TWI234180B - Ultraviolet-ray liquid treating apparatus - Google Patents

Abstract

Ultraviolet rays, emitted from a discharge lamp capable of irradiating both ultraviolet rays of less than 220 nm and ultraviolet rays of 254 nm, are irradiated to to-be-treated liquid, to thereby perform a process for decomposing organic substances in the to-be-treated liquid, etc. The discharge lamp employed here preferably has a film of metal oxide formed on the surface of a light emitting tube, so that mercury oxide produced during illumination of the discharge lamp can be prevented from being absorbed onto the surface of the light emitting tube and thus it is possible to restrain the 254 nm ultraviolet rays from deteriorating in illumination intensity over time. Because the 254 nm ultraviolet rays contribute decomposition of peroxides, maintaining the illumination intensity of the 254 nm ultraviolet rays over time can restrain a produced amount of peroxides in the to-be-treated liquid for a long period of time.

Description

1234180 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of Invention () [Technical Field to which the Invention belongs] The present invention is a discharge lamp that uses a short-wave band below 220nm and ultraviolet rays of 254 ηα to be radiated together. Liquid processing apparatus and method for performing treatment such as decomposition of organic matter in liquid. [Known technology] Ultraviolet rays in the short-wave band below 220η® have been widely used for the decomposition of harmful substances or organic substances due to their powerful energy. Fig. 10 shows an example of a conventional closed-type ultraviolet irradiation device for liquid processing. Among them, the discharge lamp 30 僳 is arranged in an outer tube (protective tube) 20, and then it is housed in a stainless steel cylinder 1. The liquid to be treated is introduced into the cylinder 1 and emitted by the discharge lamp 30. Ultraviolet radiation. The discharge lamp 30 僳 uses, for example, a low-pressure mercury vapor discharge lamp that emits both ultraviolet light in the short-wavelength band of 185η® and ultraviolet light in the 254-nm wavelength band. The lamp tube 10 of the discharge lamp 30 is made of quartz glass having excellent ultraviolet permeability. The discharge lamp 30 is housed inside an outer tube (protective tube) 20 having ultraviolet transmissivity and is liquid-tightly isolated from the liquid to be processed. This outer tube 20 is also made of quartz glass having excellent ultraviolet transmission. Both ends of the cylinder 1 are closed with flanges la, lb. The liquid to be treated introduced from the water inlet lc is irradiated with ultraviolet rays while passing through the inside of the cylinder 1, and then discharged from the water outlet Id. The liquid to be processed flows through the inside of the cylinder 1 from the water inlet lc toward the water outlet Id. However, in order to prevent the liquid to be processed from flowing out quickly, a plural number is arranged in the middle of the figure. In addition, for the sake of understanding, the 10th The figure only shows a device equipped with a discharge lamp 30, but in practice, a multi-lamp large-capacity device is often used. The ultraviolet rays emitted from the discharge lamp 30 pass through the outer tube 20 and irradiate the liquid to be processed. Photographed-4- Paper Size Applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-Order --------- 1234180 A7 B7 V. Description of the invention () The radiated ultraviolet rays have the effect of decomposing organic matter existing in water into harmless C0, C0. H 2 0 according to the following formula: 〇h2〇 + h / (1 8 5 nm) Η + 0H-based C «Hra 0 K + OH-based CO, C 0 2, Η 2 0 (η, 0 !, k is 1, 2, 3.. ♦) The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economy printed this organic matter The decomposition is effected by ultraviolet rays in the short-wavelength band of 185nm, but if the ultraviolet rays in the short-wavelength band are excessive, in addition to generating hydrogen peroxide (H 2 0 2), various undesired peroxide intermediates will be formed. In order to remove these peroxides, an ion-exchange resin is usually provided after the ultraviolet irradiation treatment so that the liquid to be treated through the ultraviolet irradiation treatment can pass therethrough. As a result, these over-gases are removed when the treated liquid passes through the ion-exchange resin, but too much over-gassing can rapidly shorten the life of the ion-exchange resin. <Problems to be Solved by the Invention> In view of the above problems, the present invention provides a liquid processing apparatus and method capable of performing liquid processing using ultraviolet rays while suppressing the generation of peroxides as much as possible. Therefore, the life of the ion exchange resin used after the ultraviolet irradiation treatment can be extended, thereby providing a liquid treatment apparatus and method with a long life, energy saving and maintenance. <Means for Solving the Problem> The ultraviolet liquid processing device of the present invention is a liquid processing device that uses a discharge lamp that can simultaneously emit ultraviolet rays below 220nia and ultraviolet rays of 254rini to perform the decomposition of organic matter of the liquid. A thin film of metal chloride is formed on the inner surface of the tube of the discharge lamp -5-(Please read the precautions on the back before filling this page)-Order ---------

