WO2007058285A1 - Procede de nettoyage de fluide et appareil de nettoyage de fluide - Google Patents

Procede de nettoyage de fluide et appareil de nettoyage de fluide Download PDF

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Publication number
WO2007058285A1
WO2007058285A1 PCT/JP2006/322921 JP2006322921W WO2007058285A1 WO 2007058285 A1 WO2007058285 A1 WO 2007058285A1 JP 2006322921 W JP2006322921 W JP 2006322921W WO 2007058285 A1 WO2007058285 A1 WO 2007058285A1
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Prior art keywords
gas
liquid
nitrous oxide
fluid
container
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PCT/JP2006/322921
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English (en)
Japanese (ja)
Inventor
Ryuji Sotoaka
Tomoyuki Azuma
Original Assignee
Mitsubishi Gas Chemical Company, Inc.
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Publication date
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Priority to JP2007545303A priority Critical patent/JPWO2007058285A1/ja
Publication of WO2007058285A1 publication Critical patent/WO2007058285A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C02F1/325—Irradiation devices or lamp constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0875—Gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0883—Gas-gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0884—Gas-liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0888—Liquid-liquid
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/32—Details relating to UV-irradiation devices
    • C02F2201/322—Lamp arrangement
    • C02F2201/3221—Lamps suspended above a water surface or pipe
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • the present invention relates to a method for purifying a fluid such as gas or liquid and an apparatus therefor.
  • Fluid is a general term for gases and liquids, and is a substance whose shape can be freely changed. In general, a lot of impurities are mixed in the fluid, causing various adverse effects in each field.
  • gases and liquids contain a large amount of organic substances such as oil and proteins.
  • Organic substances contained in the gas may cause unpleasant odors, and oils contained in the liquid may cause environmental pollution. Therefore, when purifying such a fluid, it is important to decompose and remove organic substances contained in the fluid.
  • a method for purifying organic substances a method of decomposing organic substances by causing an acid-oxidation reaction is known (see Non-Patent Documents 1 and 2).
  • Non-Patent Document 1 Naotoshi Yamanouchi, Mitsuo Takeda, “Nitrous Oxide”, High Pressure Gas, Vol. 13 No. 3 (1976) pl05 ⁇ l l l
  • Non-patent document 2 "Photochemical reaction in the gas phase", edited by The Chemical Society of Japan, Chemical Review, Journal of Inorganic Photochemistry, Publication Center No. 39, (1983)
  • gas purification is currently required in various situations. For example, when circulating air in a building, taking outside air into a room, or releasing air generated by industrial activities to the outside world.
  • Liquid purifiers are similarly required in various situations. For example, when processing to return the used liquid used in various human activities to the natural world, or processing to obtain a liquid for a specific purpose from used liquid or liquid existing in the natural world Etc. [0007] The need for such fluid purification is now increasing, and there is a need for a simple method for purifying liquids.
  • Non-Patent Document 1 nitrous oxide is a stable gas at room temperature and normal pressure, and does not decompose by visible light.
  • nitrous acid even when nitrous acid was used, it was found that the gas was difficult to handle when oxidation was performed in the gas phase.
  • Non-Patent Document 2 when nitrous oxide is irradiated with light having a wavelength shorter than 240 nm, nitrous oxide is converted into nitrogen molecules (N) and atomic oxygen (O). The knowledge that it decomposes was obtained.
  • Non-Patent Document 2 includes N O
  • the present invention has been made in view of such problems, and an object of the present invention is to provide a fluid purification method and apparatus capable of easily purifying fluid.
  • a fluid purification method in which ultraviolet light is irradiated in a state where nitrous acid nitrogen gas is in contact with a substance contained in the fluid is used.
  • the fluid purification method described above is characterized in that the fluid is a gas.
  • the fluid purification method described in any one of the above is characterized in that the fluid is a liquid.
  • the nitrous oxide gas is dissolved in the fluid.
  • V the fluid purification method described in any of the above.
  • the fluid purification method according to any one of the above, which is an ultraviolet light source power krypton iodine (Krl) excimer lamp.
  • a contact unit for bringing a substance contained in a fluid into contact with a solution containing nitrous oxide, and a light source for irradiating the substance in contact with the nitrous oxide with ultraviolet light are provided.
  • a fluid purifier for the fluid is provided.
  • the contact unit is the fluid purifier according to the above, including a storage unit that stores the fluid and the solution containing nitrous oxide. .
  • the present invention includes a contact unit for bringing a substance contained in a fluid into contact with nitrous oxide, and a light source for irradiating the substance in contact with the nitrous acid nitrogen with ultraviolet light.
  • the fluid purification apparatus described above was used.
  • the contact unit includes a container for bringing a substance contained in the fluid into contact with nitrous acid nitrogen dissolved in the fluid. This equipment was used.
  • the fluid purification apparatus according to any one of the above, wherein the ultraviolet light source is a krypton iodine (Krl) excimer lamp.
  • the ultraviolet light source is a krypton iodine (Krl) excimer lamp.
  • the substance is purified by irradiating the solution containing nitrous oxide with ultraviolet light in a state where the solution is in contact with the substance contained in the fluid. did. Therefore, the oxidation reaction can be easily controlled, and the fluid to be treated, that is, gas or liquid can be easily purified. Nitrous oxide nitrogen undergoes a separation reaction when irradiated with ultraviolet light having a wavelength that does not normally exist in nature. Therefore, for example, even if the treatment waste liquid is allowed to flow directly into the sewer, it does not have a harmful effect on the natural world.
  • the fluid can be easily purified. Further, when the fluid is a liquid, it is possible to recover the liquid to be processed without changing the concentration of the liquid to be processed. Furthermore, since no solvent for dissolving nitrous acid and nitrogen is required, purification can be carried out economically.
  • the fluid is a gas, the gas can be easily purified by oxidizing an organic substance or the like contained in the gas.
  • the fluid is a liquid
  • the liquid can be easily purified by oxidizing an organic substance or the like contained in the liquid. it can.
  • the ultraviolet light source is a krypton iodine (Krl) excimer lamp
  • Krl krypton iodine
  • excimer lamps have good rise and fall, etching can be performed only at predetermined times by turning the lamps on and off. Further, if the irradiation with ultraviolet light is stopped, the object to be processed is hardly dissolved.
  • excimer lamps have excellent characteristics such as low generation of ozone due to light emission, and can reduce environmental impact.
  • the contact substance is brought into contact with nitrous oxide or a solution containing nitrous oxide and brought into contact with nitrous oxide by the contact unit.
  • the fluid to be treated can be easily purified simply by irradiating the substance to be oxidized with ultraviolet light from the light source.
  • FIG. 1 is a schematic diagram showing a configuration of an apparatus used in a fluid purification method of the present embodiment.
  • FIG. 2 is a graph showing the results of purification in Example 1 of the fluid purification method.
  • FIG. 3 is a graph showing the results of purification in Comparative Example 1 of the fluid purification method.
  • FIG. 4 is a graph showing the results of purification in Comparative Example 2 of the fluid purification method.
  • FIG. 5 is a graph showing the results of purification in Example 2 of the fluid purification method.
  • FIG. 6 is a graph showing the results of an experiment conducted by changing the wavelength of ultraviolet light and the irradiation time using the apparatus of the example of the fluid purification method.
  • FIG. 7 is a graph showing a UV absorption spectrum of a nitrous acid-nitrogen solution.
  • FIG. 8 is a graph showing a UV absorption spectrum of oxygen.
  • FIG. 9 is a schematic diagram showing the configuration of the gas purification apparatus in Example 1 of the gas purification apparatus.
  • FIG. 10 is a schematic diagram showing the configuration of the gas purification apparatus in Example 2 of the gas purification apparatus.
  • FIG. 11 is a schematic diagram showing a configuration of a gas purifier according to another embodiment.
  • FIG. 12 is a schematic diagram showing a configuration of a gas purifier according to still another embodiment.
  • FIG. 13 is a schematic diagram showing a configuration of a gas purifier according to still another embodiment.
  • FIG. 14 is a schematic diagram showing a configuration of a gas purifier according to still another embodiment.
  • FIG. 15 is a schematic view showing a configuration of a gas purifier according to still another embodiment.
  • FIG. 16 is a schematic diagram showing a configuration of a gas purifier according to still another embodiment.
  • FIG. 17 is a schematic diagram showing the configuration of the liquid purification apparatus in Example 1 of the liquid purification apparatus.
  • FIG. 18 is a schematic diagram showing a configuration of a liquid purification device in Example 2 of a liquid state device.
  • FIG. 19 is a schematic diagram showing a configuration of a liquid purification apparatus in Example 3 of the liquid state purification apparatus.
  • FIG. 20 is a schematic view showing a configuration of a liquid purification apparatus of another example.
  • FIG. 21 is a schematic diagram showing a configuration of a liquid purifier according to still another embodiment.
  • FIG. 22 is a schematic diagram showing a configuration of a liquid purifier according to still another embodiment.
  • FIG. 23 is a schematic view showing a configuration of a liquid purifier according to still another embodiment.
  • FIG. 24 is a schematic diagram showing a configuration of a liquid purifier according to still another embodiment.
  • FIG. 25 is a schematic diagram showing a configuration of a liquid purification apparatus according to still another embodiment.
  • FIG. 26 is a schematic view showing a configuration of a liquid purifier according to still another embodiment.
  • FIG. 27 is a schematic diagram showing a configuration of a liquid purification apparatus according to still another embodiment.
  • FIG. 28 is a schematic view showing a configuration of a liquid purification apparatus according to still another embodiment.
  • fluid is a general term for gases and liquids.
  • the solution containing nitrous oxide refers to a solution obtained by dissolving nitrous acid nitrogen gas in a solvent such as water.
  • the gas to be treated refers to a gas that is an object of the purification method according to the present invention.
  • the acidified substance is a target substance to be oxidized!
  • a methylene blue solution was used as an object to be processed.
  • the concentration of methylene blue in the aqueous solution was 10 ppm.
  • the aqueous methylene blue solution has a blue color, and when purified by oxidation, the blue color disappears and becomes colorless.
  • photocatalysts In order to reduce the absorbance at 665 nm of an aqueous methylene blue (lOppm) solution to about 10% of the initial level, photocatalysts generally require several tens of minutes to several hundred minutes.
  • a purifier 11 as shown in FIG. 1 was prepared.
  • the purification apparatus 11 includes a container 12 whose upper surface is open, and a lamp (light source) 13 that emits ultraviolet light.
  • the container 12 was a Teflon (registered trademark) processed inner surface of the container.
