WO2017130523A1 - オゾン供給装置およびオゾン供給方法 - Google Patents
オゾン供給装置およびオゾン供給方法 Download PDFInfo
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- WO2017130523A1 WO2017130523A1 PCT/JP2016/083678 JP2016083678W WO2017130523A1 WO 2017130523 A1 WO2017130523 A1 WO 2017130523A1 JP 2016083678 W JP2016083678 W JP 2016083678W WO 2017130523 A1 WO2017130523 A1 WO 2017130523A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0454—Controlling adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/14—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40007—Controlling pressure or temperature swing adsorption
- B01D2259/40009—Controlling pressure or temperature swing adsorption using sensors or gas analysers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4525—Gas separation or purification devices adapted for specific applications for storage and dispensing systems
Definitions
- the present invention relates to an ozone supply device and an ozone supply method for concentrating and storing ozone using an adsorption phenomenon.
- Ozone is used as a powerful oxidant in various fields such as water purification and semiconductor cleaning. Due to the recent increase in environmental awareness, there is an increasing demand for high-concentration and high-efficiency ozone generation technology.
- the upper limit of the ozone purity of the ozone generator alone is about 20%, and ozone has a property of self-decomposition, so that it is difficult to store in a gas phase at room temperature.
- In order to perform intermittent ozone treatment it is necessary to generate ozone each time.
- a technique is disclosed in which ozone is stored and concentrated using an adsorption phenomenon, and high-purity ozonized gas is intermittently supplied (for example, Patent Documents 1 and 2).
- Patent Document 3 a method for depressurizing the adsorption tower (for example, Patent Document 3) and a method for raising the temperature of the adsorption tower (for example, Patent Document 2) are disclosed.
- Patent Documents 1-3 since ozone is desorbed after demand is generated, there is a problem that ozone cannot be supplied immediately in response to ozone demand.
- Patent Document 4 a method has been disclosed in which a standby process for performing preheating before ozone desorption is provided, and desorption is immediately started and supplied in response to a request.
- Japanese Patent Laid-Open No. 11-43307 paragraphs [0018] to [0023] and FIG. 1) JP-B-61-011881 (page 2, right column, page 3, right column to page 4, right column, and FIGS. 3, 5) Japanese Patent No. 3837280 (paragraph [0017] and FIG. 1) Japanese Examined Patent Publication No. 63-013928 (right column on page 2 to left column on page 3 and FIG. 2)
- Patent Document 4 has a problem that ozone utilization efficiency is lowered due to ozone self-decomposition during the standby process.
- the present invention has been made to solve the above-described problems, and has an object to provide an ozone supply device and an ozone supply method that can improve the responsiveness of concentrated ozone supply to ozone demand and improve the efficiency of ozone utilization.
- An ozone supply device includes an ozone generator that generates ozonized gas, an adsorption tower that adsorbs the generated ozonized gas to an internal adsorbent, and an ozonized gas that is desorbed from the adsorbent of the adsorption tower.
- the gas flow in the gas flow path connecting the gas generator, adsorption tower, standby unit, and decompression device is controlled, the generated ozonized gas is adsorbed on the cooled adsorbent, and the ozonized gas adsorbed on the adsorbent is desorbed
- a controller for concentrating ozone and the controller is configured to set the pressure in the adsorption tower in a standby state in which the desorbed ozonized gas waits in the standby part from the pressure in the adsorption tower during adsorption. To lower That.
- An ozone supply method includes an ozone generator, an adsorption tower filled with an adsorbent inside, a standby unit for waiting for ozonized gas, a decompressor, and an ozone supply unit for supplying ozonized gas.
- the ozonized gas generated by the ozone generator is introduced into the adsorption tower, and the ozonized gas is adsorbed to the cooled adsorbent
- the ozone supply device has a structure including a standby unit that waits for the ozonized gas desorbed from the adsorbent of the adsorption tower, the high-purity ozonized gas can be immediately supplied at an arbitrary timing. Ozone self-decomposition can be suppressed and ozone utilization efficiency can be improved.
- the ozone supply method according to the present invention includes a standby step of sealing and waiting for the concentrated high-purity ozonized gas inside the adsorption tower and the standby section, the high-purity ozonized gas can be immediately supplied at an arbitrary timing, Self-decomposition of ozone during standby can be suppressed, and ozone utilization efficiency can be improved.
- Embodiment 1 includes an ozone generator, an adsorption tower filled with an adsorbent inside, a standby unit for waiting for ozonized gas, a decompression device, an ozone supply unit for supplying ozonized gas, and an adsorbent
- An ozone supply device comprising a low-temperature refrigerant circulator that cools the refrigerant, and a controller that adsorbs the ozonized gas to the adsorbent and desorbs and concentrates the ozonized gas adsorbed to the adsorbent,
- an ozone supply method including an adsorption process, a concentration process, a standby process, and a supply process.
- FIG. 1 is a system schematic diagram showing the configuration of the ozone supply apparatus
- FIG. 2 is a flowchart of the ozone supply method
- an explanatory diagram of a comparative example 3 is a process schematic diagram of the ozone supply device
- FIG. 4 is a process schematic diagram of a comparative example
- FIG. 5 is a system schematic diagram showing other configurations of the ozone supply device
- FIGS. I will explain.
- the same or corresponding parts are denoted by the same reference numerals.
- the ozone purity is a term indicating the ratio of the number of ozone particles to the total number of particles in the target gas
- the ozone partial pressure is a term indicating the absolute number of ozone particles contained in a unit volume.
- FIG. 1 is a system schematic diagram showing the configuration of an ozone supply device.
- the ozone supply device 100 includes a source gas source 1, an ozone generator 2, an adsorption tower 3, a low-temperature refrigerant circulator 5, a standby unit 7, a decompression device 8, an ozone supply unit 9, and a control unit 10.
- a source gas containing oxygen is introduced from the source gas source 1 into the ozone generator 2, and the source gas is ozonized.
- the ozonized gas is introduced into the adsorption tower 3 filled with the adsorbent 4 and ozone in the ozonized gas is adsorbed on the surface of the adsorbent 4.
- the adsorption tower 3 is surrounded by a low-temperature refrigerant 6, and the low-temperature refrigerant circulator 5 maintains the temperature of the adsorbent 4 at a low temperature by circulating the low-temperature refrigerant 6 and cooling the adsorption tower 3. .
- the outer wall of the standby unit 7 is insulated from the outside air by, for example, a method of covering with a heat insulating material or vacuum insulating, thereby preventing the temperature of the ozonized gas sealed by the standby unit 7 from rising.
- the inner wall surfaces of the adsorption tower 3 and the standby unit 7 are exposed to an ozonized gas having an ozone partial pressure higher than the ozone partial pressure to be used and passivated. Is desirable.
- a valve V ⁇ b> 1 is installed at the entrance of the adsorption tower of the gas flow path connecting the ozone generator 2 and the adsorption tower 3.
- a valve V2 is installed at the standby part inlet of the gas flow path connecting the adsorption tower 3 and the standby part 7, and a valve V3 for extracting gas and discharging it out of the system is installed in this gas flow path.
- a valve V4 is provided at the inlet of the decompression device of the gas flow path connecting the standby unit 7 and the decompression device 8.
- These valves V1 to V4 are control valves and are controlled to be opened and closed by the control unit 10. That is, the control unit 10 controls the gas flow in the gas flow path by controlling the valves V1 to V4 that are control valves.
- the ozonized gas generated by the ozone supply device 100 is supplied from the ozone supply unit 9 to the supply target 11.
- the operation of the ozone supply device 100 includes an adsorption process for adsorbing ozone to the cooled adsorbent 4 and a concentration process for increasing the ozone purity in the gas in the adsorption tower 3 by depressurizing the adsorption tower 3 filled with the adsorbent 4. And a standby step of sealing the concentrated high-purity ozonized gas in the adsorption tower 3 and the standby unit 7 and waiting for an arbitrary time, and a supply step of supplying the high-purity ozonized gas to the supply object 11 .
- a source gas containing oxygen is introduced from the source gas source 1 to the ozone generator 2, and the ozone generator 2 ozonizes the source gas.