13 Paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 1234180 A7 B7 V. Description of the invention () to prevent mercury chloride (mercury oxide) generated in the discharge lamp from being adsorbed on the lamp tube The inner surface, thereby suppressing a decrease in the illuminance of ultraviolet rays of 254πη. (Please read the precautions on the back before filling out this page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed a discharge lamp that can emit ultraviolet light below 220 ηπ and ultraviolet light at 254 nm at the same time. Photochemical treatment of decomposition, and ultraviolet light in the 254 nm band mainly decomposes peroxides of intermediates, thus reducing the burden of ion exchange resins used in the latter stage of ultraviolet irradiation treatment. The UV illuminance of the discharge lamp decreases with the passage of time, but the reasons for the decrease in UV illuminance in the short-wavelength band of less than 220ηπ and the 254nm of the ultraviolet band are different. That is to say, the reduction of the ultraviolet illuminance in the short wavelength band below 220nm is due to the deterioration of the quartz glass of the tube body constituting the discharge lamp due to the deterioration of the ultraviolet light, which leads to the reduction of the ultraviolet transmittance. The reason is that the mercury oxide generated in the reaction between the oxygen in the tube and the mercury (mercury) in the discharge lamp is attached to the inner surface of the quartz glass, which reduces the ultraviolet transmittance of the quartz glass. For this reason, ultraviolet rays in the short-wave band below 220riia and ultraviolet rays in the 254 nm band, as illustrated in Fig. 9, each have different characteristics of maintaining ultraviolet illuminance, that is, the maintenance rate of 254nm is lower than that of 220riffl (for example, 185nm). Below the low C point, the peroxide increases. To this end, according to the present invention, when a thin film of a metal vapor is formed on the inner surface of a lamp tube of a discharge lamp, mercury chloride generated in the discharge lamp lighting can be prevented from adhering to the inner surface of the lamp tube, thereby effectively suppressing 254 nm ultraviolet rays. The illumination is reduced. In addition, S of the ultraviolet liquid processing device of the present invention is a pseudo tube of the discharge lamp: it uses natural crystal or silica sand as raw materials, and its sodium (Na), potassium (K), titanium (Ti) and iron The total content of the 4 elements of (Fe) is 2.5ppm to -6-. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1234180 A7 B7 The invention is printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. () And quartz glass containing OH group above 10 ppm, and a thin film of metal oxide is formed on the inner surface of the lamp tube. (Please read the precautions on the back before filling out this page.) Quartz glass made of natural crystal or silica sand contains various impurities (impurities). Of these impurities, if the amounts of four elements, such as sodium, potassium, titanium, and iron, are large, the transmittance of quartz glass will decrease. In addition, the presence of 0H groups can alleviate the decrease in transmittance of quartz glass. That is, the [Si-0] bonding chain of silicon dioxide (Si02), the main component of quartz glass, is decomposed (cut off) when it is exposed to ultraviolet energy, and free Si and At this time, when the 0H group is present, the 0H group will recombine with free Si to form "Si-0H", thereby suppressing the deterioration of the quartz glass. According to the experimental research results of the inventors, when the total content of the above four elements is set to less than 2.5 ppm, and at the same time containing 0H groups above 10 ppffl, it is found that the time (over time) of quartz glass exposed to short-wavelength ultraviolet rays can be significantly improved. Degradation. Therefore, if the material of quartz glass is selected or set according to the above, 提高 can increase the illuminance retention rate when it is irradiated with short-wavelength ultraviolet rays below 220nm, and form a metal oxide film on the inner surface of the high-performance discharge lamp. , It can further enhance the effect of suppressing the reduction of the illuminance of ultraviolet rays of 254ηπ. In addition, another feature of the ultraviolet liquid processing device of the present invention is that the discharge lamp image is a lamp tube composed of synthetic quartz glass with an inner diameter of 8 μm or more, and one end of the lamp tube is arranged at an interval of L (cm). The filament (fi 1 ament), and the inside of the lamp tube are made of inert gas (rare gas) and at least one mercury-containing metal, and the voltage V (volt), the current ampere, the distance between the filaments when lighting L (cin) and the inner diameter of the tube DU ·) meet the following formula: -7- 2¾¾ The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1234180 A7 B7 V. Description of the invention ( ) (V-vf) / l = xh yT), and 2.6 SXS 4.2 where Vf is a constant factor determined by the lighting power source, set Vf = 10 when lighting with a high frequency power source above IKHz, Set Vf = 50 when lighting with power below IKHz. It will be explained in detail later that setting the conditions as shown above can make the ultraviolet radiation in the short-wave band below 220η® efficient, and form a metal vapor film on the inner surface of the tube of such a high-performance discharge lamp. The effect of reducing the illuminance of ultraviolet rays of 254nhi can be further enhanced. According to the present invention, a preferred embodiment is that it is used to form a metal oxide film on the inner surface of a lamp tube of a discharge lamp. It is at least one or more metals selected from the group consisting of aluminum, iodine, calcium, magnesium, yttrium, junctions, and materials. The gaseous substance is composed of main components. Since these metal oxides have excellent heat resistance and chemical stability, they can effectively prevent mercury chloride from adhering to the surface of the arc tube. The liquid treatment method using ultraviolet rays of the present invention is to use a discharge lamp in which a metal chloride film is formed on the inner surface of a light-emitting tube (lamp tube) as described above, and irradiate the liquid to be treated with ultraviolet rays to perform organic liquid decomposition treatment of the liquid, etc. As a feature. <Implementation Mode of the Invention> An embodiment of the invention will be described below with reference to the drawings. Fig. 1 is an example of a discharge lamp used in the ultraviolet liquid processing apparatus and method of the present invention. First, the basic structure of the discharge lamp 31 will be described. The discharge lamp 31 has a structure that can simultaneously emit ultraviolet rays below 220nm, such as 185nm, and ultraviolet rays of 2 5 4 γπβ. It is equipped with a light-emitting tube (lamp) 11 -8-7. This paper is in accordance with Chinese national standards (CNS ) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page) f