  • the light source 13 was installed immediately above the container 12 and in a position close to the container 12, and was able to irradiate the container 12 with ultraviolet light.
  • the light source was a high-pressure mercury lamp, and its output was 1200 watts.
  • a nitrous acid-nitrogen aqueous solution used for purification of a methylene blue aqueous solution was prepared.
  • the concentration of nitrous acid nitrogen in the solution was lOOOppm.
  • a methylene blue aqueous solution and a nitrous acid / nitrogen aqueous solution were put into the container 12 and mixed to obtain a mixed solution 14. Then, the light source 13 is turned on so that the mixture 14 in the container 12 A purification treatment was performed by irradiating with external light.
  • the ambient temperature at the place where the purifier 11 was installed was 24 ° C.
  • FIG. 2 is a graph showing the results of the purification process according to this example.
  • the horizontal axis of this graph is the light irradiation time (minutes), and the vertical axis is the 665 nm absorbance of the methylene blue aqueous solution.
  • the following Equation 1 is an equation for obtaining the light transmittance (T).
  • the symbol “Ii” is the intensity of the light incident on a certain substance
  • the symbol “Io” is the intensity of the light emitted therefrom.
  • Equation 2 is an equation for obtaining absorbance.
  • Example 2 the same purification apparatus 11 as in Example 1 was used. However, in this comparative example, an aqueous solution of helium (He) was prepared instead of the aqueous nitrous oxide solution. This helium aqueous solution is obtained by forcibly dissolving helium in water, and forcibly dissolving helium expels air components (N, O, CO, etc.) dissolved in water.
  • He aqueous solution of helium
  • Helium is a well-known inert gas that does not absorb light at a wavelength of 665 nm.
  • the concentration of helium was 16 ppm.
  • FIG. 3 is a graph showing the results of the purification process according to this comparative example.
  • the graph format is shown in Fig. 1. Is the same.
  • Example 2 the same purification apparatus 11 as in Example 1 was used. All conditions were the same as in Example 1 except that the light source 13 was not turned on. The methylene blue aqueous solution was purified by the same procedure as in Example 1.
  • FIG. 4 is a graph showing the results of the purification process according to this comparative example.
  • the format of the graph is the same as in Figure 1.
  • the mixed solution 14 obtained by mixing was allowed to stand for 60 minutes in the state in which methylene blue and nitrous acid nitrous acid were dissolved and was not irradiated with light having a wavelength of 240 nm or less. Even so, it was confirmed that the absorbance at 665 nm did not change. In other words, it was confirmed from a comparison between FIG. 2 and FIG. 4 that methylene blue would not be decomposed by acid without irradiating light to nitrous acid nitrogen.
  • the same purification apparatus 11 as in the first embodiment was used. All conditions were the same as in the example except that the light source 13 was temporarily turned off during the process.
  • the methylene blue aqueous solution was purified by the same procedure as in Example 1. In this example, the lamp was turned off when 0.5 minutes had elapsed since the lamp was turned on, and the lamp was turned on again when 1.5 minutes had elapsed since the lamp was turned on. In other words, the turn-off time was 1 minute.
  • FIG. 5 is a graph showing the results of the purification process according to this example.
  • the format of the graph is the same as in Figure 1.
  • the decomposition of methylene blue started with the start of irradiation with ultraviolet light, and the decomposition of methylene blue stopped when the irradiation with ultraviolet light was stopped. After that, when UV irradiation was resumed, the decomposition of methylene blue started.
  • the irradiation time of ultraviolet light is controlled. Therefore, it was confirmed that the acid time of the substance can be controlled.
  • the generation of atomic oxygen is started at the same time as the start of ultraviolet light irradiation to nitrous oxide, and the generation of atomic oxygen is considered to stop at the same time as the irradiation of ultraviolet light is stopped. Since the life is extremely short, the acid can be started and stopped substantially by starting and stopping the irradiation with ultraviolet light.
  • an oxidation reaction occurs only when ultraviolet light is irradiated, and the gas to be treated is purified. Therefore, the oxidation reaction can be easily controlled.
  • the acid / acid reaction occurs only during irradiation with ultraviolet light, corrosion of equipment used in the purification process can be minimized. Therefore, there is an advantage that corrosion countermeasures are not required for equipment such as a gas purification apparatus used for the purification process, or a simple one can be used even when necessary.
  • FIG. 6 shows the results.
  • the horizontal axis in FIG. 6 is a wavelength range of a measurement range of 200 to 340 nm
  • the vertical axis is absorbance.
  • Curve C1 is the absorbance when not irradiated with ultraviolet light
  • curve C2 is the absorbance when irradiated with ultraviolet light for 1 minute
  • curve C3 is the absorbance when irradiated with ultraviolet light for 3 minutes.
  • the light having a wavelength of 240 ⁇ m or more had zero absorbance, and the light was not absorbed at all. In other words, the dissociation of nitrous acid and nitrogen by irradiation with light energy was not performed.
  • Table 1 shows changes in the concentration of nitrous acid-nitrogen obtained from the absorbance at a wavelength of 205 nm shown in FIG.
  • the concentration at which the irradiation time was zero was calculated as the saturation concentration (value at a water temperature of 25 ° C), and the relative values of the respective absorbances were multiplied. It can be seen that the concentration of nitrous acid and nitrogen is significantly reduced by irradiation for 3 minutes.
  • the maximum wavelength ( ⁇ max) of ozone is 260 nm.
  • the Krl excimer lamp was developed by the present inventors based on the characteristics of the UV absorption spectrum (cited from BritJAnaesth., 44, 310 (1972)) of the nitrous oxide aqueous solution shown in FIG. It is.
  • the horizontal axis represents wavelength and the vertical axis represents absorbance.
  • the UV absorption spectrum in this figure represents the absorption spectrum of water that has reached equilibrium with 100% nitrous acid, and water that has been equilibrated with helium is used as the reference cell.
  • the UV absorption spectrum of the aqueous nitrous oxide solution shows a peak exceeding 0.7 in the vicinity of 190 nm.
  • the emission wavelength of the low-pressure mercury lamp 16 is centered at 185 nm, and the absorbance at the wavelength of 185 nm is about less than 0.7, which is the peak of the UV absorption spectrum of nitrous acid-nitrogen aqueous solution. Since it is 0.05, the efficiency is extremely low.
  • an excimer lamp has characteristics suitable for the acid-oxidation reaction according to the present invention, such as good rise and fall.
  • the quartz tube is easily deteriorated by fluorine enclosed therein.
  • the fluoride excimer lamp has a problem that the compatibility between fluorine and the quartz tube is poor and the life is short.
  • the UV absorption spectrum of the aqueous nitrous oxide solution is steep near the peak, so even at a wavelength of 193 nm, the absorbance is greatly reduced compared to the peak value even though it is close to 190 nm. .
  • the present inventors have developed a Krl excimer lamp that emits light at an ultraviolet wavelength of 191 nm, which is extremely close to 190 nm, and adopted this lamp as a light source for the gas purification method and the gas purification device according to the present invention.
  • the Krl excimer lamp is manufactured by vaporizing solid iodine, measuring a predetermined amount, and enclosing it in a quartz tube.
  • the absorbance of the nitrous oxide aqueous solution with an emission wavelength of 19 lnm of the Krl excimer lamp L is about 0.65, which is close to the absorbance at the peak of the UV absorption spectrum of the aqueous nitrous oxide solution, and is efficient. Therefore, considering the generation of oxygen atoms due to the photodissociation of nitrous acid and nitrogen, for example, the Krl excimer lamp L is replaced with the low-pressure mercury lamp 16 because the low-pressure mercury lamp 16 has an absorbance of about 0.05 at an emission wavelength of 185 nm. Compared to conventional light sources, the generation efficiency of oxygen atoms is extremely high compared to conventional light sources.
  • the Krl excimer lamp has the general characteristics of the excimer lamp, which is suitable for the oxidation reaction according to the present invention, such that the rise and fall are good, and the quartz tube is deteriorated by the enclosed iodine. There is an advantage in that the life is long because the compatibility between KUGUI iodine and the quartz tube is good.
  • the ultraviolet light with a wavelength of 191 nm emitted by the Krl excimer lamp L is almost the same as the ultraviolet light with a wavelength of 185 nm emitted by the low-pressure mercury lamp, and is sufficiently large to decompose nitrous oxide and perform an oxidation reaction. Have energy.
  • the Krl excimer lamp L also has an excellent characteristic that ozone is not generated by light emission.
  • FIG. 8 shows the UV absorption spectrum of oxygen (cited from J. Chem. Phys., 21, 1206 (1953)). In the powerful spectrum, in the region from the wavelength of about 175 nm to the wavelength of about 200 nm, a very slight periodic fluctuation of the absorption coefficient is observed. Such a region is called the Syumanrunge band.
  • the wavelength of 191 nm emitted by the Krl excimer lamp L is included in the Syumann Runge band, corresponds to the so-called valley portion between the 5-0 band and the 4-0 band, and has a small absorption coefficient. Therefore, the dissociation of oxygen molecules with less absorption by oxygen molecules and the subsequent generation of ozone are small.
  • the Krl excimer lamp L is easy to handle because there is little generation of ozone as an environmental burden.
  • the wavelength of 185 nm of ultraviolet light emitted by a low-pressure mercury lamp is located on the 8-0 band in the Schmannmannge band and has a large absorption coefficient. Therefore, if there is an atmosphere between the low-pressure mercury lamp and the nitrous oxide solution, ultraviolet energy is absorbed by oxygen molecules and a large amount of ozone is generated immediately. The efficiency of the oxidation reaction is low, and the structure of the apparatus equipped with this becomes complicated, design problems, large size, and high cost.
  • the Krl excimer lamp L has the following advantages. In other words, even if the atmosphere exists between the Krl excimer lamp L and the nitrous acid solution, the ultraviolet light generated by the Krl excimer lamp L force is not absorbed by the oxygen molecules and the ultraviolet light is absorbed. Nitrous oxide can decompose nitrous oxide with high efficiency, which is difficult to weaken up to a nitrogen solution.
  • an ultraviolet ray is applied to a gas to be treated in a state where nitrous oxide (NO) contained in a nitrous oxide-containing solution is in contact with an oxidizable substance contained in the gas to be treated. It is a method of purifying gas by irradiating light to oxidize a substance to be oxidized and decompose and remove it.
  • NO nitrous oxide
  • the "oxidized substance” refers to, for example, an organic substance.
  • organic substances include oils and proteins that are decomposed by acid-acid reactions.