- the control unit 10 opens the valve V1 and the valve V3, closes the valve V2 and the valve V4, the ozonized gas is introduced into the adsorption tower 3, and ozone is adsorbed by the cooled adsorbent 4.
- a material that preferentially adsorbs ozone is selected as compared with gas species other than ozone (hereinafter referred to as source gas species), such as oxygen, nitrogen, nitrogen oxides, etc. contained in the ozonized gas.
- source gas species such as oxygen, nitrogen, nitrogen oxides, etc. contained in the ozonized gas.
- silica gel is used as the adsorbent 4. Due to the adsorption characteristics of the adsorbent 4, the ozone purity on the surface of the adsorbent 4 is higher than the ozone purity in the ozonized gas. The lower the temperature of the adsorbent 4, the greater the amount of ozone adsorbed on the adsorbent 4.
- the low-temperature refrigerant circulator 5 circulates the low-temperature refrigerant 6 around the adsorption tower 3 and maintains the temperature of the adsorbent 4 at a low temperature. Unadsorbed ozone and source gas species are discharged out of the system through the valve V3. If the adsorbent 4 reaches a certain amount of ozone, a certain time elapses, or a process transition signal is input from the outside, the process proceeds to the concentration process.
- the ozone purity is improved by preferentially desorbing and exhausting the source gas species adsorbed by the adsorbent 4.
- the valve V1 and the valve V3 are closed, the valve V2 and the valve V4 are opened, and the pressure in the adsorption tower 3 is reduced using the pressure reducing device 8.
- a vacuum pump or an ejector is used as the decompression device 8.
- the secondary side of the vacuum pump has a positive pressure. Therefore, the pressure of the supply target 11 does not need to be lower than the pressure of the adsorption tower 3, and the degree of freedom of the supply target 11 is increased. Rise.
- the ozone in the adsorption tower 3 is reduced when the adsorption tower 3 is depressurized. Source gas species other than those are preferentially exhausted, and the ozone purity in the adsorption tower 3 is increased.
- the pressure in the adsorption tower 3 is lower than the gas phase pressure of the supply target 11 by providing the decompression device 8 having a secondary side having a positive pressure, such as a vacuum pump, in front of the supply target 11.
- the ozonized gas can be supplied to the supply object 11.
- the control unit 10 closes the valve V1, the valve V3, and the valve V4, and the ozonized gas in the adsorption tower 3 whose ozone purity has been increased through the concentration process is contained in the adsorption tower 3 and the standby part 7. It will be sealed.
- the control unit 10 maintains the valve V1, the valve V3, and the valve V4 in a closed state for an arbitrary time, and waits for an ozone request signal.
- the ozone supply device 100 moves to the supply process, and the decompression device 8 is used to make the adsorption tower 3 negative.
- the ozone supply unit 9 supplies the high-purity ozonized gas to the supply target 11.
- the ozone supply unit 9 is, for example, a gas pipe or an ejector when the supply target 11 requires gas-phase ozone, and is an air diffuser, an ejector, or the like when the supply target 11 requires liquid-phase ozone.
- the functions of the decompression device 8 and the ozone supply unit 9 may be handled by a single ejector.
- a process for generating and supplying a high-purity ozonized gas by applying the ozone supply method including the adsorption process, the concentration process, the standby process, and the supply process described above will be described with reference to the flowchart of FIG. .
- the ozone supply method of the first embodiment includes an ozone generator 2, an adsorption tower 3 filled with an adsorbent 4 inside, a standby unit 7 for waiting for ozonized gas, a decompression device 8, an ozone
- the ozone supply device 100 including the ozone supply unit 9 that supplies the chemical gas to the supply target is used, and includes the following steps 1 (S01) to 4 (S04). In the flowchart of FIG. 3, the operation continuation determination process is added to step 5 (S05), and the operation can be continued.
- Step 1 the ozonized gas generated by the ozone generator 2 is introduced into the adsorption tower 3, and the ozonized gas is adsorbed to the cooled adsorbent 4.
- Step 2 the adsorption tower 3 is decompressed by the decompression device 8 to increase the ozone purity in the gas in the adsorption tower 3.
- Step 3 (S03) the concentrated high-purity ozonized gas is sealed inside the adsorption tower 3 and the standby unit 7 and waits for an arbitrary time.
- Step 4 (S04) high-purity ozonized gas is supplied from the ozone supply unit 9.
- step 5 (S05) it is determined whether or not the operation is continued. When the operation is continued, the process returns to the adsorption process in step 1 (S01). If the operation is not continued, the operation of the ozone supply device 100 is terminated.
- the ozone supply apparatus of the comparative example includes a raw material gas source 1, an ozone generator 2, an adsorption tower 3, and a low-temperature refrigerant circulator 5, and supplies concentrated ozonized gas to a supply object 11.
- the ozonized gas introduced into the ozone generator 2 from the source gas source 1 and introduced into the adsorption tower 3 filled with the adsorbent 4 is adsorbed on the surface of the adsorbent 4 by the ozone in the ozonized gas. Is done.
- the low-temperature refrigerant circulator 5 maintains the temperature of the adsorbent 4 at a low temperature by circulating the low-temperature refrigerant 6 and cooling the adsorption tower 3.
- the valve V1 and the valve V3 are in an open state and the valve V2 is in a closed state, and when a predetermined amount of ozone is adsorbed by the adsorbent, the generation of ozone is stopped.
- the valve V 1 and the valve V 3 are closed, the valve V 2 is opened, and ozone is desorbed from the adsorbent 4 in the adsorption tower 3, so that high-purity ozonized gas is produced. Supply intermittently.
- a typical method for desorbing ozone there are a method of depressurizing the adsorption tower 3 and a method of raising the temperature of the adsorption tower 3.
- the ozone supply device of the comparative example since it is not necessary to operate the ozone generator 2 continuously, it is possible to suppress power consumption and raw material gas consumption, and high purity ozone (purity of 50% or more) that cannot be generated by the ozone generator alone. A gas can be supplied.
- the ozone supply device of the comparative example since ozone desorption is started after the demand for ozone is generated, there is a problem that ozone cannot be supplied immediately in response to the ozone request from the supply target 11.
- the ozone supply device 100 of the first embodiment not only has the standby unit 7 and the standby process, but it is important to provide a standby process between the concentration process for depressurizing the adsorption tower 3 and the ozone supply process. .
- the order of the standby process has not been set appropriately.
- the concentration step and the supply step are generally performed continuously.
- the standby part 7 is installed just before the decompression device 8, and the ozone part request
- the time difference from the supply of high purity ozone to the supply of ozone can be reduced, and the self-decomposition of ozone in the standby process can be greatly suppressed.
- FIG. 4 shows an example of changes over time in the adsorption tower 3 pressure, ozone purity, and ozone partial pressure in the adsorption process, concentration process, standby process, and supply process of the ozone supply apparatus 100 of the first embodiment.
- A represents the pressure in the adsorption tower 3
- B represents the ozone request signal.
- C represents the ozone purity in the adsorption tower 3
- D represents the ozone partial pressure in the adsorption tower 3
- E represents the ozone decomposition amount during standby.
- the ozone decomposition amount (E) during standby corresponds to the difference in ozone partial pressure in the adsorption tower 3 at the start and end of the standby process.
- FIG. 5 shows an example of changes over time in the pressure in the adsorption tower 3, the ozone purity, and the ozone partial pressure in the ozone supply apparatus of the comparative example in which the standby process is provided before the concentration process.
- A represents the pressure in the adsorption tower 3
- B represents the ozone request signal.
- C represents the ozone purity in the adsorption tower 3
- D represents the ozone partial pressure in the adsorption tower 3
- E represents the ozone decomposition amount during standby.
- the amount of ozone decomposition (E) during standby corresponds to the difference in ozone partial pressure in the adsorption tower 3 at the start and end of the standby process.
- the ozonized gas in the adsorption tower 3 that has finished the concentration step has a high ozone purity. Therefore, the high ozone purity is maintained in the standby step. As a result, the high-purity ozonized gas can be supplied immediately upon shifting to the supply process.