• n ϋ ϋ · ϋ ϋ ϋ ϋ ϋ ^ 1 ^ 1 n II Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1234180 A7 B7 V. Description of the invention (), which is arranged on one of the two ends of the filament 11 2 1 a, 2 1 b, sealing portions 2 a, 2 b and caps 3 a, 3 b provided at both ends of the lamp tube 11. The lamp tube 11 may be, for example, a synthetic quartz glass tube with an inner diameter and a wall thickness of Ihi®, and a thin film 44 of a metal oxide is formed on the inner surface thereof. The thin film 44 may be made of, for example, a substance having excellent heat resistance and chemical stability such as alumina. The two filaments 21a and 21b are oppositely arranged at a distance of about 153 cm. The aforementioned filaments 21a, 21b are composed of an emitter layer coated with, for example, barium oxide strips, and are supported by internal wires 22a-22d extending from the sealing portions 2a, 2b, respectively. The caps 3a and 3b are made of ceramic, and one cap 3a is provided with a pair of electrical terminals 31a and 31b. The sealing portions 2a and 2b electrically connect the filaments 21a and 21b to the electrical terminals 31a and 31d using the planing foils 24a to 24d and the external leads 25a, 25n, and 26. The arc tube 11 is sealed with about 20 mg of mercury and about 400 pa of inert gas. In addition, in the example shown in the figure, the discharge lamp 31 is configured as a two-terminal discharge lamp. That is, one end of the filament 21a is connected to one side of the electrical terminal 31a via the internal lead 22b, molybdenum foil 24b, and external lead 25a, and one end of the other filament 21b is via the internal lead 22c, molybdenum foil 24c, and external leads 26b, 26. It is connected to the other electric terminal 31b. As mentioned above, the UV illuminance of the discharge lamp decreases with the use of time, and the decrease of the UV illuminance in the 254 ηπ wavelength band is caused by the reaction between oxygen and mercury generated in the lamp during the discharge lamp lighting. The surface causes the ultraviolet transmittance of quartz glass to decrease. This is because the ultraviolet light of 254 μmα is the resonance light of mercury. This ultraviolet light will be absorbed by itself due to the presence of mercury. When mercury oxide is attached to the inner surface of the glass, the ultraviolet transmittance of 254γιβι will be selectively reduced. In view of this, the discharge used in the present invention -9 a 2f paperless scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

-ϋ 1 II n I 1: 0V snnnn ϋ 1 ϋ I Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers ’Cooperatives of the Ministry of Economic Affairs and the Consumer Cooperatives of the Ministry of Economic Affairs and printed by 1234180 A7 __B7 _ V. Description of the invention () Lamp, its light-emitting tube 11 A feature is that a thin film 44 of a metal oxide (alumina according to this embodiment) is formed on the inner surface of the glass, whereby the thin film 44 prevents the oxidants from adhering to the inner surface of the glass, thereby suppressing the illuminance of 254 nm ultraviolet rays from decreasing. In addition, the thin film 44 can be easily formed before coating the filament by coating a solution of alumina fine powder and a binder-suspended in butyl acetate on the inner surface of a glass tube, and then drying it in an oxidizing atmosphere. . In this embodiment, the discharge lamp 31 configured as described above is used as an ultraviolet light emitting source of the liquid processing apparatus. The liquid processing device may be a closed type liquid processing device as shown in Fig. 10, or it may be a liquid processing device of open water type. The discharge lamp 31 used in a stack of liquid processing devices is not limited to one, and most of them may be used. The light-emitting tube (lamp tube) 11 of the discharge lamp 31 used in this embodiment may be fused silica glass made of natural crystal or silica sand as a raw material, or may be synthetic quartz glass. First, the lamp tube 11 made of fused silica glass will be described. The quartz glass is composed of 4 elements of sodium (Na), potassium (K), titanium (Τί) and iron (Fe), the total content of which is 2.5 ppm or less, and gas fused silica glass of 0H or more and lOppia. The quartz glass having the above composition can suppress deterioration with time due to short-wavelength ultraviolet radiation. Fig. 2 is a graph showing the maintenance rate of the ultraviolet intensity of each of the lamp tubes 11 having the above-mentioned components through long-term lighting experiments. The shape and size of the discharge lamp are the same. In the figure, the horizontal axis represents the number of hours of lighting, and the vertical axis represents the ultraviolet intensity at a wavelength of 185 nm when the initial value of the intensity of the discharge lamp is 100 ¾. The composition of the quartz glass corresponding to the discharge lamps of curves A, B, C, and D is shown in the following table. 10-2 | The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) (Notes to fill out this page)