  • the gas to be treated includes, for example, indoor air to be cleaned, outside air taken into the room, exhaust from industrial activities such as factories, especially exhaust containing organic substances such as organic solvents, and decay caused by decay of organic substances such as living organisms.
  • the purified gas obtained by the purification treatment can be used in various applications and is useful. For example, clean room air or outside air can be used as room air!
  • An oxidation reaction performed by irradiating an oxidizable substance in contact with nitrous oxide with ultraviolet light has the following characteristics.
  • nitrous oxide When nitrous oxide is irradiated with ultraviolet light of 240 nm or less, dissociation of nitrous oxide occurs and atomic oxygen (O) is generated. When there is an oxidizable substance such as an organic substance, the oxidized substance is oxidized by the generated atomic oxygen (O).
  • the substance is oxidized only when irradiated with ultraviolet light, it can be said that nitrous acid nitrogen is stable unless irradiated with ultraviolet light. Therefore, if the light irradiation time is controlled, the oxidation time is controlled, and an acid-oxidation reaction can be caused only for a desired time. Further, by controlling the light irradiation region, the oxidation region can be controlled, and an acid-oxidation reaction can be caused only in a desired region.
  • the gas purification method of the present embodiment uses atomic oxygen generated by irradiation with ultraviolet light for the oxidation reaction. Since the oxygen has an extremely high acidity, organic substances are strongly decomposed. There are advantages to doing it.
  • nitrous oxide particularly a nitrous oxide-containing solution
  • nitrous oxide-containing solution has excellent characteristics that were not found in conventional oxide substances and thought to be contradictory. Yes.
  • nitrous acid-nitrogen has a property of high safety. Specifically, the aqueous nitrous oxide solution is harmless. Highly safe nitrous acid has the advantage of being easy to handle with low environmental impact.
  • nitrous acid-nitrogen having high safety has an advantage that a process for removing the purified gaseous nitrous acid-nitrogen is not necessarily required, and is preferable in terms of device fabrication. If a removal process such as a decomposition treatment is unnecessary, it is preferable because the gas purification process can be simplified.
  • nitrous oxide with excellent stability is easy to store for a long time.
  • Nitrous acid nitrogen is capable of causing an acid-acid reaction in a liquid, and has a characteristic that when an oxidation reaction is generated in a liquid, generation of ozone can be suppressed. Oxidation reactions occur all at once in the ultraviolet irradiation region, so that rapid purification treatment by oxidation is realized.
  • the gas purification method using nitric acid which is a strong acid as an oxidant, has a problem in that it is costly to take measures against corrosion of the device and costly to reduce the risk during production. is there. According to the gas purification apparatus of the present invention These points do not become a problem.
  • the nitrous oxide in the nitrous oxide-containing solution is contacted with the substance to be oxidized contained in the gas to be treated. It is necessary to let it be in a state where
  • Examples of the contacting step of bringing nitrous oxide into contact with the substance to be oxidized include a step of mixing a gas to be treated and a nitrous oxide-containing solution, and a step of causing nitrous oxide to be present in the gas to be treated. be able to.
  • a method of mixing the gas to be treated and the nitrous oxide-containing solution for example, a method of containing the gas to be treated and the nitrous oxide-containing solution in the same container, or a fluid in the container after containing the gas.
  • the method of mixing by stirring etc. can be mentioned.
  • Examples of the method for causing nitrous oxide to be present in the gas to be treated include a method for releasing the nitrous oxide-containing solution into the gas to be treated, a method for releasing the gas to be treated into the nitrous oxide-containing solution, and the like. Can be mentioned.
  • Examples of the method for releasing the nitrous oxide-containing solution into the gas to be treated include a so-called jetting method in which a nitrous acid-nitrogen solution is discharged, jetted, jetted or sprayed into the gas to be treated. it can.
  • Examples of the method for releasing the gas to be treated into the nitrous oxide-containing solution include a so-called jetting method in which the gas to be treated is discharged, jetted or jetted into the nitrous acid / nitrogen-containing solution. . More specifically, a publishing method can be mentioned.
  • the light source used in the gas purification method according to the present invention is preferably one that generates light having a wavelength of 240 nm or less.
  • Examples thereof include a high-pressure mercury lamp and a krypton iodine (Krl) excimer lamp (hereinafter referred to as a Krl excimer lamp).
  • the lamp output is not particularly limited. In general, when the same lamp is used, the rate of oxidative decomposition is affected by the output. In other words, when the lamp output is small, the rate of oxidative decomposition decreases, and conversely, when the lamp output is large, the rate of acidification decomposition increases.
  • the lamp output can be appropriately selected according to the desired oxidative decomposition rate.
  • a pretreatment step for improving the irradiation efficiency of ultraviolet light may be performed.
  • Examples of the pretreatment step include a dilution step of diluting the gas to be treated.
  • An example of the dilution step is the step of adding the treated gas or clean air that has been purified in advance.
  • the oxidative decomposition reaction during ultraviolet light irradiation is accelerated, and the purification rate and purification rate are improved.
  • gas purification was performed using a gas purification device.
  • the gas purification device generally has a configuration like the gas purification device shown in FIG. That is, this gas purifier will be described with reference to FIG. 9.
  • the lamp 25 was an electrolytically coupled high-frequency discharge lamp using krypton-iodine, that is, a Krl excimer lamp, and the output of the lamp 25 was 1200 watts. Details of the device configuration will be described later.
  • the gas purification apparatus of the present embodiment includes a contact unit for bringing an oxidant contained in a gas to be treated into contact with nitrous oxide contained in a nitrous oxide-containing solution, and the nitrous oxide. And a light source for irradiating the contacted acid-containing material with ultraviolet light.
  • the contact unit brings the oxidant substance such as an organic substance into contact with the nitrous oxide in the nitrous oxide-containing solution, and the oxidant substance in the state of contacting the nitrous oxide. Irradiate ultraviolet light from a light source to oxidize non-oxides, thereby oxidizing and decomposing oxidizable substances to purify the gas to be treated.
  • the contact unit includes a container for bringing the substance to be oxidized into contact with nitrous oxide in the nitrous oxide-containing solution.
  • the container include an open container having an opening and a sealed container used in a sealed state in terms of whether or not the force is open to the outside.
  • a mixed fluid when irradiating ultraviolet light to a fluid in which a gas to be treated and a nitrous oxide-containing solution are mixed (hereinafter referred to as a mixed fluid), it is determined whether or not the fluid can flow the mixed fluid.
  • a mixed fluid a fluid in which a gas to be treated and a nitrous oxide-containing solution are mixed
  • Examples of the open-type container include a processing tank for batch processing having an opening at the upper end, and a groove-shaped container having an upper end opened.
  • Examples of the sealed container include a tube-shaped container such as a sealed chamber and a pipe.
  • Examples of the storage container include the above-described batch processing chamber and chamber.
  • Examples of the fluid-type container include the above-described groove-shaped container and tube-shaped container.
  • the flow-through container preferably has a shape that ensures a wide ultraviolet light irradiation area.
  • the wide flow passage means a flow passage having a structure in which the flow passage width is wider than the depth of the mixed fluid flowing through the flow passage, for example, in the case of a flow-type and open container.
  • the ultraviolet light from the light source is applied to the mixed fluid in the container from the opening of the flow path.
  • a wide flow passage is, for example, a side corresponding to a surface irradiated with stronger ultraviolet light when the cross-sectional shape of the flow path is a quadrangle. It is a flow passage with a structure in which the thickness dimension of the channel cross section that intersects the irradiation direction is shorter than the width dimension.
  • examples of the sealed container include a container having a plurality of or many thin tubes, a flat cross-sectional tube having an elongated cross-sectional shape, and the like. In this way, even if the flow path cross-sectional area is the same, the ultraviolet light irradiation area is increased, and the ultraviolet light irradiation efficiency is improved.
  • a material for a sealed container such as a tube, a material having a higher ultraviolet light transmittance, such as glass, is preferred, and a material is more preferred.
  • the gas to be treated can be supplied from the opening, or the treated gas can be recovered from the opening, which is suitable for such treatment.
  • the sealed container is suitable as a container used in an apparatus in which the object to be treated is a gas, such as a gas purification apparatus.
  • the storage container is suitable, for example, when purifying a large amount of gas to be processed.
  • the fluid-type container is suitable for purification while circulating the gas to be treated and the mixed fluid.
  • the contact unit has a mixing means for positively contacting the oxidant contained in the gas to be treated with nitrous oxide.
  • Examples of the mixing means include a liquid supply unit that supplies a nitrous oxide-containing solution into the gas to be processed and a process gas supply unit that supplies the gas to be processed into the nitrous oxide-containing solution. It is preferable to have at least one of these! /.
  • a liquid supply device such as a liquid supply pipe for pouring a solution containing nitrous acid and nitrogen, such as an aqueous solution of nitrous acid and nitrogen, or nitrous oxide in the gas to be treated
  • a liquid discharger that discharges the solution.
  • the liquid discharger include a discharger, a sprayer, a sprayer, or a sprayer of a nitrous oxide-containing container.
  • Examples of the gas supply part to be processed include a gas discharger to be processed that discharges the gas to be processed into the nitrous oxide-containing solution.
  • Examples of the gas discharger to be processed include a discharger or an ejector for the gas to be processed.
  • the contact unit includes stirring means such as a stirrer for stirring the mixed fluid in order to ensure that the oxidant contained in the gas to be processed and nitrous oxide come into contact with each other! Good.
  • stirring means such as a stirrer for stirring the mixed fluid in order to ensure that the oxidant contained in the gas to be processed and nitrous oxide come into contact with each other! Good.
  • Examples of the gas purifier include a diluent supply unit that supplies a gas for dilution that improves the transparency of the gas to be processed into the gas to be processed.
  • Examples of the gas for dilution include treated gas and clean air. The diluent supply unit supplies at least one of these dilution gases. When the gas to be treated is diluted in this way, the ultraviolet light transmission efficiency is improved and the irradiation efficiency is improved.
  • a gas purification device particularly a gas purification device including a flow-type container
  • a device equipped with a circulation device that circulates a treated gas such as a mixed fluid or a gas to be treated that has been purified once.
  • a circulation device that circulates a treated gas such as a mixed fluid or a gas to be treated that has been purified once.
  • the purification process can be repeatedly performed on the gas to be treated.
  • Examples of the gas purification apparatus according to the present invention may further include a heating unit that heats the fluid to be processed and a cooling unit that cools the fluid to be processed.