- the adsorption tower 3 is depressurized in the standby process, and the ozone purity is higher but the ozone partial pressure is lower than in the adsorption process.
- the standby unit 7 is also decompressed in the same manner as the adsorption tower 3.
- the ozone supply apparatus of the comparative example as shown in FIG.
- the self-decomposition reaction of ozone is suppressed, and the generated ozone can be used efficiently.
- the suppression effect of ozone self-decomposition reaction is described.
- the ozone self-decomposition reaction is a phenomenon in which ozone reacts with each other before it reacts with the object to be treated and returns to oxygen molecules.
- the utilization efficiency of the generated ozone decreases.
- the ozone autolysis reaction rate v R is obtained by setting the ozone partial pressure as Coz [/ cm 3 ].
- v R k R ⁇ Coz 2 [/ s] (Formula 3) It is expressed. That is, even if the ozone purity is the same, the higher the temperature and the higher the ozone partial pressure, the faster the autolysis reaction.
- the ozone partial pressure at 2 atmospheres is twice the ozone partial pressure at atmospheric pressure, so the ozone autolysis reaction rate at 2 atmospheres is the ozone self-decomposition reaction at atmospheric pressure. 4 times the speed.
- the adsorption tower is made to stand by in a heated state, the temperature in the adsorption tower in the standby process becomes higher than that in the adsorption process, and the ozone self-decomposition proceeds faster, so the efficiency of use of the generated ozone is increased. It will decline.
- the ozone self-decomposition reaction rate in the ozone supply apparatus 100 of Embodiment 1 is calculated, and the effect with respect to the ozone supply apparatus of a comparative example is demonstrated concretely.
- the ozone self-decomposition rate during standby is calculated.
- ozone desorption is not started and the standby process is started.
- the temperature in the standby process is 0 ° C.
- the ozone purity is atmospheric pressure
- 35 wt% 26 vol% or more.
- the ozone supply device 100 of the first embodiment for example, when adsorption is performed at ⁇ 15 ° C. with an ozone purity of 9.3 vol%, the pressure in the adsorption tower 3 is reduced to 20 kPa as an absolute pressure, thereby reducing 47 vol%. Is obtained.
- the standby unit 7 is provided to wait in a state where the ozonized gas has a high ozone purity.
- the ozonized gas has a high ozone purity.
- a standby process is provided for waiting in the state. For this reason, when the ozone request
- the adsorption tower 3 and the standby unit 7 are maintained in a reduced pressure state, and the ozone self-decomposition rate is reduced, so that ozone consumption during standby is suppressed and ozone utilization efficiency is improved.
- an ozone supply device having a configuration different from that of the ozone supply device 100 according to the first embodiment will be sequentially described.
- the ozone supply apparatus 101 whose system schematic diagram is shown in FIG. 6 will be described.
- the difference from the ozone supply device 100 is that the standby unit 7 is cooled by the low-temperature refrigerant 6.
- the temperature of the standby unit 7 in the standby process becomes a low temperature equivalent to the temperature of the adsorption tower 3, and the ozone self-decomposition rate in the standby unit 7 is reduced.
- the utilization efficiency of the stored ozone improves.
- the low-temperature refrigerant 6 flows in the order of the standby unit 7 and the adsorption tower 3, but the flow direction may be reversed, and the adsorption tower 3 and the standby unit 7 are cooled in parallel. Also good.
- the ozone supply apparatus 102 whose system schematic diagram is shown in FIG. 7 will be described.
- the difference from the ozone supply device 100 is that the adsorption tower 3 also has the function of the standby unit 7.
- the control unit 10 closes the valve V2 and shifts to the stand-by standby step.
- the standby process since the inside of the adsorption tower 3 is in a reduced pressure state, the ozone self-decomposition rate can be kept small.
- the adsorption tower 3 is configured to have the function of the standby unit 7 as described above, the response of supplying high-purity ozone in response to an ozone request from the supply target 11 is slightly reduced as compared with the ozone supply device 100.
- the standby unit 7 and the valve V4 are omitted, the number of members necessary for the ozone supply device is reduced, and the valve control by the control unit 10 is simplified.
- the difference from the ozone supply device 100 is that a path for circulating and introducing the gas exhausted from the adsorption tower 3 in the adsorption step to the ozone generator 2 again is provided.
- the ozonized gas (hereinafter referred to as exhaust gas) discharged from the adsorption tower 3 in the adsorption step is introduced into the ozone decomposition tower 21 via the valve V3.
- Ozone in the ozonized gas that has not been adsorbed by the adsorbent 4 is decomposed in the ozone decomposition tower 21 to become oxygen. Since the exhaust gas contains oxygen, it can be reused as a raw material gas.
- the exhaust gas that has passed through the ozonolysis tower 21 is pressurized by the gas compressor 22 and then reintroduced into the ozone generator 2 as a raw material gas. If the exhaust gas exhausted from the adsorption tower 3 is circulated and introduced again into the ozone generator 2 in this way, the raw material gas is reused, so that the ozone production cost is reduced. If the ozone in the ozonized gas is completely adsorbed by the adsorbent 4 in the adsorption step and the gas discharged from the adsorption tower does not contain ozone, the ozone decomposition tower 21 may be omitted.
- the ozone supply apparatus 104 whose system schematic diagram is shown in FIG. 9 will be described.
- the difference from the ozone supply device 100 is that a branch path for supplying the source gas from the source gas source 1 to the adsorption tower 3 without going through the ozone generator 2, and a flow rate controller 23 for controlling the flow rate of the source gas in the branch path, It is a point which has.
- the ozone purity in the ozonized gas output from the ozone supply device has a one-to-one correspondence with the pressure in the adsorption tower 3 during the supply process.
- the decompression device 8 or the ozone supply unit 9 does not have a pressure adjusting function, the ozonized gas having the maximum ozone purity is always output in the supply process.
- the raw material gas is introduced into the adsorption tower 3 in the ozone supply process, and the pressure in the adsorption tower 3 is adjusted by changing the flow rate of the raw material gas so that the ozone gas is desorbed from the adsorbent 4. Can control the ozone purity.
- the ozone supply device 104 even when the decompression device 8 and the ozone supply unit 9 do not have a pressure adjustment function, an ozonized gas having a desired purity below the maximum generated ozone purity can be supplied to the supply target 11.
- the ozone supply device 100 includes the ozone generator, the adsorption tower filled with the adsorbent, the standby unit for waiting for the ozonized gas, the decompression device, and the ozonization.
- An ozone supply unit that supplies gas, a low-temperature refrigerant circulator that cools the adsorbent, and a controller that adsorbs ozonized gas to the adsorbent and desorbs and concentrates the ozonized gas adsorbed to the adsorbent.
- the standby unit waits in a state where the ozonized gas has a high ozone purity.
- the ozone supply method includes an adsorption process, a concentration process, a standby process, and a supply process, and the standby process waits in a state in which the ozonized gas has a high ozone purity. For this reason, the ozone supply apparatus and the ozone supply method of Embodiment 1 can supply high-purity ozonized gas immediately when an ozone request
- FIG. The ozone supply device according to the second embodiment is configured such that a pressure gauge is added to the ozone supply device 100 according to the first embodiment to control the pressure in the adsorption tower 3 and the standby unit 7.
- FIG. 10 is a system schematic diagram showing the configuration of the ozone supply device of the second embodiment
- FIG. 11 is a characteristic diagram showing the relationship between the pressure in the adsorption tower and the ozone purity
- the basic configuration of the ozone supply apparatus according to the second embodiment is the same as that of the ozone supply apparatus 100 according to the first embodiment, but the ozone supply apparatus 200 is provided with a pressure gauge 204 at the rear stage of the adsorption tower 3.
- the pressure gauge 204 measures the pressure after the adsorption tower 3 in the concentration step and transmits the measurement result to the control unit 10.
- the control unit 10 outputs a transition command to the standby process on the condition that the measured value of the pressure gauge 204 is lower than a preset pressure value in the concentration process.
- FIG. 11 shows the dependence of the ozone purity in the supplied ozonized gas on the pressure in the adsorption tower 3 when the temperature in the adsorption tower 3 is changed, and this dependence does not change with the temperature in the adsorption tower 3. It is clearly shown.