-ϋ 1 ϋ ϋ 1 «n« ϋ ον I I ϋ ϋ amamm ϋ 1_Β — —Bi I A7 1234180 B7_ 5. Description of the invention () 1. (Please read the precautions on the back before filling this page) Table 1 Curves Total content of Ha, K, Ti, Fe 0H group content A 2 · 5ρρηι ΙΟΟρρηι Β 4.2ρρηι 100 pp in C 4.5ppm lppm below D 6 · 4ppbi lOppiB The following curve A is a quartz glass that satisfies the total content of the four elements Na, K, Ti, and Pe as defined in this embodiment, is less than 2.5 ppro, and contains OH groups above 10 ppffl, and curves 3, C, and D are not satisfied. Those who set the conditions. Figure 2 shows that the result of the best performance of curve A is that when the amounts of the four elements and the 0H group are set according to the present invention, the ultraviolet illuminance retention rate of the short-wavelength band can be greatly improved. In the experiment shown in Fig. 2, since ozone (〇3) occurs in the reaction to ultraviolet rays in the atmosphere, and this ozone enters between the discharge lamp and the ultraviolet intensity meter, it will cause a deviation in the measured value. It is placed outside the discharge lamp and measured. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the technical field where the present invention uses ultraviolet rays for organic matter decomposition treatment and the like, regardless of the input density of the discharge lamp, the UV maintenance rate after one year of use is generally set to 70¾. From this point of view, the quartz glass having the composition obtained by the curve A in Fig. 2 is effective, and the quartz glass having the composition obtained by the curves B, C, and D is obviously not effective. He also said that the total of the four elements Na, K, Ti ·, Fe, etc. of the impurity of quartz glass is -11- _ Zhang scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperative. Printed 1234180 A7 ___ Β7__ 5. Description of the invention () The content is below 2.5 pphi, which can ensure that the UV maintenance rate for one year is above 70%. In addition, when the content of 0H group is 10 ppsa (curves c, D), the recombination effect of Si-OΗ cannot be fully expressed. In addition, the quartz glass with the above composition can be used for any component and device exposed to ultraviolet rays in the wave band below 220 η, in addition to the lamp tube of the discharge lamp itself, such as the outer tube (protective tube) shown in FIG. 20 . This type of container for receiving the outer tube of the discharge lamp, that is, the shape of the container is not limited to a cylindrical shape, and any other shape may be used. In addition, the fused quartz glass of the lamp tube constituting the discharge lamp 31 of this embodiment is not limited to the gas fusion type described above, but may also be an electric fusion type quartz glass. In addition, another embodiment of the above-mentioned discharge lamp 31 of this embodiment is that the lamp tube 11 is composed of synthetic quartz glass. In this case, the size of the discharge lamp 31 is determined according to a predetermined condition that ultraviolet rays with a wavelength of 185 nm can emit light efficiently. (卽 The inner diameter of the lamp tube or the distance between the filaments, etc.). This can not only improve the short-wavelength UV illuminance maintenance rate of the discharge lamp, but also improve the short-wavelength UV irradiation efficiency (see details later). It is highly desirable to use such a high-performance discharge lamp that can reduce the illuminance of ultraviolet rays of 2 54 nm for the ultraviolet irradiation device for liquid processing, because it can greatly increase the processing capacity and increase the life of the device. When forming the lamp tube 11 of the discharge lamp 31 from synthetic quartz glass, an example of the setting conditions of the size of the discharge lamp 31 (dimensions of the lamp inner diameter or filament pitch, etc.) is as follows. According to this embodiment, in order to efficiently emit ultraviolet light with a wavelength of 185 nm, the inner diameter D (unit: mm) of the lamp tube 11 made of synthetic quartz glass is set to 8 mffl or more, and the distance between the filaments 21a and 21b is set to L (unit is cm) Paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