  • the gas to be processed Mention may be made of those provided with a condenser for liquidizing the moisture in the treated gas.
  • the gas purification apparatus includes a light source that emits ultraviolet light.
  • the light source preferably generates light having a wavelength of 240 nm or less.
  • Examples include high-pressure mercury lamps and Krl excimer lamps.
  • the ultraviolet light irradiated by the Krl excimer lamp is easily absorbed by nitrous oxide, but has excellent resolution of nitrous oxide which is difficult to be absorbed by oxygen. Therefore, the oxidation reaction is performed efficiently, and gas purification is performed with high efficiency.
  • the generation of ozone is small, it is not always necessary to install a device for countermeasures against ozone, which contributes to simplifying and downsizing the structure of the gas purification device used when carrying out the gas purification method according to the present invention. .
  • the gas purification apparatus may include a controller that controls the output of the lamp.
  • An example of the controller is one that controls the output (illuminance) of ultraviolet light.
  • the output control method for example, on / off control can be mentioned.
  • Examples of the lamp for the light source that emits ultraviolet light include an external lamp installed outside the contact unit and an internal lamp installed inside the contact unit. More specifically, examples of the lamp include an external lamp installed outside the container of the contact unit and an internal lamp installed inside the container of the contact unit.
  • the container is an open-type container and the lamp is an external lamp
  • ultraviolet light is irradiated into the container from the opening of the container.
  • the open container has a portion made of an ultraviolet light transmissive material such as glass, the partial force container can be irradiated with ultraviolet light.
  • the container When the container is a sealed container and the lamp is an external lamp, the container needs to have a portion that also has an ultraviolet light transmitting material force. This partial force is also irradiated into the container by ultraviolet light.
  • the container material does not have to be an ultraviolet light transmissive material, regardless of whether it is an open type or a sealed type. Rather, a material that does not transmit ultraviolet light is preferred.
  • the lamp includes a fixed lamp fixed to the contact unit or the container, and a transfer lamp.
  • a moving lamp that is movably installed.
  • An example of the moving lamp is one that is integrated with a stirring device that stirs the fluid to be treated.
  • the contact unit may be provided with a plurality of containers for bringing the substance to be oxidized contained in the gas to be treated into contact with nitrous oxide.
  • a plurality of containers it is only necessary to irradiate ultraviolet light into one or more selected containers without the necessity of irradiating ultraviolet light of light source power into all the containers.
  • the first container for mixing the gas to be treated and the nitrous oxide-containing material, and the flow destination of the mixed fluid of the first container force. Irradiates the mixed fluid with ultraviolet light.
  • a second container for the purpose.
  • the gas purification apparatus 20 of the present embodiment includes a treatment tank (contact unit container) 21 to which a treatment target gas A to be purified is supplied and a treatment target gas A in the treatment tank 21.
  • Gas supply pipe 22 for supplying gas, nitrous oxide aqueous solution Nw tank 23, and nitrous acid / nitrogen aqueous solution Nw for supplying nitrous acid / nitrogen aqueous solution Nw from tank 23 to treatment tank 21
  • the tube 24 is provided with a lamp 25 for irradiating ultraviolet light into the processing tank 21 and a recovery device 26 for recovering the gas existing near the opening of the processing tank 21 by suction.
  • the treatment tank 21 is an open-type container having an opening at the upper end. And the processing tank 21 is provided with the discharge port 21a for discharging
  • the inner surface of the treatment tank 21 is processed with Teflon (registered trademark).
  • the gas supply pipe 22 to be processed is provided with an ejector 27 for jetting the gas to be processed on the downstream side thereof.
  • the ejector 27 includes a large number of ejection ports 27a for ejecting a gas to be processed.
  • the ejection port 27a communicates with the inside of the processing tank 21 through a vent 21b formed in the bottom surface of the processing tank 21. Yes. Therefore, the gas to be processed supplied through the gas supply pipe 2 to be processed is ejected from the ejector 27 into the treatment tank 21.
  • the lamp 25 is an electrolytic coupling type high frequency discharge lamp using krypton iodine, that is, a Kr I excimer lamp.
  • the output of lamp 25 was 1200 watts.
  • the collector 26 is installed with the suction port 26a facing the opening at the upper end of the treatment tank 21. ing.
  • the suction port 26a may be installed so as to cover the processing tank 21 or connected to the opening of the processing tank!
  • the nitrous acid / nitrogen aqueous solution Nw is caused to flow from the nitrous oxide supply pipe 24 into the treatment tank 21. Then, the gas to be processed A is supplied to the ejector 27 through the gas supply pipe 22 to be processed, and the gas to be processed A is ejected from the ejector 27 to the treatment tank 21. Then, the gas A to be treated is released into the nitrous oxide aqueous solution Nw in a so-called published state. As a result, an oxidizable substance such as an organic substance in the gas A to be treated comes into contact with the nitrous oxide dissolved in the nitrous oxide aqueous solution Nw.
  • the lamp 25 is turned on, and ultraviolet light is irradiated into the processing tank 21.
  • the nitrous acid-nitrogen dissolved in the nitrous acid-nitrogen aqueous solution Nw dissociates to produce atomic oxygen (O), and this atomic oxygen is converted into organic substances such as oil and protein (acidic substances).
  • O atomic oxygen
  • organic substances such as oil and protein (acidic substances).
  • the gas A to be treated is purified. That is, the organic substance is removed from the gas A to be processed by being decomposed into water, carbon dioxide, etc. by the acid.
  • the purified gas that is, the treated gas Ac of the gas to be treated A is released from the surface of the aqueous nitrous oxide solution Nw. Then, the released treated gas Ac is sucked into the collecting device 26 and collected.
  • the gas purification apparatus 30 of the present embodiment includes a sealed chamber 31, a nitrous oxide aqueous solution Nw tank 32, and a nitrous oxide aqueous solution Nw in the tank 32.
  • Nitrous oxide supply pipe 33 supplied to the chamber 31, a nitrous oxide aqueous solution Nw from the supply pipe 33, a jet 34 for ejecting the nitrous oxide aqueous solution Nw, a gas supply pipe 22 to be treated, and ultraviolet light toward the chamber 31.
  • a lamp 25 for irradiating.
  • the chamber 31 includes a drain port 31a for discharging the liquid in the chamber 31, and an exhaust port 3 lb for discharging the gas in the chamber 31.
  • the chamber 31 is a part of it. As described above, a glass transmission part 31c having excellent ultraviolet light transmission performance is provided. Therefore, ultraviolet light can be irradiated into the chamber 31 from the transmission part 31c.
  • the gas A to be treated is purified by such a gas purification device 30, the nitrous acid / nitrogen aqueous solution Nw is ejected into the chamber 31 by the ejector 34, and the gas to be treated is supplied. 22 Force Processed gas A is ejected into the chamber 31. As a result, a state is obtained in which the nitrous oxide in the aqueous nitrous oxide solution Nw contacts the oxidizable substance in the gas A to be treated.
  • the lamp 25 is turned on to irradiate the chamber 31 with ultraviolet light.
  • the substance to be oxidized contained in the gas to be treated A is decomposed by the oxidation reaction, and the gas to be treated A is purified.
  • the gas obtained by purification that is, the treated gas Ac of the gas to be treated A is discharged from the exhaust port 31b of the chamber 31 to the outside of the chamber 31 and collected.
  • the gas purification apparatus 20 of Example 1 is configured such that the opening force at the upper end of the treatment tank 21 can also irradiate the treatment tank 21 with ultraviolet light. Therefore, the material of the treatment tank 21 does not necessarily have to be excellent in ultraviolet light transmittance. However, the treatment tank 21 may have a high transmittance of ultraviolet light, particularly light having a wavelength of 190 ⁇ m, and the material may be used partially or entirely. When such a treatment tank 21 is used, the treatment gas A in the treatment tank 21 is purified by irradiating with ultraviolet light from the side or the lower side of the treatment tank 21 that only requires the opening force at the upper end of the treatment tank 21. Can be promoted.
  • the container of the gas purification apparatus 20 of Example 1 may be a force-sealed container that is a treatment tank 21 that is a so-called open container.
  • An example of the sealed container is a chamber 31 shown in FIG. Further, it may be composed of a container, that is, a processing tank 21 of the gas purification device 40 shown in FIG. 11 and a lid 21c that closes the upper end opening thereof.
  • the processing tank 21 and Z or part or all of the lid 21c thereof are made of a material having ultraviolet light transmission so that the processing tank 21 can be irradiated with ultraviolet light.
  • the lid 21c is made of glass.
  • the containers 21, 31 used in the gas purification apparatuses 20, 30 of the above embodiment are storage-type containers, but may be fluid-type containers. That is, a tube-shaped container 61 as shown in FIG. 12 may be used.
  • the container 61 is composed of a plurality of tubes 61a having a circular cross section, and a mixed fluid of the gas to be processed A and the nitrous oxide aqueous solution Nw is circulated in each tube 61a.
  • Each tube 61a is made of glass so that the mixed fluid in the tube 61a can be irradiated with external force ultraviolet light. Therefore, the gas to be treated A is purified by being irradiated with ultraviolet light when it flows through the tube 61a.
  • various methods can be used to recover the gas obtained by purification, that is, the processed gas A of the gas to be processed A.
  • the processed gas A of the gas to be processed A For example, as shown in FIG. A separation tank 61c is provided, and the treated gas Ac of the gas to be treated A is recovered from the exhaust port 6 Id connected to the storage tank 61c, and the spent liquid of the nitrous oxide aqueous solution Nw is removed from the drain port 61e. Let's collect it.
  • the container 62 shown in Fig. 13 may be used as the sealed and fluid type container.
  • the container 62 is formed of a tube 62a having a so-called flat cross-sectional shape in which the cross-sectional shape in the tube is an elongated shape, and is formed of a resin having ultraviolet light permeability.
  • a wider ultraviolet light irradiation area is secured even if the flow path cross-sectional area is the same. Further, since the channel thickness is thin, it becomes easy to transmit ultraviolet light to the mixed fluid flowing in the tubes 61a and 62a. For example, even if the mixed fluid is turbid, the entire gas to be processed can be irradiated with ultraviolet light. If the irradiated ultraviolet light passes through the mixed fluid, it is preferable because the entire mixed fluid flowing therethrough can be irradiated with ultraviolet light. Thus, if these containers 61 and 62 are used, the ultraviolet light irradiation efficiency can be improved.
  • the gas purifier 70 includes a circulator 71 that circulates the mixed fluid in a container such as the processing tank 21 so that the mixed fluid can be introduced into the processing tank 21 a plurality of times. But it ’s okay.