- shaft of FIG. 11 is the pressure (arbitrary unit) in an adsorption tower, and a vertical axis
- shaft is the ozone density (arbitrary unit) of an adsorption tower exit.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device is configured such that a pressure gauge is added to the ozone supply device according to the first embodiment to control the pressure in the adsorption tower and the standby unit. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, high-speed control responsiveness can be obtained by controlling the process with reference to the pressure.
- Embodiment 3 FIG.
- the ozone supply device according to the third embodiment is configured to add an ozone meter to the ozone supply device 100 according to the first embodiment to control the ozone purity and the ozone partial pressure in the adsorption tower 3 and the standby unit 7. is there.
- FIG. 12 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply device 300 according to the third embodiment is the same as that of the ozone supply device 100 according to the first embodiment, but the ozone supply device 300 is provided with an ozone meter 24 at the rear stage of the adsorption tower 3. .
- the ozone meter 24 measures the ozone purity and ozone partial pressure in the adsorption tower 3 in the concentration step, and transmits the measurement result to the control unit 10.
- the control unit 10 enables the transition to the standby process when both of the following two conditions are satisfied.
- (Condition 1) The ozone purity in the adsorption tower 3 in the concentration step has reached a purity equal to or higher than a preset target ozone purity.
- (Condition 2) The ozone partial pressure in the adsorption tower 3 in the concentration step is lower than the ozone partial pressure in the adsorption tower 3 in the adsorption step.
- the value of ozone purity and ozone partial pressure can each be set as conditions which can transfer from a concentration process to a standby process. It is possible to control the ozone partial pressure during the transition from the concentration process to the standby process by setting the conditions that allow the transition of the ozone purity and the ozone partial pressure, and the self-decompression effect of ozone can be obtained to a desired extent .
- the ozone supply apparatus 300 of Embodiment 3 when the two conditions of ozone purity and ozone partial pressure were satisfied, the transition to the standby process was made possible, but when either one of the conditions was satisfied, the standby was performed. Transition to the process can also be made possible.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device of the third embodiment is configured to add the ozone meter to the ozone supply device of the first embodiment to control the ozone purity and the ozone partial pressure in the adsorption tower and the standby unit. Is. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, the ozone self-decomposition rate can be arbitrarily controlled, and a desired ozone utilization efficiency improvement effect can be obtained.
- Embodiment 4 FIG.
- the ozone supply device according to the fourth embodiment is obtained by adding a thermometer and a refrigerant temperature control unit for controlling the temperature of the low-temperature refrigerant to the ozone supply device 100 according to the first embodiment.
- FIG. 13 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply device 400 according to the fourth embodiment is the same as that of the ozone supply device 100 according to the first embodiment.
- a thermometer 25 that measures the temperature in the adsorption tower 3 and A refrigerant temperature control unit 26 for controlling the temperature of the low-temperature refrigerant 6 is provided.
- the control unit 10 controls the temperature in the adsorption tower 3 using the thermometer 25 and the refrigerant temperature control unit 26.
- the temperature in the adsorption tower 3 in the standby process is set to a temperature equal to or lower than the temperature in the adsorption tower 3 in the adsorption process.
- the self-decomposition rate coefficient of ozone represented by Formula 2 in the standby process is reduced, and ozone self-decomposition is suppressed.
- the heat of vaporization is taken from the adsorbent 4 and the surrounding gas. It is considered that the cold heat required for 6 is extremely small.
- the difference in ozone decomposition amount depending on whether or not the adsorption tower 3 is cooled in the standby step is calculated, and the power cost required for cooling is compared with the ozone production cost corresponding to the difference in ozone decomposition amount for cooling. It is advisable to set the temperature of the adsorption tower 3 in the standby step so that the power cost is lower than the ozone production cost.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device is obtained by adding a thermometer and a refrigerant temperature control unit for controlling the temperature of the low-temperature refrigerant to the ozone supply device according to the first embodiment. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, the self-decomposition rate coefficient of ozone during standby can be reduced, and ozone self-decomposition can be suppressed.
- Embodiment 5 FIG.
- the ozone supply device of the fifth embodiment is obtained by adding a communication unit for transmitting and receiving signals between the supply target and the control unit to the ozone supply device 100 of the first embodiment.
- FIG. 14 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply apparatus 500 according to the fifth embodiment is the same as that of the ozone supply apparatus 100 according to the first embodiment, but in the ozone supply apparatus 500, signals are exchanged between the supply target 11 and the control unit 10.
- a communication unit 27 is provided for the purpose.
- a valve V5 is provided in the gas flow path connecting the decompression device 8 and the ozone supply unit 9.
- the control unit 10 waits for an ozone request signal in a state where the adsorption process and the concentration process are completed in advance and the process proceeds to the standby process.
- the supply target 11 outputs an ozone request signal when ozone is required, and the ozone request signal is input to the control unit 10 through the communication unit 27.
- the control unit 10 Upon receiving the ozone request signal, the control unit 10 starts the operation of the decompression device 8 and simultaneously opens the valves V4 and V5 to supply high-purity ozone to the supply target 11.
- an ozone discharge valve may be provided after the valve V5, and the ozonized gas discharged from the decompression device in the concentration step may be discharged from the ozone discharge valve.
- an ozonized gas having a purity lower than the set purity can be discharged from the ozone discharge valve in the concentration step. For this reason, the ozonized gas below the set purity is not supplied to the supply target 11, and the ozonized gas having a stable purity can be supplied to the supply target 11.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device is obtained by adding a communication unit for transmitting and receiving signals between the supply target and the control unit to the ozone supply device according to the first embodiment. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, even when the load of ozone treatment fluctuates rapidly in the supply target, and there is a sudden demand for ozone, the effect of being able to supply high-purity ozone immediately can be obtained.
- Embodiment 6 FIG.
- the ozone supply device of Embodiment 6 is provided with a plurality of standby units 7 in parallel, assuming that ozonized gas is supplied to a plurality of supply targets.
- the ozone supply device according to the seventh embodiment will be described with a focus on differences from the first embodiment, based on FIG. 15 which is a system schematic diagram showing the configuration.
- FIG. 15 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply apparatus 600 according to the sixth embodiment is the same as that of the ozone supply apparatus 100 according to the first embodiment.
- two standby units first standby unit 7A, second standby unit
- a standby unit 7B and two decompression devices (first decompression device 8A and second decompression device 8B) are provided in parallel.
- the valve V6 is provided in the gas flow path connecting the adsorption tower 3 and the second standby part 7B
- the valve V7 is provided in the gas flow path connecting the second standby part 7B and the second decompression device 8B.
- a valve V8 is provided in the gas flow path connecting the first pressure reducing device 8A and the ozone supply unit 9, and a valve V9 is provided in the gas flow path connecting the second pressure reducing device 8B and the ozone supply unit 9. Yes. Further, a valve V10 for discharging the gas outside the system is provided at the outlet of the first pressure reducing device 8A, and a valve V11 for discharging the gas outside the system is provided at the outlet of the second pressure reducing device 8B. In the ozone supply device 600, the control unit 10 controls the valves V1 to V4 and V6 to V11 to supply high purity ozonized gas to the supply target 11.
- the ozone supply device 600 provided with two standby parts (first standby part 7A, second standby part 7B) and two pressure reduction devices (first pressure reduction device 8A, second pressure reduction device 8B) is the ozone stored in the adsorption step. Is made to wait on the first standby unit 7A using the first pressure reducing device 8A. Thereafter, the valve V3 and the valve V10 are closed and the valve V8 is opened at a desired timing to supply the high purity ozonized gas to the supply object 11. While the high purity ozonized gas is being supplied from the standby unit 7A, ozone is stored in the adsorption tower 3, and then the second standby unit 7B is made to wait for the high purity ozonized gas using the second decompression device 8B.
- the valves V6, V8, V10, V11 are closed, the valve V9 is opened, and the high purity ozonized gas is supplied from the standby unit 7B to the supply target 11 Supply. If it does in this way, it will become possible to supply high purity ozonization gas to supply object 11 continuously.