_ ϋ IV II n ϋ I: OJI · ϋ I 1 _ϋ 1 I 1234180 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (), the voltage when lighting is set to V (the unit is volts), When the current is set to 1 (in amps), each value must be set to a system that satisfies the following formula: (V-Vf) / L =), and 2 · 6 SXS 4.2 In the above formula, Vf is the anode reduction Voltage, this value is a constant factor determined by the lighting power. For example, set Vf = 10 when lighting with a high-frequency power source above IKΗζ, and set Vf = 50 when lighting with a power source less than IKΗζ. The above-mentioned closed pseudo-image under the condition that the ultraviolet rays with a wavelength of 185nia can emit light efficiently is derived as follows. The present inventors performed experiments on various discharge lamps having different basic sizes of the basic structure of the discharge lamp 31 shown in FIG. 1 to evaluate the relationship between the electric characteristics of the discharge lamp and the ultraviolet intensity at 185 nm. The size of each tube used in this experiment was a synthetic quartz glass tube with an inner diameter of 8mm, 13mia, 18mm, and 23mffl, a wall thickness of Imni, and a length of 100-160c®. The filament pitch L was set to 95-153cm. In the experiment, a T-shaped glass tube was installed in a central part of a T-shaped glass tube by installing a branch tube for measuring the ultraviolet intensity at 185 nm in the center, and nitrogen gas was filled in the glass tube, and cooling water was flowed on the outside. There are two types of electronic ballasts (stabilizers) of about 40KHz and electromagnetic ballasts (stabilizers) of commercial frequency. The lamp current when lighting is set to 0, 4A, 0.6A, 0.8A, Ι, Five stages of 〇Α and 1.4A (ampere). 1 85 ηη ultraviolet light intensity was measured using a UV light meter UH85 (trade name) manufactured by Oku Manufacturing Co., Ltd. Under the above conditions, various electrical characteristics such as lamp voltage V, lamp current I, lamp power, and ultraviolet light intensity at 185 nm were measured while changing the cooling water temperature while keeping the current approximately constant. The reason for changing the cooling water temperature is to change the size of the paper. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

1234180 A7 B7 ^ ____ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Invention description () Mercury vapor pressure. That is, in order to confirm the fact that the ultraviolet radiation efficiency and electrical characteristics of 185 nm in general depend on the vapor pressure of mercury. By changing the temperature of the cooling water, the temperature of the coldest part where excess mercury is trapped is changed, thereby changing the vapor pressure of mercury. In other words, since the lamp voltage depends on the mercury vapor pressure in the lamp tube, that is, the evaporation amount, the lamp voltage can be set by changing the temperature of the coldest part. For a discharge lamp composed of a certain physical size, the lamp current I is also a constant factor determined by the ballast. The factor that can control the UV intensity of 185 η π is mainly the lamp voltage V. Therefore, changing the temperature of the cooling water can change the value of the lamp voltage V, so measuring the value of the lamp voltage V and measuring the UV intensity at 185 nm can know the UV intensity of the 185 nm under the condition of the actual scale and consisting of the predetermined lamp current I Correlation with lamp voltage V. Therefore, the measurement is performed as described above. According to the measurement results, from the viewpoint of "ultraviolet intensity per unit power consumption" in terms of ultraviolet intensity at 185nm, the value of the measured lamp power divided by the measured ultraviolet intensity of 185ηπ is used as the index of "radiation efficiency" ( That is "185ηπι ultraviolet radiation efficiency"). In terms of lamp voltage, from the viewpoint of "voltage per unit length", the value of the measured lamp voltage V (volts) is subtracted from the fixed value Vf (volts) of the reduced anode voltage (Vf), and then The value obtained, that is, V-Vf, divided by the filament L, is used as the "potential gradient (ie, the lamp electricity per unit length of the filament)." That is, the measured "185 n hi UV intensity" and "lamp voltage V" are converted into "185 ηπ ultraviolet emission rate" and "potential gradient", respectively, and the "185 ηηι ultraviolet emission efficiency" of each value of "potential gradient" can be compared. Value, so that you can grasp the best conditions for radiation efficiency. In addition, the anode lowers the voltage Vf. As described above, when lighting with a high-frequency power source above IKΗζ, set Vf = 10. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please first Read the Zhuyin on the back? Matters need to fill in this page)