  • the circulator 71 includes a recovery pipe 71a, a three-way valve 71b installed in the middle, a circulation pipe 71c connected to the recovery pipe 71a through the three-way valve 71b, and a halfway of the circulation pipe 71c. And a downstream end of the circulation pipe 71c is connected to the supply pipe 22 of the gas A to be processed. If such a circulator 71 is installed, it is possible to irradiate ultraviolet light to the repeatedly processed gas Ac as necessary. The treated gas A can be purified with certainty.
  • a circulator 72 may be provided for the nitrous acid-nitrogen aqueous solution Nw.
  • This circulator 72 is similar to the circulator 71 of the treated gas Ac, and is connected to the recovery pipe 72a, a three-way valve 72b installed in the middle, and a circulation pipe connected to the recovery pipe 72a via the three-way valve 72b.
  • Pipe 72c and a circulation pump 72d installed in the middle of the circulation pipe 72c.
  • the downstream end of the circulation pipe 72c is connected to the tank 23 of the nitrous acid / nitrogen aqueous solution Nw. If such a circulator 72 is installed, the aqueous nitrous oxide solution Nw can be used repeatedly as necessary.
  • the mixing in the container is performed.
  • a movable mechanism that swings, vibrates, or rotates the container may be provided. A more homogeneous mixed fluid can be obtained by moving the container with a movable mechanism.
  • the gas purification device 80 may be provided with a stirring means for stirring the mixed fluid in a container such as the processing tank 21.
  • the gas purification device 80 shown in FIG. 15 includes a stirring tool 83 as stirring means.
  • the stirrer 83 includes a stir bar 83b extending in the horizontal direction at the tip of a bar-like support member 83a extending vertically.
  • the support member 83a can move up and down and rotate. Therefore, when the support member 83a is operated, the stirring rod 83b moves up and down and Z or rotates, and the mixed fluid in the processing tank 21 is stirred.
  • nitrous oxide can be brought into contact with the material to be oxidized for the entire mixed fluid.
  • the residence time of the gas to be treated A in the liquid is extended, so that the gas to be treated A is purified more reliably.
  • the supply device for supplying the gas to be processed A may be a mobile device that is not fixed to a container such as the gas purification device 90 or the processing tank 21, It may be portable.
  • an injector 94 that can be installed in or removed from the treatment tank 21 is used. This injector 94 is used.
  • the injector 94 injects the gas to be processed A into the nitrous oxide aqueous solution Nw that has flowed into the processing tank 21, and includes a large number of injection holes 94a. Therefore, the gas A Nitrous acid / nitrogen aqueous solution Nw can be supplied by publishing.
  • the injector 94 may be formed integrally with another device.
  • it may be formed integrally with the stirring rod 83b at the tip of the stirring tool 83 shown in FIG. With this configuration, it is possible to supply the gas A to be treated into the nitrous oxide aqueous solution Nw while stirring the nitrous oxide aqueous solution Nw with the stirring tool 84.
  • the lamp 25 is installed outside the container such as the processing tank 21 and the chamber 41.
  • the installation position of the lamp 25 is not limited to the outside of the container, and may be inside the container such as the treatment tank 21 as in the gas purification device 80 shown in FIG. If the installation position of the lamp 25 is in the container, the light source is installed very close to the gas to be processed A, and the ultraviolet light irradiation efficiency is improved.
  • the material of the container is not necessarily an ultraviolet light transmitting material, but is preferably a material that does not transmit ultraviolet light. If a material that does not transmit ultraviolet light is used, the ultraviolet light irradiation efficiency is improved.
  • the lamp 25 may be a movable or portable lamp that may not be fixed to the gas purifier or the container.
  • a lamp may be installed at the tip of the stirring tool 83 shown in FIG.
  • the mixed fluid can be uniformly mixed by stirring, and the entire mixed fluid can be uniformly irradiated with ultraviolet light.
  • the gas purification apparatus may include a controller that controls the execution and stop of the purification process by the on / off control of the Krl excimer lamp.
  • nitrous oxide is used as the substance to be oxidized contained in the liquid to be treated.
  • the "oxidized substance” refers to, for example, an organic substance.
  • organic substances include oils and proteins that are decomposed by acid-acid reactions. Therefore, according to the liquid purification method of the present invention, it is possible to purify various liquids to be treated containing an oxidizable substance such as an organic substance.
  • liquids to be treated include domestic waste liquids, industrial waste liquids, rainwater or groundwater, dams, lakes, rivers, and water taken by sea.
  • the purified liquid obtained by the purification process can be used in various applications and is useful.
  • it can be used as water for middle water used in so-called middle water.
  • middle water More specifically, it includes toilet water, cleaning water, dust prevention water to be sprayed to prevent dust from splashing, water for hitting water, cooling water used in various devices equipped with heating units, so-called miniature gardens and running water devices. Examples include running water used in displays.
  • the oxidation reaction can be easily controlled, corrosion of the equipment used for the liquid cleaner is minimized. In other words, the occurrence of equipment malfunctions due to corrosion is minimized. Therefore, there is an advantage that a countermeasure against corrosion is unnecessary for equipment such as a liquid purification device used when the liquid purification method according to the present invention is carried out.
  • the state in which the oxidant is brought into contact with nitrous oxide can be obtained, for example, by performing the following contact process.
  • the contacting step includes a step of mixing the liquid to be treated and nitrous oxide gas, a step of exposing the liquid to be treated to the nitrous acid-nitrogen gas, a step of allowing nitrous oxide to be present in the liquid to be treated, or nitrous acid. Examples thereof include a step of allowing an oxidizable substance to be present in a nitrous acid-containing nitrogen gas.
  • nitrous oxide gas refers to nitrous oxide that is not limited to nitrous oxide alone. It also includes gas containing elemental gases.
  • the liquid to be treated and the nitrous oxide gas for example, the liquid to be treated and at least one of the nitrous oxide gas and the nitrous oxide-containing solution are the same.
  • the method of accommodating in a container and the method of further stirring after accommodation can be mentioned.
  • Examples of the method of exposing the liquid to be treated to nitrous acid nitrogen gas include a method of covering nitrous acid nitrogen gas in the atmosphere of the liquid to be treated.
  • Examples of the method for allowing nitrous oxide to be present in the liquid to be treated include a method for releasing nitrous oxide gas into the liquid to be treated, and a method for adding nitrous oxide-containing water to the liquid to be treated. be able to.
  • the method for releasing nitrous acid nitrogen gas into the liquid to be treated includes, for example, a so-called jetting method in which nitrous acid nitrogen gas is discharged, jetted or jetted into the liquid to be treated. Can do. More specifically, a publishing method can be mentioned.
  • Examples of the method for causing the substance to be oxidized to exist in the nitrous acid-nitrogen gas include a method of releasing the liquid to be treated into the nitrous acid-nitrogen gas. More specifically, a so-called jetting method in which the liquid to be treated is discharged, jetted, jetted or sprayed can be mentioned.
  • the method of bringing nitrous oxide into contact with the oxidant contained in the liquid to be treated can be broadly classified by focusing on the state of the liquid to be treated.
  • a method of contacting nitrous oxide with nitrous oxide, a method of bringing nitrous oxide into contact with an oxidizable substance in a vapor of the liquid to be treated, and an oxidization contained in a gas-liquid coexisting material in which a part of the liquid to be treated is vaporized It is roughly classified into the method of contacting the substance with nitrous oxide.
  • the substance to be oxidized is brought into contact with nitrous oxide in a state in which the liquid to be treated remains in a liquid state, a gas state, or a gas-liquid two-phase state.
  • Examples of suitable methods for bringing part or all of the liquid to be treated into a gas state include a method of spraying, a method of vaporizing by heating, and a method of reducing the pressure of the liquid to be treated. .
  • the lamp (light source) used in the liquid purification method according to the present invention preferably generates light having a wavelength of 240 nm or less.
  • high-pressure mercury lamps and krypton iodine (Krl) Excimer lamps (hereinafter referred to as Krl excimer lamps) can be mentioned.
  • the lamp output is not particularly limited. In general, when the same lamp is used, the rate of oxidative decomposition is affected by the output. In other words, when the lamp output is small, the rate of oxidative decomposition decreases, and conversely, when the lamp output is large, the rate of acid decomposition increases.
  • the lamp output can be appropriately selected according to the desired oxidative decomposition rate.
  • a pretreatment step for improving the irradiation efficiency of ultraviolet light may be performed.
  • Examples of the pretreatment step include a dilution step of diluting the liquid to be treated.
  • Examples of the dilution step include a step of adding water and a step of adding nitrous oxide-containing water.
  • the diluted liquid to be processed has improved light transmittance. Therefore, the irradiation efficiency of ultraviolet light is improved.
  • a liquid purifier 11 having the same configuration as that of Example 1 was used except that the lamp 13 was a Krl excimer lamp.
  • a nitrous oxide aqueous solution used for purification was also prepared.
  • the concentration of nitrous acid nitrogen in the solution was lOOOppm.
  • the same methylene blue aqueous solution as that purified in Example 1 was subjected to the purification treatment.
  • a methylene blue aqueous solution and a nitrous oxide aqueous solution were put into the container 12 and mixed to obtain a mixed solution 14.
  • ramp 13 was turned on and the ultraviolet-ray was irradiated to the liquid mixture 14 in the container 12, and the cleansing process was performed.
  • the ambient temperature of the place where the liquid purifier 11 was installed was 24 ° C.
  • the purification performance was equivalent to or better than that of the apparatus of Example 1 using a high-pressure mercury lamp.
  • the trichlorethylene concentration which was present in a small amount in the mixed solution before the ultraviolet light irradiation, was lowered in the solution after the ultraviolet light irradiation.
  • the liquid purification apparatus of the present embodiment includes a contact unit for bringing an oxidant contained in a liquid to be treated into contact with nitrous oxide, and a light source for irradiating the oxidant with contact with the nitrous oxide with ultraviolet light. are provided.
  • nitrous oxide is contacted with an oxidizable substance such as an organic substance in the contact unit.
  • the non-oxide is oxidized by irradiating UV light from the light source to the oxidant in contact with the nitrous oxide, thereby oxidizing and decomposing the oxidant to purify the liquid to be treated. .
  • the contact unit for bringing the substance to be oxidized contained in the liquid to be treated into contact with nitrous oxide includes a container for bringing the substance to be oxidized into contact with nitrous oxide.
  • Examples of the container include an open container having an opening and a sealed container used in a sealed state from the viewpoint of whether or not the container is open to the outside.