- the first standby unit 7 ⁇ / b> A and the second standby unit 7 ⁇ / b> B supply the same supply object 11, but each standby unit (the first standby unit 7 ⁇ / b> A and the second standby unit 7 ⁇ / b> B) is a separate supply target. You may supply. Further, even when there are three or more standby units, while ozone gas is supplied from one standby unit, ozone is stored in the adsorption tower 3 and then another standby unit waits for the ozonized gas. The operation is similar. Moreover, the adsorption tower 3 may also include a plurality of adsorption towers corresponding to the standby unit. In that case, since ozone can be stored in another adsorption tower while supplying ozonized gas from one adsorption tower, there is no waste in time.
- an ozone supply device having two standby units (first standby unit 7A, second standby unit 7B) and two decompression devices (first decompression device 8A, second decompression device 8B) in parallel.
- first standby unit 7A, second standby unit 7B two standby units
- decompression device 8A, second decompression device 8B two decompression devices
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device is obtained by adding a plurality of standby units and decompression devices to the ozone supply device according to the first embodiment. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Further, when the supply target issues a long-time ozone request, it is possible to continuously supply high-purity ozonized gas. Moreover, even when there are a plurality of supply targets, it is possible to supply high-purity ozonized gas to each supply target at an arbitrary timing.
- Embodiment 7 FIG.
- the ozone supply device according to the seventh embodiment is obtained by adding a storage unit that stores at least one of the ozone supply interval and the ozone supply time to the ozone supply device 100 according to the first embodiment.
- FIG. 16 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply apparatus 700 according to the seventh embodiment is the same as that of the ozone supply apparatus 100 according to the first embodiment, but the ozone supply apparatus 700 stores at least one of the ozone supply interval and the ozone supply time.
- a storage unit 28 is provided.
- the storage unit 28 estimates the time interval until the next ozone supply using the ozone supply interval or ozone supply time data accumulated therein, and transmits the estimated time interval to the control unit 10. Alternatively, the storage unit 28 may transmit the ozone supply interval or the ozone supply time data to the control unit 10, and the control unit 10 may estimate the time interval until the next ozone supply.
- the control unit 10 which has obtained the time interval until the next ozone supply, the ozone generator 2 and the adsorption tower so as to finish the adsorption process and the concentration process immediately before the next ozone supply start time and shift to the standby process. 3 and valves V1 to V4 are controlled.
- the storage unit 28 is provided outside the control unit 10, but the control unit 10 may also have the function of the storage unit 28.
- the control unit 10 may also have the function of the storage unit 28.
- not only the ozone supply interval but also the supply ozone purity, the supply ozonized gas flow rate, the ozonized gas purity during the adsorption process, the pressure in the adsorption tower 3 during the adsorption process, etc. may be stored in the storage unit 28 together. In the next ozone supply, it becomes easy to output the ozonized gas under the same conditions, and the time required for adjusting these parameters can be shortened.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device of the seventh embodiment is obtained by adding a storage unit that stores at least one of the ozone supply interval and the ozone supply time to the ozone supply device of the first embodiment. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, since the standby time in the standby process can be shortened, the amount of ozone self-decomposition can be reduced and the ozone utilization efficiency can be improved.
- Embodiment 8 In the ozone supply device of the eighth embodiment, the inner wall surfaces of the adsorption tower 3 and the standby section 7 are subjected to surface treatment in order to suppress ozone decomposition inside the adsorption tower 3 and the standby section 7.
- FIG. 1 is a system schematic diagram showing the basic configuration of the ozone supply device, focusing on the differences from the first embodiment.
- the ozone supply device 1 of the first embodiment since the ozone partial pressure is low in the standby process, ozone self-decomposition in the gas phase is suppressed as compared with a state where the ozone partial pressure is high, and the adsorption tower 3 and the standby The influence of the ozonolysis reaction on the wall surface of the part 7 is relatively increased.
- the inner wall surface is provided with an adsorption tower 3 and a standby unit 7 subjected to surface treatment for suppressing ozone decomposition.
- a treatment for suppressing ozonolysis a treatment for reducing surface irregularities by mechanical polishing, electropolishing, etc., a treatment for reducing chemical reactivity of the surface by a fluororesin coat, a metal oxide coat, or the like can be applied.
- surface treatment can also be performed only on the inner wall surface of either the adsorption tower 3 or the standby unit 7.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device of the eighth embodiment aims to suppress ozone decomposition in the standby process, and ozone is applied to the inner wall surfaces of the adsorption tower 3 and the standby unit 7 of the ozone supply device 100 of the first embodiment.
- a surface treatment that suppresses decomposition is applied. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, ozone decomposition on the inner surfaces of the adsorption tower and the standby part can be suppressed in the standby process, and ozone utilization efficiency can be further improved.
- Embodiment 9 FIG.
- the ozone supply device according to the ninth embodiment is provided with a liquid supply unit and a gas-liquid mixing device in the ozone supply device 100 according to the first embodiment, assuming that the ozone supply device is supplied in a state of an ozone solution. .
- FIG. 17 is a system schematic diagram showing the configuration.
- the same or corresponding parts as those in FIG. 1 of the first embodiment are denoted by the same reference numerals.
- the basic configuration of the ozone supply device 900 according to the ninth embodiment is the same as that of the ozone supply device 100 according to the first embodiment. However, the ozone supply device 900 is assumed to be supplied in a state of an ozone solution to a processing target.
- the liquid supply unit 29 and the gas-liquid mixing device 30 are provided.
- As the liquid water is mainly used in many cases, but in some cases, a solution to which a pH adjusting agent such as an acid or hydroxide is added, or sludge may be used.
- the control unit 10 controls the liquid supply unit 29 to supply the liquid to the gas-liquid mixing device 30.
- the control unit 10 opens the valve V2 and the valve V4, sucks the ozonized gas from the adsorption tower 3 and the standby unit 7 using the decompression device 8, and the gas-liquid mixing device 30 An ozonized gas is supplied to generate an ozone solution 31.
- the ozonized gas supplied to the gas-liquid mixing device 30 has a positive pressure in order to prevent backflow of the liquid.
- vacuum pumps in which the primary side (front stage) of the decompression device 8 has a negative pressure and the secondary side (rear stage) has a positive pressure are suitable.
- the secondary side of the decompression device 8 is set to a positive pressure, the ozone partial pressure becomes very large due to the high ozone purity and positive pressure in the ozonized gas on the secondary side, and the ozone self-decomposition reaction becomes active. For this reason, it is desirable to make the gas flow path connecting the decompression device 8 and the gas-liquid mixing device 30 as short as possible.
- the ozone solution 31 can be immediately supplied to the supply target 11 that requires ozone treatment in the liquid phase in response to the ozone request.
- ozone self-decomposition during standby is suppressed, so ozone utilization efficiency is improved.
- the standby unit 7 may be cooled by the low-temperature refrigerant 6 as in the ozone supply device 101 (FIG. 6).
- the adsorption tower 3 may have the function of the standby part 7 like the ozone supply apparatus 102 (FIG. 7).
- the ozone supply device As described above, the ozone supply device according to the ninth embodiment is assumed to be supplied in a state of an ozone solution to the processing target, and the liquid supply unit and the gas-liquid mixing device are added to the ozone supply device 100 according to the first embodiment. It is equipped with. Therefore, similarly to the ozone supply device of the first embodiment, when the ozone request is generated in the supply target, the high-purity ozonized gas can be immediately supplied, and the ozone consumption during standby is suppressed, Utilization efficiency can be improved. Furthermore, the ozone solution can be immediately supplied to the supply target that requires ozone treatment in the liquid phase in response to the ozone demand.
- the present invention can be freely combined with each other within the scope of the present invention, and the embodiments can be appropriately modified or omitted.
- this invention can improve the responsiveness of the concentrated ozone supply to the ozone demand and improve the ozone utilization efficiency, it can be widely applied to an ozone supply apparatus and an ozone supply method for concentrating and storing ozone.