1234180 A7 B7 V. Description of the invention (), and when lighting with a power source less than 1KΗζ, set Vf = 50. Figure 3 illustrates the physical conditions of a discharge lamp using a synthetic quartz tube with a wall thickness of liB®, an inner diameter of 13mm, a length of 154mm, and a filament pitch of 147eifi, and the lamp current I 1A (ampere) and the use of electronic ballast at about 40KHz The measurement results of the "potential gradient" and "185nra ultraviolet radiation efficiency" under the electrical conditions of the device (ie, Vf = 10). In the figure, the horizontal axis is a value of "potential gradient", and the vertical axis is a value corresponding to "185 nib ultraviolet radiation efficiency" of the potential gradient. As mentioned above, the lamp voltage V is changed by changing the temperature of the cooling water. As shown in Fig. 2, when the "potential gradient" is about 0.88 (V / cra), the "185nm ultraviolet radiation efficiency" shows the highest value (about 6). From this, it can be seen that as long as the above physical and electrical conditions are set, "The 185nm ultraviolet radiation efficiency j falls within a suitable tolerance range including its highest value, that is, a high peak value (the example in Fig. 2 is about 6). A discharge lamp and an ultraviolet irradiation device capable of emitting 185πε ultraviolet rays with high efficiency can be provided. This allowable range can be included in the allowable range by observing the actual ultraviolet irradiation state, and about 60-70% (60-70¾) of the "185nm ultraviolet radiation efficiency" of the high peak. Taking Figure 3 as an example, as long as the value of "185nm ultraviolet radiation efficiency" is at least 3.6 or more, it can be regarded as radiation that can emit efficiently. In this case, as can be seen from the figure, it is sufficient to set each condition so that the "potential gradient" falls within the range of about 0.72-1.16. This time illustrates another measured result. Use the same discharge lamp with the inner diameter of 13mm, the length of 1.34cir, and the filament pitch of 147c® as shown in Figure 3, and change the lamp current I to explore the "185nm UV radiation efficiency" of each lamp current value to reach a high peak. Optimal potential gradient. The optimum value of each obtained lamp current value (vertical axis) "potential -15-2 German paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the note on the back? Matters? (Fill in this page) f · 1111 — Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1234180 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Gradient ”(horizontal axis) is depicted, and the result is shown in Figure 4 As shown. From this figure, we know that the most suitable "potential gradient" is approximately inversely proportional to the square root (/ 7) of the lamp current value (I). According to the same method as described above, for the above-mentioned full-scale discharge lamp used in this experiment, the result of exploring the most suitable "potential gradient" of "185nro ultraviolet radiation efficiency" which can reach a high peak, and found that the discharge lamp of any tube diameter (inner diameter), the The most suitable "potential gradient" is approximately inversely proportional to the square root (fi) of the lamp current value (I). In addition, using the pipe diameter (D) as a parameter to describe the result of the "potential gradient", as shown in Figure 5, at any current, the "potential gradient" is also approximately inversely proportional to the square root (ΐΓ5) of the pipe diameter (D). That is, when the discharge lamp with a tube diameter (D) of 8-23nim is operated in the range of lamp current of 0.4-1.4A, its most suitable "potential gradient" to obtain the maximum ultraviolet radiation efficiency of 185nm is found to be related to the tube diameter (D) and The square root (γΐ) and (/ Γ) of the current (I) are inverse 1: b. This is proof that whether it is a high frequency electronic ballast or a commercial frequency electromagnetic ballast, as long as the constant factor of the lighting current is considered, the results in the stated range can be obtained. According to the above, when the "potential gradient" is most suitable, the "potential gradient" 卽 (V-Vf) / L is inversely proportional to the square root (Vi) of the tube diameter (D) and the square root (^ 1) of the lamp current (I). Off. By setting the proportionality constant to X, it can be expressed as the following equation: (V-Vf) / L = X / (/ d ^ 7)