  • a fluid in which the liquid to be treated and Z or a vaporized product thereof and at least one of nitrous acid-nitrogen gas, nitrous oxide gas, or nitrous acid-nitrogen-containing solution are mixed (
  • a storage type container and a fluid type container can be mentioned from the viewpoint of whether or not the mixed fluid is flowed.
  • Examples of the open-type container include a processing tank for batch processing having an opening at the upper end, and a groove-shaped container having an upper end opened.
  • Examples of the sealed container include a tube-shaped container such as a sealed chamber and a pipe.
  • Examples of the storage container include the above-described batch processing chamber and chamber.
  • Examples of the fluid-type container include the above-described groove-shaped container and tube-shaped container.
  • the flow-through container preferably has a shape that ensures a wide ultraviolet light irradiation area.
  • the wide flow passage means a flow passage having a structure in which the flow passage width is wider than the depth of the mixed fluid flowing through the flow passage, for example, in the case of a flow-type and open container.
  • the ultraviolet light from the light source is applied to the mixed fluid in the container from the opening of the flow path.
  • a wide flow passage is, for example, a side corresponding to a surface irradiated with stronger ultraviolet light when the cross-sectional shape of the flow path is a quadrangle. It is a flow passage with a structure in which the thickness dimension of the channel cross section that intersects the irradiation direction is shorter than the width dimension.
  • examples of the sealed container include a container having a plurality of or many thin tubes, a flat cross-sectional tube having an elongated cross-sectional shape, and the like. In this way, even if the flow path cross-sectional area is the same, the ultraviolet light irradiation area is increased, and the ultraviolet light irradiation efficiency is improved.
  • a material for a sealed container such as a tube, a material having a higher ultraviolet light transmittance, such as glass, is preferred, and a material is more preferred.
  • the open-type container is suitable as a container used when the treatment liquid is subjected to purification treatment in a liquid state or when the purification treatment is performed using a nitrous oxide-containing solution.
  • the hermetic container is suitable as a container used when purifying the vaporized material to be treated or when performing purification using nitrous oxide gas.
  • the storage container is suitable for purifying a large amount of liquid to be treated, for example.
  • the fluid-type container is suitable for purifying while circulating the liquid to be treated and the above mixed fluid.
  • an open and fluidized container is used when using a method in which the liquid to be treated is exposed to nitrous acid or nitrogen gas, or when purifying while circulating the liquid to be treated. Speak properly.
  • a closed and sealed container is used when circulating the vapor of the liquid to be treated or when using nitrous oxide gas and purifying the liquid to be treated or the vaporized liquid while circulating it. Is suitable.
  • the contact unit is preferably one having a mixing means for positively contacting the oxidized substance contained in the liquid to be treated and nitrous oxide.
  • a liquid supply unit for supplying a nitrous oxide-containing solution into the liquid to be processed or the vaporized liquid to be processed, and nitrous oxide gas to be supplied into the liquid to be processed or the vaporized liquid to be processed.
  • Gas supply unit to supply, liquid to be processed to supply liquid to be processed in nitrous oxide-containing solution or nitrous oxide gas, vaporized liquid to be processed in nitrous oxide-containing solution or nitrous oxide gas
  • the liquid supply unit includes, for example, a liquid feeder such as a liquid supply pipe for pouring a solution containing nitrous acid and nitrogen, such as a nitrous acid and nitrogen aqueous solution, into the container, Mention may be made of a liquid discharger that discharges a nitrous oxide-containing solution into the vapor.
  • a liquid discharger include a discharger, a sprayer, a sprayer, or a sprayer of a nitrous oxide-containing container.
  • Examples of the gas supply unit include a gas discharger that discharges nitrous oxide gas into the liquid to be processed and the vaporized liquid of the liquid to be processed.
  • a gas discharger for example, gas
  • gas There may be mentioned a discharger, an ejector or an injector. More specifically, examples of the discharger that discharges gas into the liquid to be treated include so-called publishing equipment. Further, when nitrous oxide gas is released toward the liquid to be treated, the liquid to be treated is placed in the nitrous oxide gas atmosphere.
  • the treatment liquid supply section includes, for example, a liquid supply device such as a treatment liquid supply pipe for pouring the treatment liquid into the container, or a treatment liquid discharger that discharges the treatment liquid into nitrous oxide gas.
  • a liquid supply device such as a treatment liquid supply pipe for pouring the treatment liquid into the container
  • a treatment liquid discharger that discharges the treatment liquid into nitrous oxide gas.
  • the treatment liquid discharger include a discharge liquid, an ejector, an injector, or a sprayer of the treatment liquid.
  • Examples of the vaporized substance supply unit include a vaporized substance discharger that discharges vaporized substances to be treated into a nitrous oxide-containing solution and nitrous oxide gas.
  • Examples of the vaporizer ejector include a sprayer of a liquid to be treated, a vaporizer ejector, and an injector. More specifically, examples of the discharger that discharges the vaporized material into the nitrous oxide-containing solution include a so-called publishing device.
  • the vaporized substance supply unit includes not only those in which all substances to be supplied are vaporized substances to be treated but also those in which at least a part is vaporized substances. Examples of means for vaporizing part or all of the liquid to be treated include a sprayer, a heater, and a decompressor.
  • the contact unit includes stirring means such as a stirrer for stirring the mixed fluid in order to reliably contact the oxidant contained in the liquid to be treated with nitrous oxide! It's good.
  • stirring means such as a stirrer for stirring the mixed fluid in order to reliably contact the oxidant contained in the liquid to be treated with nitrous oxide! It's good.
  • Examples of the liquid purifier include a diluent supply unit that supplies a diluent for improving the transparency of the liquid to be processed into the liquid to be processed.
  • Examples of the diluent include water and water containing nitrous acid and nitrogen. The diluent supply unit supplies at least one of these diluents.
  • liquid purification devices particularly liquid purification devices including flow-type containers, include those equipped with a circulation device that circulates the liquid to be treated that has been exposed to the mixed fluid or nitrous acid-nitrogen gas. be able to. By circulating, the liquid to be treated can be repeatedly purified.
  • Examples of the liquid purification apparatus according to the present invention may further include a heating unit that heats the fluid to be processed and a cooling unit that cools the fluid to be processed.
  • the fluid to be treated is a gas
  • a fluid having a condenser for liquidating the fluid to be treated can be mentioned.
  • the liquid purifier according to the present invention includes a light source for irradiating ultraviolet light.
  • the light source preferably generates light having a wavelength of 240 nm or less.
  • Examples include high-pressure mercury lamps and Krl excimer lamps.
  • the liquid purification apparatus may include a controller for controlling the output of the lamp.
  • An example of the controller is one that controls the output (illuminance) of ultraviolet light.
  • the output control method for example, on / off control can be mentioned.
  • Examples of the lamp for the light source that emits ultraviolet light include an external lamp installed outside the contact unit and an internal lamp installed inside the contact unit. More specifically, examples of the lamp include an external lamp installed outside the container of the contact unit and an internal lamp installed inside the container of the contact unit.
  • the container is an open-type container and the lamp is an external lamp
  • ultraviolet light is irradiated into the container from the opening of the container.
  • the open container has a portion made of an ultraviolet light transmissive material such as glass, the partial force container can be irradiated with ultraviolet light.
  • the container When the container is a hermetically sealed container and the lamp is an external lamp, the container needs to have a portion that also has an ultraviolet light transmitting material force. This partial force is also irradiated into the container by ultraviolet light.
  • the material of the container does not need to be an ultraviolet light transmissive material, regardless of whether it is an open type or a sealed type. Rather, a material that does not transmit ultraviolet light is preferred.
  • examples of the lamp include a fixed lamp fixed to the contact unit or the container, and a moving lamp installed so as to be movable.
  • An example of the moving lamp is one that is integrated with a stirring device that stirs the fluid to be treated.
  • the contact unit may be provided with a plurality of containers for bringing the substance to be oxidized contained in the liquid to be treated into contact with nitrous oxide. And if you have more than one container, It is not necessary to irradiate the container with ultraviolet light of light source power. It is sufficient that one or more selected containers are irradiated with ultraviolet light. Specifically, it is the first container for mixing the liquid to be treated and the nitrous oxide-containing material, and the outlet of the mixed fluid such as the first container force, and ultraviolet light is applied to the inflowed mixed fluid. Mention may be made of a second container for irradiation.
  • the liquid purification apparatus 120 of the present embodiment includes a treatment tank (contact unit container) 121 to which a treatment liquid F to be purified is supplied, and a treatment liquid F to the treatment tank 121.
  • a treatment tank (contact unit container) 121 to which a treatment liquid F to be purified is supplied
  • a treatment liquid F to the treatment tank 121 Liquid supply pipe 122 to be supplied, a nitrous oxide aqueous solution Nw tank 123 in which nitrous oxide is dissolved, and a nitrous oxide aqueous solution Nw supplied from the tank 123 to the treatment tank 121
  • a nitrogen supply pipe 124 and a lamp 125 for irradiating ultraviolet light toward the inside of the treatment tank 121 are provided.
  • the treatment tank 121 is an open-type container having an opening at the upper end.
  • the processing tank 121 includes a discharge port 121a for discharging the liquid in the processing tank 121.
  • the inner surface of the treatment tank 121 is processed with Teflon (registered trademark)!
  • the lamp 125 is an electrolytically coupled high-frequency discharge lamp using krypton-iodine, that is, a Krl excimer lamp.
  • the output of lamp 125 was 1200 watts.
  • the liquid to be treated is supplied to the treatment tank 121.
  • the liquid to be treated F is introduced from 122 and the nitrous acid-nitrogen aqueous solution Nw is introduced from the nitrous acid-nitrogen supply pipe 124.
  • the liquid F and the nitrous acid aqueous solution Nw are mixed in the treatment tank 121, and the nitrous oxide in the aqueous nitrous oxide solution Nw comes into contact with the oxidized material in the liquid F to be processed.
  • a state is obtained.
  • the mixed fluid M accommodated in the treatment tank 121 is a liquid.
  • the lamp 125 is turned on and ultraviolet light is irradiated toward the inside of the processing tank 121.
  • the nitrous oxide dissolved in the mixed fluid M in the ultraviolet light irradiation region dissociates and the atomic acid is dissociated.
  • Elemental oxygen (O) is generated, and this atomic oxygen is decomposed by strongly oxidizing the organic matter (oxidized substance) with oil and protein! That is, the organic substance is decomposed into water, carbon dioxide, etc. by oxidation, so that the liquid to be treated is removed.