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Abstract
Description
これに対し、オゾン脱着前に予備加熱を行う待機工程を設け、要求に対して即時に脱着を開始し供給する手法が開示されている(例えば、特許文献4)。
実施の形態1は、オゾン発生器と、内部に吸着剤が充填された吸着塔と、オゾン化ガスを待機させる待機部と、減圧装置と、オゾン化ガスを供給するオゾン供給部と、吸着剤を冷却する低温冷媒循環器と、オゾン化ガスを吸着剤に吸着させ、吸着剤に吸着させたオゾン化ガスを脱着させて濃縮する制御部とを備えるオゾン供給装置、
および吸着工程と、濃縮工程と、待機工程と、供給工程とを備えるオゾン供給方法に関するものである。
なお、系統概略図において、同一あるいは相当部分は、同一の符号を付している。
本説明において、オゾン純度は対象ガス中の全粒子数に対するオゾン粒子数の割合を示す用語、オゾン分圧は単位体積に含まれるオゾン粒子の絶対数を示す用語として、両者を区別して使用する。
図1は、オゾン供給装置の構成を示す系統概略図である。オゾン供給装置100は、原料ガス源1、オゾン発生器2、吸着塔3、低温冷媒循環器5、待機部7、減圧装置8、オゾン供給部9、および制御部10を備える。
吸着塔3は、周囲を低温冷媒6で囲まれており、低温冷媒循環器5は、低温冷媒6を循環させ、吸着塔3を冷却することで吸着剤4の温度を低温に維持している。
また待機部7の外壁は、例えば断熱材で被覆する、または真空断熱する方法で外気と断熱することで、待機部7に封じ切られたオゾン化ガスの温度上昇を防止する。
吸着塔3および待機部7の内壁面は、実際にオゾン供給装置100を使用する前に、使用予定オゾン分圧よりも高いオゾン分圧を有するオゾン化ガスに曝露して不動態化しておくことが望ましい。吸着塔3および待機部7の内壁面を不動態化しておくことで、内壁面とオゾンとが接触することで生じるオゾンの分解を抑制することができる。
オゾン供給装置100で生成されたオゾン化ガスは、オゾン供給部9から供給対象11に供給される。
オゾン供給装置100の動作は、冷却された吸着剤4にオゾンを吸着する吸着工程と、吸着剤4が充填された吸着塔3を減圧して吸着塔3内のガス中オゾン純度を高める濃縮工程と、濃縮された高純度オゾン化ガスを吸着塔3および待機部7内に封じ切り、任意の時間待機する待機工程と、高純度オゾン化ガスを供給対象11に供給する供給工程と、から成る。
吸着工程において、酸素を含む原料ガスが原料ガス源1からオゾン発生器2へ導入され、オゾン発生器2は原料ガスをオゾン化する。制御部10は、バルブV1およびバルブV3を開状態、バルブV2およびバルブV4を閉状態とし、オゾン化ガスは吸着塔3へと導入され、冷却された吸着剤4にオゾンが吸着される。
吸着剤4は、酸素、窒素、窒素酸化物等、オゾン化ガスに含まれるオゾン以外のガス種(以降、原料ガス種と記載する)に比べ、オゾンを優先的に吸着するものを選定する。吸着剤4として、例えばシリカゲルが使用される。吸着剤4の吸着特性により、吸着剤4表面でのオゾン純度はオゾン化ガス中のオゾン純度よりも高くなる。
吸着剤4の温度は低いほど、吸着剤4へのオゾンの吸着量は多くなる。このため、低温冷媒循環器5は吸着塔3の周囲に低温冷媒6を循環させ、吸着剤4の温度を低温に維持する。吸着されなかったオゾンおよび原料ガス種はバルブV3を通り系外に排出される。
吸着剤4へのオゾンの吸着量が一定量に達するか、一定時間が経過するか、または工程移行信号が外部より入力される等、予め設定した条件を満たすと、濃縮工程に移行する。
減圧装置8としては、例えば真空ポンプ、エジェクタが使用される。減圧装置8として真空ポンプを使用した場合、真空ポンプの二次側は正圧となるため、供給対象11の圧力を吸着塔3の圧力よりも低くする必要はなく、供給対象11の自由度が高まる。
吸着剤4の吸着特性により、原料ガス種の吸着剤4からの脱着率に比べ、オゾンの吸着剤4からの脱着率は低いため、吸着塔3が減圧されると、吸着塔3内のオゾン以外の原料ガス種が優先的に排気され、吸着塔3内のオゾン純度が高まる。
このように、供給対象11の前段に真空ポンプ等のように二次側が正圧となる減圧装置8を備えることで、供給対象11の気相圧力よりも、吸着塔3内の圧力が低い状態で、オゾン化ガスを供給対象11に供給することができる。
制御部10はバルブV1、バルブV3、およびバルブV4を任意の時間閉状態に維持し、オゾン要求信号を待機する。
予め設定した任意の時間経過する、又は外部からオゾン要求信号が入力される等、設定した条件を満たすと、オゾン供給装置100は供給工程に移行し、減圧装置8を用いて吸着塔3を負圧に維持したまま、オゾン供給部9により供給対象11へ高純度オゾン化ガスを供給する。
オゾン供給部9は、供給対象11が気相オゾンを要求する場合、例えばガス配管、エジェクタ等であり、供給対象11が液相オゾンを要求する場合、例えば散気管、エジェクタ等である。エジェクタを用いた場合、減圧装置8とオゾン供給部9との機能を一つのエジェクタで担当させてもよい。
なお、図3のフローチャートでは、ステップ5(S05)に運転継続判定処理を追加して、運転を継続できるフローとしている。
比較例のオゾン供給装置は、原料ガス源1、オゾン発生器2、吸着塔3、低温冷媒循環器5を備え、濃縮したオゾン化ガスを供給対象11に供給する。
原料ガス源1からオゾン発生器2に導入され、オゾン化されたオゾン化ガスは、吸着剤4が充填された吸着塔3へと導入され、オゾン化ガス中のオゾンが吸着剤4表面に吸着される。低温冷媒循環器5は低温冷媒6を循環させ、吸着塔3を冷却することで吸着剤4の温度を低温に維持している。吸着工程において、バルブV1およびバルブV3は開状態、バルブV2は閉状態であり、所定量のオゾンが吸着剤に吸着されると、オゾン発生を停止する。オゾンを供給対象11に供給する際には、バルブV1およびバルブV3は閉状態、バルブV2を開状態とし、吸着塔3内の吸着剤4からオゾンを脱着させることで、高純度オゾン化ガスを間欠的に供給する。
比較例のオゾン供給装置によれば、オゾン発生器2を連続運転する必要がないため電力消費および原料ガス消費を抑制できるとともに、オゾン発生器単体では生成できない高い純度(純度50%以上)のオゾン化ガスを供給することが可能である。
しかし、比較例のオゾン供給装置においては、オゾン需要が生じてからオゾンの脱着を開始するため、供給対象11からのオゾン要求に対して即時にオゾンを供給することができないという問題があった。
これに対し本発明では、待機部7を減圧装置8の直前に設置し、濃縮工程を経た後の高純度オゾン化ガスを待機部7に待機させることで、供給対象11からオゾン要求を受けてから高純度オゾンを供給するまでの時間差を低減するとともに、待機工程におけるオゾンの自己分解を大幅に抑制することができる。
実施の形態1のオゾン供給装置100の吸着工程、濃縮工程、待機工程、供給工程の各工程における吸着塔3内圧力、オゾン純度、およびオゾン分圧の時間変化の例を図4に示す。
図4において、Aは吸着塔3内の圧力を表し、Bはオゾン要求信号を表している。Cは吸着塔3内のオゾン純度を表し、Dは吸着塔3内のオゾン分圧を表し、Eは待機時のオゾン分解量を表している。なお、待機時のオゾン分解量(E)は、待機工程の開始時と終了時の吸着塔3内のオゾン分圧の差に相当する。
濃縮工程の前に待機工程を設けた比較例のオゾン供給装置における、吸着塔3内の圧力、オゾン純度、およびオゾン分圧の時間変化の例を図5に示す。