According to the example in Figure 3, the inner diameter D = 13mffi and the lamp current I = 1A, so (/!) · / T) is about 3.605, so that the "potential gradient" falls within the above-mentioned tolerance of about 0.72-1 · 16 Within the range, the proportionality constant X is set to about 2 · 6 $ XS Wide Θ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • --- I ---- ^ ---- --------- Order --------- (Please read the note on the back? Matters before filling out this page) I234180 A7 B7 1. Description of the invention () 4 ♦ 2 can. According to the above experimental results, using the discharge lamp 31 of the lamp tube 11 composed of synthetic quartz glass shown in Fig. 1, the inner diameter D of the lamp tube 11 (the unit is set to 8 la m or more, the filament 2 1 a, When the distance between 2 1 b is set to L (unit em), the lamp voltage when lighting is set to V (volts), and the lamp current is set to 1 (amps), set the width of each value in the following formula: It is necessary to achieve 185nm high-efficiency ultraviolet radiation; (V_Vf) / L = · 7ΐ), and 2.6SX S4,2 Here, as mentioned above, the anode reduction voltage Vf of the factor determined by the lighting power source , Set to Vf = l0 when lighting with a high-frequency power source above IKΗζ, set to Vf = 50 when lighting with a power source that is not full IKΗζ. An example of a discharge lamp 31 manufactured according to the above conditions is a lamp tube with an inner diameter of 13mm and a filament pitch of 153c®. The lamp tube 11 is made of synthetic quartz glass and a metal oxide is formed on the inner surface of the lamp tube as shown in FIG. 1 ( (Eg alumina) film. Fig. 6 shows the measurement results of the maintenance rate of the ultraviolet illuminance obtained from the long-term lighting experiment of the discharge lamp 31 described above. In the figure, the horizontal axis is the lighting time, and the vertical axis is the UV illuminance at a wavelength of 185ηπ and 254η® when the initial value of the illuminance of the discharge lamp is set to 100¾. As a result of the aluminum oxide film 44 formed on the inner surface of the lamp tube 11, as a result, the decrease in the ultraviolet illuminance in the 254 nm band is hardly seen, which greatly improves the illuminance maintenance rate compared to the conventional discharge lamp shown in FIG. 9 above. The UV illuminance maintenance rate of the belt also improved significantly. The ultraviolet liquid processing device of the present invention, that is, the ultraviolet irradiation device can be applied to, for example, the purification of ultrapure water used in semiconductor manufacturing processes. Here the 24G paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ------- Order · ——-- -Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1234180 A7 _B7_ V. Description of the invention () (Please read the precautions on the back before filling this page) Occasionally, it is required to be able to be used continuously for at least 3 years. When the discharge lamp of the present invention is used, not only the decomposition treatment capability of TOC (total organic carbon) can be improved, but also the multiplication effect of reducing the burden of the ion exchange resin can be achieved. Therefore, the present invention is extremely suitable for ultra-pure water refining processing used in semiconductor manufacturing processes and the like. Of course, in addition to the above-mentioned application methods, it is also suitable for a wide range of applications requiring liquid treatment such as the production of beverages, foods, medical treatment, water treatment and other organic matter decomposition treatment, disinfection, and disinfection. FIG. 7 is an ultraviolet irradiation device equipped with a discharge lamp using conventional technology and an ultraviolet irradiation device A equipped with a discharge lamp according to an embodiment of the present invention. The raw water having a TOC concentration of 10 ppb is treated to a processing capacity below Ippb. A graph of measured data comparing the flow of electricity consumption per unit. In the figure, the initial value of the conventional device is set to 100¾. As can be seen from the figure, the performances of the conventional device B and the device A of the present invention are greatly different in the initial stage, and the differences are enlarged over time. The improvement of the TOC processing capacity is due to the improvement of the ultraviolet radiation efficiency and maintenance rate of 185 ηπ, but when the ultraviolet in the short-wave band is too much, as mentioned above, the life of the ion exchange resin will be shortened. However, when using the discharge lamp of the present invention, It can suppress the decrease of the illuminance of ultraviolet rays of 254m, so it can reduce the burden of ion exchange resin. Printed in Figure 8 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The specific resistance of the treated water measured at the exit of the ion exchange resin project at the rear stage of the liquid using the conventional ultraviolet irradiation device B and the ultraviolet irradiation device A of the present invention. Graph. The vertical axis represents specific resistance, and the horizontal axis represents lighting time. The specific resistance varies depending on the concentration of peroxide. The higher the concentration of peroxide, the lower the specific resistance. That is, due to the deterioration of the ion exchange resin, the loss of peroxide I will increase and the specific resistance will be reduced. Therefore, the change in the specific resistance at the exit of the ion exchange resin project will become the degradation of the ion exchange resin. This paper applies Chinese national standards (CNS) ) A4 specification (210 X 297 mm) 1234180 A7 B7 V. Specification of invention (). The specific resistance of the device at the initial stage of use, the conventional device B and the device A of the present invention are both higher than 1 80M Ω, but one year after the start of use, the specific resistance of the conventional device B is reduced to 16M Ω of the ion exchange resin replacement target. about. In this regard, the specific resistance of the device A of the present invention is only slightly reduced, which proves that the burden on the ion exchange resin is reduced. This is because the UV illuminance maintenance rate in the 254η «I wavelength band has been greatly improved and the peroxide processing capacity has been maintained. As described above, the present invention uses a discharge lamp that can simultaneously emit a short wavelength band below 220 nm and ultraviolet light at 254 nm, and forms a thin film of metal oxide on the inner surface of the lamp tube to improve the ultraviolet illuminance maintenance rate at 254 nm. A new invention in which ultraviolet rays emitted from a discharge lamp perform treatment such as decomposition of organic matter on a liquid to be treated, thereby promoting decomposition of an undesired intermediate product. In the above embodiment, a description is given of a discharge lamp composed of a synthetic quartz glass whose lamp size is determined according to the condition that it can emit ultraviolet rays with a wavelength of 185 nm in a highly efficient manner. However, the present invention is not limited to the described embodiment. The (natural) quartz glass lamp can also achieve the desired effect. In addition, the metal chloride for the thin film formed on the inner surface of the lamp tube of the discharge lamp will be described using alumina as an example, but at least one metal selected from silver, silicon, potassium, money, yttrium, junction, and supply is used. The above oxides are also effective as the main constituents. In addition, as long as the shape of the discharge lamp is a discharge lamp that can simultaneously emit short-wave bands below 220nm and 254nm ultraviolet rays, whether it is a discharge lamp sealed with mercury or other amalgam, or a continuous heating type discharge lamp heated by a filament, Discharge lamps such as a type provided with a filament and an anode are applicable to the present invention and exert the same effect. -19- 2 ί 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) w 1: aJ ϋ ϋ I i_i / am— Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1234180 A7 B7 V. Description of the invention () "Effects of the invention" From the above description, it can be seen that according to the present invention, the use of ultraviolet rays that can emit a band under 220 ηη K and 2 5 4 ηιη UV at the same time is used. The discharge lamp can improve the maintenance rate of ultraviolet radiation of 2 5 4 ηη, and increase the radiation efficiency of ultraviolet rays at 220 η® Μ to improve the maintenance rate of radiation. When the discharge lamp is installed in a liquid processing device, various equipment can be improved. The durability of the machine achieves economic benefits of saving energy and saving maintenance. Brief description of the drawings. Fig. 1 is a schematic longitudinal sectional view of an example of a discharge lamp used in the ultraviolet liquid processing device of the present invention. Fig. 2 is a view of using quartz glass (containing sodium, potassium, titanium, and iron elements) defined by the present invention. And 0Η) graphs of the UV intensity maintenance rate curves of various discharge lamps produced through long-term lighting experiments; where A is those who meet the defined conditions of the present invention, and B, C, and D do not meet the defined conditions of the present invention; Figure 3 is a graph showing the relationship between the "potential gradient" and the 185nm ultraviolet radiation efficiency according to the experimental results of the discharge lamp of the present invention; The relationship curve of “potential gradient j” is suitable; FIG. 5 is the relationship between the inner diameter of the lamp tube obtained from the experimental results of the discharge lamp of the present invention and the most suitable “potential gradient”, corresponding to the values of “lamp current” Graph; Fig. 6 is a graph of-example of the maintenance rate of ultraviolet illuminance of 185n® and 254ηιπ of the discharge lamp of the present invention; -20- 'This paper size applies Chinese National Standard (CN S) A4 size (21〇 X 297 mm) (Please read the notes on the back before filling this page)