  • the substance to be oxidized contained in the liquid F to be processed is decomposed by the oxidation reaction, and the liquid F to be processed is purified. Thereafter, the treated liquid in the treatment tank 121 is discharged from the discharge port 121a, and the treated liquid is recovered.
  • liquid purifier according to the next embodiment will be described. Note that the same components as those of the liquid purification device 120 (Example 1 of the liquid purification device) are denoted by the same reference numerals, and the description thereof is omitted. The same applies to the embodiments described below.
  • the liquid purification apparatus 130 of the present embodiment includes a treatment tank 121, a treatment liquid supply pipe 122 that supplies a treatment liquid F, and nitrous acid nitrogen gas Ng.
  • the treatment tank 121 is provided with a vent hole 121b on the bottom surface thereof, and the gas ejector 132 is provided with a gas jet hole 132a connected to the vent hole 121b. Therefore, nitrous acid nitrogen gas Ng can be supplied into the treatment tank 121 from the gas ejection holes 132a.
  • the lamp 125 was a Krl excimer lamp.
  • the liquid to be processed F is caused to flow into the processing tank 121. Then, nitrous acid nitrogen gas Ng is ejected from the gas ejector 132. Then, nitrous oxide gas Ng is released into the liquid F to be treated in a so-called publishing state. As a result, nitrous oxide is dissolved in the liquid F to be treated, and a state in which the nitrous oxide is in contact with the substance to be oxidized in the liquid F to be processed is obtained.
  • the lamp 125 is turned on and ultraviolet light is irradiated into the processing tank 121.
  • the substance to be oxidized contained in the liquid to be treated F is decomposed by the oxidation reaction, and the liquid to be treated F is purified.
  • the mixed fluid M in the treatment tank 121 is discharged from the discharge port 121a, and the processed liquid is recovered.
  • Example 3 of liquid purifier> Next, a liquid purification apparatus of Example 3 will be described.
  • the liquid purification apparatus 140 of the present embodiment includes a sealed chamber 141, a gas cylinder 142 storing nitrous oxide gas Ng, and a nitrous oxide in the gas cylinder 142.
  • Gas supply pipe part 143 for supplying elementary gas Ng to chamber 141, liquid to be processed supply pipe 122, liquid ejector 144 for injecting liquid F to be processed into chamber 141, and ultraviolet light toward chamber 141 A lamp 125 for irradiating is provided.
  • the chamber 141 includes a discharge port 141a for discharging the fluid in the chamber 141. Further, the chamber 141 includes a glass transmission part 14 lb having excellent ultraviolet light transmission performance. Therefore, ultraviolet light can be irradiated into the chamber 141 from the transmission part 141b.
  • the liquid F to be treated is purified with such a liquid purification apparatus 140, first, the chamber 141 is filled with nitrous acid nitrogen gas Ng. Then, the liquid F to be treated is ejected from the liquid ejector 144 into the chamber 141. As a result, the liquid F to be treated is ejected into the nitrous oxide gas Ng filled in the chamber 141. As a result, a state is obtained in which the nitrous oxide in the aqueous nitrous acid solution contacts the oxidizable substance in the liquid F to be treated. In this case, the mixed fluid M accommodated in the chamber 141 is in a gas state or a gas-liquid mixed state.
  • the lamp 125 is turned on to irradiate the chamber 141 with ultraviolet light.
  • the substance to be oxidized contained in the liquid to be treated F is decomposed by the oxidation reaction, and the liquid to be treated F is purified.
  • the mixed fluid M in the chamber 141 is discharged from the discharge port 141a. Thereby, the treated liquid is recovered.
  • the opening force at the upper end of the treatment tank 121 can also irradiate the treatment tank 121 with ultraviolet light. Therefore, the material of the processing tank 121 does not necessarily have to be excellent in ultraviolet light transmittance.
  • a material in which a material having a high transmittance of ultraviolet light, particularly light having a wavelength of 190 nm is used in part or in whole may be used. If such a treatment tank 121 is used, ultraviolet light is irradiated from the side or lower side of the treatment tank 121 only from the opening at the upper end of the treatment tank 121, so that the inside of the treatment tank 121 is irradiated. It is possible to promote the purification of the liquid F to be treated.
  • the containers of the liquid purification apparatuses 120 and 130 of Example 1 and Example 2 may be force-sealed containers that are processing tanks 121 that are so-called open containers.
  • An example of the sealed container is the chamber 141 of Example 3.
  • it may be a sealed container including a processing tank 121 and a lid 121c that closes the upper end opening thereof.
  • the processing tank 121 and Z or a part or all of the lid body thereof are made of a material having ultraviolet light transmittance so that the processing tank 121 can be irradiated with ultraviolet light.
  • the lid 121c is made of glass.
  • a connection tool (not shown) that can removably connect the tips of the liquid supply pipe 122 and the nitrous oxide supply pipe 124 is attached to the lid 121c, and the lid 121c is attached to the treatment tank 121.
  • the nitrous oxide aqueous solution and the nitrous acid / nitrogen gas may be supplied into the treatment tank 121 in a state where it is attached and sealed. If the treatment tank 121 can be supplied in a sealed state, nitrous oxide does not leak and can be used effectively. Note that the case where a sealed container such as the chamber 141 of the third embodiment is used has already been described in the third embodiment, and a description thereof will be omitted.
  • the container used in the liquid purification apparatus of the above embodiment is a storage-type container, but may be a fluid-type container. That is, a groove-shaped container 151 as shown in FIG. In this groove-shaped container 151, the liquid F to be treated and the aqueous nitrous oxide solution Nw flow in the container toward the discharge part 151a on the downstream side of the container 151 that does not stay in the container. .
  • a container 151 shown in FIG. 21 includes a rotating shaft 151b extending in the horizontal direction on the upstream side portion thereof.
  • the rotary shaft 151b is supported by a support member (not shown), and can move up and down the discharge portion 151a on the downstream side of the container 151. Therefore, move the discharge part 151a upward.
  • the flow rate of the mixed fluid M in the container 151 decreases, and when the discharge part 151a is moved downward, the flow rate of the mixed fluid M increases.
  • the fluid container may be an open container such as the groove-shaped container 151, but may be a closed fluid container. That is, it may be a tube-shaped container 161 as shown in FIG.
  • the container 161 is composed of a plurality of tubes 161a having a circular cross section, and the mixed fluid M is circulated in each tube 161a.
  • Each tube 161a is made of glass so that the fluid in the tube can be irradiated with external force ultraviolet light.
  • a container 162 shown in Fig. 23 may be used as a sealed and fluid type container.
  • the container 162 is made of a tube 162a having a so-called flat cross-section with an elongated cross-sectional shape inside the tube, and is made of a resin having ultraviolet light permeability.
  • the liquid purification apparatus 170 includes a circulator 171 that circulates the mixed fluid M in a container such as the processing tank 121 so that it can be introduced into the processing tank 121 a plurality of times. It may be prepared.
  • the circulator 171 includes a recovery pipe 171a, a three-way valve 171b installed in the middle, a circulation pipe 171c connected to the recovery pipe 171a via the three-way valve 171b, and a circulation pipe 17 lc.
  • a circulation pump 17 Id installed in the middle is connected, and the downstream end of the circulation pipe 17 lc is connected to the supply pipe 122 of the liquid F to be treated. If such a circulator 171 is installed, the mixed fluid M can be repeatedly irradiated with ultraviolet light as necessary, and the liquid F to be treated can be purified more reliably.
  • the liquid purification apparatus 180 may include a plurality of containers, specifically, two containers.
  • the liquid purifier 180 is a container having a groove shape into which the mixed fluid M discharged from the treatment tank 121 and its discharge port 121a flows as containers. 181.
  • the groove-shaped container 181 has the same shape as the groove-shaped container 151 described with reference to FIG. 21, and includes a rotation shaft 181a corresponding to the rotation shaft 151b. Therefore, detailed description is omitted.
  • the liquid purification apparatus 180 mixes the liquid F to be treated and the aqueous nitrous oxide solution Nw.
  • the obtained mixed fluid M is poured into a downstream groove-shaped container 181 where it is irradiated with ultraviolet light to be purified.
  • the mixed fluid M can be reliably irradiated with ultraviolet light in the groove-shaped container 181, and the liquid F to be treated can be reliably purified.
  • the mixing in the container is performed.
  • a means for more uniformly mixing the fluid M it may be provided with a movable mechanism that swings, vibrates or rotates the container. A more homogeneous mixed fluid can be obtained by moving the container with a movable mechanism.
  • the liquid purifier 191 may be provided with a stirring means for stirring the mixed fluid M in a container such as the processing tank 121.
  • a liquid purifying device 191 shown in FIG. 26 includes a stirring tool 183 as stirring means.
  • the stirrer 183 includes a stir bar 183b extending in the horizontal direction at the tip of a bar-like support member 183a extending vertically.
  • the support member 183a can move up and down and rotate. Therefore, when the support member 183a is operated, the stirring rod 183b moves up and down and Z or rotates, and the mixed fluid M in the treatment tank 121 is stirred. As a result, for the entire mixed fluid M, the oxidized material can be contacted with nitrous acid and nitrogen.
  • the liquid purification apparatus 191 may be further equipped with a dilute supply pipe 184 that supplies the dilute liquid W of the liquid F to be treated.
  • the diluent is water, but in addition, an aqueous solution of nitrous acid and nitrogen can be mentioned.
  • the diluent supply pipe 184 supplies at least one of these diluents.
  • the case where the liquid F is low in the UV light transmittance, such as when the liquid F to be treated is cloudy, is considered. In such a case, when a diluent is added, the ultraviolet light transmittance of the mixed fluid M is improved by the dilution, and the purification efficiency is improved. improves.
  • the liquid purification apparatus may further include a heating unit that heats the mixed fluid M and a cooling unit that cools the mixed fluid M.
  • the liquid purification apparatus includes a condenser that liquid-cleans the mixed fluid M after the purification treatment.
  • the lamp 125 is installed outside the container such as the processing tank 121 and the chamber 141.
  • the installation position of the lamp 125 is not limited to the outside of the container, and may be inside the container such as the processing tank 121 as in the liquid purification apparatus 192 shown in FIG. If the installation position of the lamp 125 is in the container, the light source is installed very close to the liquid F to be processed, and the ultraviolet light irradiation efficiency is improved.
  • the material of the container is not necessarily an ultraviolet light transmitting material, but is preferably a material that does not transmit ultraviolet light. If a material that does not transmit ultraviolet light is used, the efficiency of irradiation with ultraviolet light is improved.