図5において、Aは吸着塔3内の圧力を表し、Bはオゾン要求信号を表している。Cは吸着塔3内のオゾン純度を表し、Dは吸着塔3内のオゾン分圧を表し、Eは待機時のオゾン分解量を表している。図5においても、待機時のオゾン分解量(E)は、待機工程の開始時と終了時の吸着塔3内のオゾン分圧の差に相当する。
一方、比較例のオゾン供給装置では、図5に示すように、待機工程時に吸着塔3内オゾン純度は低いがオゾン分圧は高い状態となっている。このため、オゾンの供給要求が発生した際に濃縮工程を実施するため時間の遅延が生じる。また、待機時のオゾン自己分解に起因する無効消費が大きいことが、図4、5の待機時のオゾン分解量(E)の差から明らかである。
オゾン自己分解反応とは、オゾンが処理対象と反応する前にオゾン同士で反応して酸素分子に戻ってしまう現象であり、オゾン自己分解反応が起こると生成したオゾンの利用効率が低下する。
O3+O3→3O2 (式1)
式1の反応速度係数kRの報告例は少ないが、「NIST Chemical Kinetics Database, Standard Reference Database 17, Version 7.0 (Web Version) Release 1.6.8 http://kinetics.nist.gov/kinetics/」では温度をT[K]として
kR=7.47×10-12×exp(-9310/T)[cm6/s](式2)
と報告されている。
オゾン自己分解反応速度vRは、オゾン分圧をCoz[/cm3]として、
vR=kR×Coz2[/s] (式3)
と表される。即ち、オゾン純度が同じであっても、高温であるほど、また、オゾン分圧が高いほど、自己分解反応は速くなる。
まず、比較例のオゾン供給装置を例にとり、待機時のオゾン自己分解速度を計算する。比較例では、オゾン脱着を開始せずに待機工程に入り、待機工程における温度は0℃、オゾン純度は大気圧で、35wt%=26vol%以上である。このとき、オゾン分圧はCoz=7.09×1018[/cm3]であるから、式3より、オゾン自己分解速度はvR=3.57×1011[/s] となる。
オゾン供給装置100では、吸着塔3を減圧してオゾンを脱着させた状態で待機工程に移行するので、待機工程におけるオゾン分圧はCoz=2.76×1018[/cm3]である。また、濃縮工程および待機工程において吸着塔3および待機部7を昇温しないため、吸着塔3および待機部7の温度は-15℃以下であり、オゾン自己分解速度はvR=7.26×109[/s]以下となる。即ち、比較例のオゾン供給装置のように高温かつ高オゾン分圧で待機工程に移行する場合のオゾン自己分解速度に比べ、実施の形態1のオゾン供給装置100では、待機工程におけるオゾン自己分解速度はおよそ1/50程度になり、待機工程中でのオゾン消費が大幅に抑制される。
まず、図6に系統概略図を示すオゾン供給装置101について説明する。
オゾン供給装置100との違いは、待機部7を低温冷媒6により冷却している点である。このように待機部7を低温冷媒6により冷却することで、待機工程における待機部7の温度が吸着塔3の温度と同等の低温になり、待機部7内でのオゾン自己分解速度が低減される。このため、貯蔵したオゾンの利用効率が向上する。
図6のオゾン供給装置101では、低温冷媒6は待機部7、吸着塔3の順で流れているが、流れる方向は逆順でもよく、また吸着塔3と待機部7とを並列に冷却してもよい。
オゾン供給装置100との違いは、吸着塔3が待機部7の機能を併せ持つ点である。
濃縮工程において吸着塔3が減圧され、吸着塔3内の圧力が予め設定した値を下回ると、制御部10はバルブV2を閉状態として、吸着塔3を封じ切り待機工程に移行する。待機工程においては、吸着塔3内は減圧状態となっているため、オゾン自己分解速度を小さく維持できる。
このように吸着塔3が待機部7の機能を併せ持つ構成にすれば、オゾン供給装置100に比較して、供給対象11からオゾン要求を受けて高純度オゾンを供給する応答性は若干低下する。しかし、待機部7およびバルブV4が省略されるため、オゾン供給装置に必要な部材が少なくなるとともに、制御部10によるバルブ制御が簡略化される。
オゾン供給装置100との違いは、吸着工程において吸着塔3から排気されるガスを再びオゾン発生器2に循環導入させる経路を有する点である。
吸着工程において吸着塔3から排出されたオゾン化ガス(以降、排出ガスと記載する)は、バルブV3を経てオゾン分解塔21に導入される。吸着剤4に吸着されなかったオゾン化ガス中のオゾンはオゾン分解塔21において分解され、酸素となる。
排出ガスは酸素を含むため、原料ガスとして再利用可能である。したがって、オゾン分解塔21を通過した排出ガスは、ガス圧縮器22で昇圧された後、原料ガスとしてオゾン発生器2に再導入される。
このように吸着塔3から排気される排出ガスを再びオゾン発生器2に循環導入させる構成にすれば、原料ガスの再利用がなされるため、オゾン製造コストが低減される。
吸着工程においてオゾン化ガス中のオゾンが吸着剤4に全量吸着され、吸着塔から排出されるガスにオゾンが含まれない場合、オゾン分解塔21は省略してもよい。
オゾン供給装置100との違いは、原料ガス源1からオゾン発生器2を介さずに吸着塔3へ原料ガスを供給する分岐経路と、分岐経路における原料ガスの流量を制御する流量制御器23とを有する点である。
オゾン供給装置から出力するオゾン化ガス中のオゾン純度は、供給工程時の吸着塔3内の圧力と一対一に対応している。しかし、減圧装置8またはオゾン供給部9が圧力調整機能を有さない場合、供給工程においては常に最大オゾン純度のオゾン化ガスが出力される。
オゾン供給装置104では、オゾン供給工程において吸着塔3内に原料ガスを導入し、原料ガスの流量を変化させることで、吸着塔3内圧力を調整し、吸着剤4から脱着させるオゾン化ガス中のオゾン純度を制御できる。
オゾン供給装置104の構成にすれば、減圧装置8およびオゾン供給部9が圧力調整機能を有さない場合でも、最大発生オゾン純度以下で所望の純度のオゾン化ガスを供給対象11へ供給できる。
このため、実施の形態1のオゾン供給装置およびオゾン供給方法は、供給対象でオゾン要求が発生した際には、即時に高純度オゾン化ガスを供給することができる。さらに、待機工程において吸着塔および待機部が減圧状態に維持され、オゾンの自己分解速度が低減されることで、待機中のオゾン消費が抑制され、オゾン利用効率が向上する。
実施の形態2のオゾン供給装置は、実施の形態1のオゾン供給装置100に圧力計を追加して、吸着塔3および待機部7内の圧力を制御する構成としたものである。
制御部10は、濃縮工程において圧力計204の測定値が、予め設定した圧力値を下回ったことを条件として、待機工程への移行指令を出力する。
図11は、吸着塔3内温度を変化させた場合の、供給オゾン化ガス中オゾン純度の吸着塔3内圧力依存性を示しており、この依存性が吸着塔3内温度によって変化しないことを明確に示している。なお、図11の横軸は吸着塔内の圧力(任意単位)であり、縦軸は吸着塔出口のオゾン密度(任意単位)である。
本実施の形態2において、オゾン供給装置101(図6)のように待機部7を低温冷媒6で冷却してもよい。またオゾン供給装置102(図7)のように吸着塔3が待機部7の機能を兼ね備えてもよい。またオゾン供給装置103(図8)のように酸素リサイクル機構を備えてもよい。またオゾン供給装置104(図9)のようにオゾン純度調整用原料ガス導入ラインを設けてもよい。
実施の形態3のオゾン供給装置は、実施の形態1のオゾン供給装置100にオゾン計を追加して、吸着塔3および待機部7内のオゾン純度およびオゾン分圧を制御する構成としたものである。
オゾン計24は、濃縮工程における吸着塔3内のオゾン純度およびオゾン分圧を測定し、測定結果を制御部10に送信する。