ϋ an «1 1 · — I substitute! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ν4 1234180 A7 B7 V. Description of the invention Drawing of the change curve; UV line diagram of 185nai and 254nm of the discharge lamp; and Figure 7 of an example of the ultraviolet irradiation device of the discharge lamp is a graph showing the use of the liquid conventional device of the present invention; Figure 8 is the above each Measured at the exit of the resin-loading project. Figure 9 is an example of a conventional illuminance maintenance rate. Figure 10 is a schematic diagram of the conventional vertical section. Symbol Description 2a, 2b____Sealing section 11____Light tube 2 1 a, 2 1 b ... filament 2 4 a-2 4 d____molybdenum foil 3 1 ··· .discharge lamp 3a, 3b____cover 20——outer tube (protective tube) 22a-22d .... inner wire 25a, 25b, 26 · ·· External guides 31a, 31b · .. Electric terminals (Please read the phonetic on the back? Matters before filling out this page) Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 1-4 This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 male %)

Claims (1)

1234180 I Announcement I—92 * m No. 91 123626 Patent Application Supplementary and Revised Unlined Specification Replacement Sheet in Triplicate 1. An ultraviolet liquid processing device; it will be capable of reducing ultraviolet light below 220ηπι and 254nm The ultraviolet rays emitted by the discharge lamp which emits ultraviolet rays at the same time are used to irradiate the liquid to be treated to decompose the organic matter of the liquid. The special feature is that the discharge lamp is formed on the inner surface of the lamp tube with aluminum, Silicon oxide, calcium oxide, magnesium oxide, yttrium oxide, and metal oxide films composed of at least one or more vapors of selected metals as the main component. 2. For example, the ultraviolet liquid treatment device of the scope of patent application, wherein the lamp tube of the discharge lamp is made of natural crystal or silica sand, and the content of four elements such as pin, potassium, titanium, and iron is 2, Quartz glass composed of 0 ppm or less and 5 ppm or more of 0H group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. For example, the ultraviolet liquid skull processing device of the first patent application scope, wherein the discharge lamp 傺 is a lamp tube formed of synthetic quartz glass with an inner diameter of 8111a or more, separated by L (cm ) The interval is set at one of the two ends of the lamp tube. It is made of a pair of light green and a rare gas enclosed in the lamp tube and at least one metal including mercury. At the same time, the lamp voltage V (volt), the lamp current 1 (Ampere), filament pitch Ucm), and the inner diameter D (mni) of the discharge lamp have the following relationship; (V-Vf) / L = XM # ♦), and -22- this paper size applies to China Standard (CNS) A4 specification (21 × X: 297 mm) 1234180 2.6 SX ^ 4.2 where Vf is a constant factor determined by the lighting power source, and set to Vf = 10 when lighting with a high-frequency power source above 1KHz. When the power is less than IKHz, set Vf = 50 (Please read the precautions on the back before drawing). The paper printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS) A4 specification (210X29). ? Mm)