  • the lamp 125 may be a movable or portable lamp that may not be fixed to the liquid purification apparatus 193 or the container.
  • the lamp 125 is installed at the tip of the stirring tool 183.
  • the mixed fluid M can be uniformly mixed by stirring, and the entire mixed fluid M can be uniformly irradiated with ultraviolet light.
  • the feeder for supplying the nitrous oxide gas or the nitrous oxide aqueous solution is not fixed to the container such as the liquid purifier 193 or the treatment tank 121. It can be mobile or portable.
  • the stirrer 183 is also an injector 185 that supplies nitrous acid nitrogen gas Ng. That is, the stirring tool 183 includes a hollow support member 183a and a hollow stirring bar 183b, and nitrous acid and nitrogen gas can be circulated through the support member 183a and the stirring bar 183b! / , Ru
  • the stirring rod 183b is formed with a number of injection holes (not shown) for injecting the nitrous acid nitrogen gas Ng.
  • the stirring tool 183 is also a publishing device for nitrous acid nitrogen gas Ng. Therefore, while stirring with a stirrer 183, nitrous acid nitrogen gas N in the mixed fluid M g can be supplied by publishing.
  • the Krl excimer lamp 125 is excellent in the light intensity rising performance at the start of irradiation and the light intensity falling performance at the end of irradiation. Therefore, by turning on / off the lamp 125, it is possible to easily perform on / off control of the acid-acid reaction. Therefore, the liquid purification apparatus may include a controller that controls the execution and stop of the purification process by the on / off control of the Krl excimer lamp.
  • the nitrous oxide gas can be supplied by a gas cylinder of compressed gas such as liquid gas filled in the high-pressure vessel, and this can be installed in the vicinity of the fluid purification device. It can also be supplied from a large-scale high-pressure vessel at a factory or factory using centralized piping. A small container such as a cassette-type gas cylinder may be installed and supplied to the fluid purification device, and a nitrous oxide production device is installed in the fluid purification device, in the vicinity of the fluid purification device, or in the workplace, and is produced by this production device. Nitrous acid nitrogen may be directly supplied to a container such as a processing tank in the fluid purification device.
  • Nitrous acid nitrogen gas can be produced as follows. Industrial methods include (1) ammonia oxidation method in which ammonia is heated at 200 ° C to 500 ° C in the presence of a metal oxide catalyst using oxygen or air, and (2) ammonia nitrate. Pyrolysis of ammonia, or ammonium nitrate decomposition method in which sodium nitrate is heated to produce a mixture of ammonium sulfate. (3) Sulfuric acid is divided into two or more stages to supply, or sulfuric acid is supplied. The method of reacting sulfamic acid and nitric acid while adding can be used on a practical scale.
  • nitrous acid and nitrogen can be generated by passing ozone gas and nitrogen gas through glass glass used in gas chromatography and the like, and a small amount of nitrous acid and nitrogen gas is efficiently produced. Suitable for producing well.
  • a diffuser plate or a diffuser tube made of a porous material made of plastic or ceramic is placed so as to be immersed in the solvent;
  • a method of supplying nitrous acid / nitrogen gas to this diffuser plate or diffuser tube from a gas cylinder or generator of the gas generator and publishing it in the solvent (2) Pressurized solvent using an ejector Using a negative nozzle, the nitrous oxide gas is sucked into the solvent and dissolved, and a pressurized tray tower, packed tower, shower tower, bubble tower, etc. are used.
  • Nitrous oxide nitrogen gas and solvent are brought into contact with each other and dissolved, and the solvent in contact with nitrous acid nitrogen gas pressurized in a pressure vessel is stirred and dissolved, pressurized in a small pressure vessel
  • Porous made of hydrophobic resin such as polytetrafluoroethylene
  • Uses membrane hollow fiber to improve hydrophobicity of resin and gas permeability of pores To dissolve the gas in the liquid, or to dissolve the gas that has permeated the resin in the liquid using a non-porous gas permeable membrane hollow fiber using the gas dissolution / diffusion mechanism inside the resin.
  • these methods can be used in combination with an ultrasonic wave or a magnetic field having a gradient to improve the dissolution amount and dissolution rate of the nitrous acid-nitrogen gas in the solvent.
  • a method for dissolving nitrous acid nitrogen gas in a solvent in a short time with efficiency that is wasted It is preferable to use a hollow fiber membrane.
  • Nitrous oxide-nitrogen in the solvent is almost constant by dissolving the nitrous acid-nitrogen gas in the solvent by the above-mentioned predetermined method and controlling the solution time, gas supply pressure, etc. It is possible to maintain the concentration. Therefore, there is an advantage that it is not always necessary to detect, record and manage the nitrous oxide concentration in the solvent in the fluid purification device.
  • nitrous oxide concentration can be performed as follows. (1) Has two or more electrolytic electrodes, working electrode and counter electrode, and if necessary, regenerative electrode, an ion exchange membrane that partitions the electrodes, and an electrolyte containing halogen ions Electrolysis method using an electrolytic cell that measures the current flowing when electrolyzing nitrous oxide or the total number of cron at that time, and (2) ultraviolet light having a predetermined wavelength containing nitrous oxide A spectrophotometric method in which the cell stored in a solvent is irradiated and the absorbance is measured by a light receiving system placed across the cell and facing the light source.
  • TN all specified in JIS K0102
  • Nonrogen Non-dispersed infrared absorption by transferring nitrous oxide dissolved in the solvent into the gas phase by pumping and diffusing inert gas in the nitrous oxide-containing solvent
  • a method of measuring the concentration of nitrous oxide in the gas phase using an ultraviolet light absorption altitude method or an electrochemical measurement sensor based on an oxygen ion conductive solid decomposition product It can be used for management of a state before supply of a solution such as a nitrous oxide aqueous solution used in the fluid purification method or the fluid purification apparatus according to the present invention, or for solution management in a container such as a treatment tank.
  • the fluid purification device does not need to be equipped with a device for decomposing and removing nitrous oxide.
  • nitrous acid nitrogen inhibits these treatments. There is nothing to do. Therefore, it is possible to carry out sludge treatment and the like without treating nitrous acid nitrogen in the treated liquid. Furthermore, nitrous oxide does not cause abnormal decomposition like oxidants such as hydrogen peroxide. Therefore, when the treated liquid containing nitrous oxide is transported to another work place or waste disposal site, there is an advantage that it is not necessary to treat the nitrous oxide in the waste liquid before transportation.
  • a method of decomposing waste water by irradiating it with ultraviolet light for a certain period of time (2) A method of electrolysis using a noble metal such as platinum as an anode, (3) Hydrogen in the presence of a catalyst
  • a noble metal such as platinum as an anode
  • Hydrogen in the presence of a catalyst include a method of reducing and decomposing by reaction with gas, and (4) a method of decomposing by utilizing microorganisms that breathe using oxygen in nitrous acid nitrogen in an anaerobic state.
  • the solvent of nitrous acid-nitrogen is not limited to the water described above, and the function of generating atomic oxygen dissociated by ultraviolet light irradiation is not impaired, and the generated atomic oxygen is consumed. Otherwise, it may be an organic solvent such as methanol, ethanol, isopropanol, methylcyclohexane, cyclohexane, acetonitrile, hexane, dioxane, glycerin, n-pentane, dichloromethane and the like.
  • the maximum soluble amount of nitrous oxide varies depending on the type of solvent. Since it is preferable that the maximum soluble amount is large, the maximum soluble amount is also taken into consideration when selecting a solvent.
  • a thickener for improving the viscosity may be added to a nitrous oxide-containing solution such as an aqueous nitrous oxide solution.
  • a thickener those that do not impair the function of generating atomic oxygen and do not consume the generated atomic oxygen are preferable.
  • the oxidant contained in the fluid to be treated is brought into contact with a solution containing nitrous oxide, there is! /, And is irradiated with ultraviolet light in this state.
  • the fluid to be treated can be easily purified.
  • the contact unit brings the oxidized material contained in the fluid to be treated into contact with nitrous oxide or a solution containing nitrous oxide, and the oxidized material in contact with the nitrous oxide.
  • the fluid to be treated can be easily purified simply by irradiating the substance with ultraviolet light of the light source.

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Abstract

L'invention concerne un procédé de nettoyage de fluide et un appareil de nettoyage de fluide permettant de nettoyer facilement un fluide. Une substance contenue dans le fluide est nettoyée par irradiation d'une solution contenant de l'oxyde nitreux avec des rayons ultraviolets, la solution venant en contact avec la substance contenue dans le fluide.
PCT/JP2006/322921 2005-11-21 2006-11-17 Procede de nettoyage de fluide et appareil de nettoyage de fluide WO2007058285A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2015046014A1 (fr) * 2013-09-24 2015-04-02 旭有機材工業株式会社 Dispositif de stérilisation par ultraviolet
WO2017126237A1 (fr) * 2016-01-22 2017-07-27 株式会社日立製作所 Dispositif et procédé de traitement de produit de culture et dispositif de purification de produit de culture
JP2018017728A (ja) * 2016-07-15 2018-02-01 ルーテック株式会社 汚染水処理装置、汚染水処理システム及び汚染水処理方法

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JPS63111930A (ja) * 1986-10-28 1988-05-17 Ebara Res Co Ltd ガス混合物中の亜酸化窒素の分解除去法
JP2006008499A (ja) * 2004-05-21 2006-01-12 Mitsubishi Gas Chem Co Inc 物質の酸化方法およびその酸化装置

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JPS63111929A (ja) * 1986-10-28 1988-05-17 Ebara Res Co Ltd ガス混合物中の亜酸化窒素の分解除去方法
JPS63111930A (ja) * 1986-10-28 1988-05-17 Ebara Res Co Ltd ガス混合物中の亜酸化窒素の分解除去法
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Publication number Priority date Publication date Assignee Title
WO2015046014A1 (fr) * 2013-09-24 2015-04-02 旭有機材工業株式会社 Dispositif de stérilisation par ultraviolet
JPWO2015046014A1 (ja) * 2013-09-24 2017-03-09 旭有機材株式会社 紫外線殺菌装置
WO2017126237A1 (fr) * 2016-01-22 2017-07-27 株式会社日立製作所 Dispositif et procédé de traitement de produit de culture et dispositif de purification de produit de culture
JP2018017728A (ja) * 2016-07-15 2018-02-01 ルーテック株式会社 汚染水処理装置、汚染水処理システム及び汚染水処理方法

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