Ti (first) a cerium oxide-based composite oxide fiber composed of a composite oxide of 2 phases), wherein the ratio of the presence of Ti constituting the metal oxide of the second phase is increased obliquely toward the surface layer of the fiber. Or the water purification device of the two items, wherein the surface of the flat non-woven fabric has an average ultraviolet light intensity of 1 to 10 mW/cm2. The water purification apparatus according to claim 1 or 2, wherein the flat non-woven fabric surface is arranged to intersect perpendicularly or obliquely with respect to the flow direction. 5. The water purifying apparatus according to claim 1 or 2, wherein the flat non-woven fabric is disposed in two or more, and the ultraviolet ray irradiation means is disposed between the flat non-woven fabrics. The water purifying device of the jth or the second aspect of the invention, wherein the ultraviolet ray irradiation means is an ultraviolet lamp which can illuminate ultraviolet rays having a peak wavelength of (8) coffee and Mm. A method for purifying a ruler, characterized in that the water of 9 ϋ purified water flows through a flat non-woven fabric composed of fibers having a photocatalytic function, and has a shape elongated in a longitudinal direction and is disposed such that the longitudinal direction is opposite to the flat non-woven fabric The parallel ultraviolet irradiation hand & irradiated the flat non-woven fabric with ultraviolet rays having a peak wavelength of i 8G 〜m and 25Q 〜26Qnm. 8. In the water purification method according to item 7 of the patent application, the photocatalyst-functional fiber is composed of a phase of an oxide phase mainly composed of a cerium oxide component and a metal oxide phase containing T! a oxidized dream-based composite oxide fiber composed of a composite oxide of 2 phases), wherein the ratio of the presence of Ti constituting the metal oxide of the second phase increases obliquely toward the surface layer of the fiber. The water purification method according to Item 7 or 8, wherein the ultraviolet ray is irradiated so that the average ultraviolet ray intensity of the surface of the woven fabric is 1 〜. 1〇·If you apply for the water purification method in Section 7 or 8 of the patent application, you should use the 氽 二 々 々 々 ’ 流动 流动 流动 流动 朝 朝 朝 朝 朝 朝 朝 朝 朝 朝 朝 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Egg 1 or oblique XI, 囷: as the next page 27