(条件1)濃縮工程における吸着塔3内のオゾン純度が、予め設定した目標オゾン純度以上の純度に到達している。
(条件2)濃縮工程における吸着塔3内のオゾン分圧が、吸着工程における吸着塔3内のオゾン分圧よりも低い。
(条件1)を満たした場合、待機工程から供給工程への移行時に即時に高純度オゾン化ガスを供給できる。また、(条件2)を満たした場合、待機工程中でのオゾン自己分解が抑制される。
なお、実施の形態3のオゾン供給装置300では、オゾン純度およびオゾン分圧の2つの条件を満たした場合、待機工程への移行を可能としたが、いずれか一方の条件を満たした場合、待機工程への移行を可能とすることもできる。
実施の形態4のオゾン供給装置は、実施の形態1のオゾン供給装置100に温度計と低温冷媒の温度を制御するための冷媒温度制御部を追加したものである。
実施の形態5のオゾン供給装置は、実施の形態1のオゾン供給装置100に供給対象と制御部との間で信号授受をするための通信部を追加したものである。
オゾン要求信号を受信した制御部10は減圧装置8の動作を開始させると同時にバルブV4およびV5を開状態とし、高純度オゾンを供給対象11に供給する。
実施の形態6のオゾン供給装置は、複数の供給対象にオゾン化ガスを供給することを想定し、待機部7を複数並列に備えたものである。
以下、実施の形態7のオゾン供給装置について、構成を示す系統概略図である図15に基づいて、実施の形態1との差異を中心に説明する。図15において、実施の形態1の図1と同一あるいは相当部分は、同一の符号を付している。
オゾン供給装置600では、吸着塔3と第二待機部7Bとを接続するガス流路にはバルブV6が、第二待機部7Bと第二減圧装置8Bとを接続するガス流路にはバルブV7が、第一減圧装置8Aとオゾン供給部9とを接続するガス流路にはバルブV8が、第二減圧装置8Bとオゾン供給部9とを接続するガス流路にはバルブV9が設けられている。さらに、第一減圧装置8Aの出口にはガスを系外に排出するバルブV10が、第二減圧装置8Bの出口にはガスを系外に排出するバルブV11が設けられている。
オゾン供給装置600では、制御部10が各バルブV1~V4、V6~V11の制御を行うことで、高純度オゾン化ガスを供給対象11に供給する。
待機部7Aから高純度オゾン化ガスを供給している間に、吸着塔3にオゾンを貯蔵した後、第二減圧装置8Bを用いて第二待機部7Bに高純度オゾン化ガスを待機させる。第一待機部7Aからの高純度オゾン化ガス供給が完了した後に、バルブV6、V8、V10、V11を閉とし、バルブV9を開として、待機部7Bから供給対象11に高純度オゾン化ガスを供給する。このようにすれば、供給対象11に対して連続的に高純度オゾン化ガスを供給することが可能となる。
また、吸着塔3についても、待機部に対応した複数の吸着塔を備えていてもよい。その場合、一つの吸着塔からオゾン化ガスを供給している間に、他の吸着塔にオゾンを貯蔵することができるため、時間的に無駄がない。
実施の形態7のオゾン供給装置は、実施の形態1のオゾン供給装置100にオゾン供給間隔またはオゾン供給時間のうち少なくとも一方を記憶する記憶部を追加したものである。
次回のオゾン供給までの時間間隔を得た制御部10は、次回オゾン供給が開始される予定時間の直前に吸着工程および濃縮工程を終えて待機工程に移行するよう、オゾン発生器2、吸着塔3およびバルブV1~バルブV4を制御する。
また、記憶部28に、オゾン供給間隔だけでなく供給オゾン純度、供給オゾン化ガス流量、吸着工程時のオゾン化ガス純度、吸着工程時の吸着塔3内圧力等を併せて記憶させておけば、次回オゾン供給においても同様の条件でオゾン化ガスを出力することが容易になり、これらパラメータの調整に要する時間を短縮できる。
実施の形態8のオゾン供給装置は、吸着塔3および待機部7の内部でのオゾン分解を抑制するために、吸着塔3および待機部7の内壁面に表面処理を施したものである。
実施の形態8のオゾン供給装置では、内壁面にオゾン分解を抑制する表面処理を施した吸着塔3および待機部7を備えている。
オゾン分解を抑制する表面処理としては、機械研磨、電界研磨等により表面の凹凸を減ずる処理、およびフッ素樹脂コート、金属酸化物コート等により表面の化学反応性を減ずる処理等が適用できる。
なお、吸着塔3および待機部7いずれか1方の内壁面にのみ表面処理を施すこともできる。
実施の形態9のオゾン供給装置は、処理対象にオゾン溶液の状態で供給することを想定し、実施の形態1のオゾン供給装置100に、液体供給部および気液混合装置を備えたものである。
液体としては主に水を使用することが多いが、場合により酸又は水酸化物等のpH調整剤を添加した溶液や、汚泥等を使用する場合もある。
気液混合装置30としては、例えばエジェクタまたは散気管が使用される。
制御部10は供給対象11においてオゾン要求が生じると、液体供給部29を制御して気液混合装置30に液体を供給する。気液混合準備が整った時点で、制御部10はバルブV2およびバルブV4を開状態とし、減圧装置8を用いて吸着塔3および待機部7からオゾン化ガスを吸引し、気液混合装置30へオゾン化ガスを供給してオゾン溶液31を生成する。
この場合、減圧装置8としては、減圧装置8の一次側(前段)が負圧となり二次側(後段)が正圧となるような真空ポンプ類が適している。ただし、減圧装置8の二次側を正圧にすると、二次側のオゾン化ガスでは高オゾン純度かつ正圧のためオゾン分圧が非常に大きくなり、オゾン自己分解反応が活発になる。このため、減圧装置8と気液混合装置30とを接続するガス流路はできる限り短くすることが望ましい。
Claims (12)
- オゾン化ガスを生成するオゾン発生器と、
生成した前記オゾン化ガスを内部の吸着剤に吸着させる吸着塔と、
前記吸着塔の前記吸着剤から脱着させた前記オゾン化ガスを待機させる待機部と、
前記吸着塔および前記待機部の圧力を低下させる減圧装置と、
前記脱着させたオゾン化ガスを供給対象に供給するオゾン供給部と、
前記吸着剤を冷却する低温冷媒循環器と、
前記オゾン発生器、前記吸着塔、前記待機部、および前記減圧装置を接続するガス流路のガス流を制御し、生成した前記オゾン化ガスを冷却された前記吸着剤に吸着させ、前記吸着剤に吸着させた前記オゾン化ガスを脱着させてオゾンを濃縮する制御部とを備え、
前記制御部は、前記脱着させたオゾン化ガスを前記待機部に待機させる待機状態のときの前記吸着塔内の圧力を、前記吸着のときの前記吸着塔内の圧力よりも低くするオゾン供給装置。 - 前記供給対象の前段に前記減圧装置を備え、前記減圧装置により、前記オゾン化ガスを前記供給対象に供給する際、前記供給対象の気相圧力よりも前記吸着塔内の圧力を低くする請求項1に記載のオゾン供給装置。
- 前記吸着塔と前記待機部との間の前記ガス流路に圧力計を備え、前記制御部は、前記吸着塔内の圧力が予め設定した圧力を下回ったことを条件として、前記待機状態に移行させる請求項1または請求項2に記載のオゾン供給装置。
- 前記吸着塔と前記待機部との間の前記ガス流路にオゾン計を備え、
前記オゾン計はガス流路内のオゾン分圧を測定し、
前記制御部は、前記吸着において前記オゾン発生器から前記吸着塔に導入される前記オゾン化ガス中のオゾン分圧よりも低い任意のオゾン分圧を工程移行条件として設定し、前記吸着塔内のオゾン分圧が前記工程移行条件として設定したオゾン分圧を下回ったことを条件として、前記待機状態に移行させる請求項1から請求項3のいずれか1項に記載のオゾン供給装置。 - 前記吸着塔と前記待機部との間の前記ガス流路にオゾン計を備え、
前記オゾン計は前記ガス流路内のオゾン純度を測定し、
前記制御部は、前記吸着塔内のオゾン純度が予め設定したオゾン純度以上の純度に達したことを条件として、前記待機状態に移行させる請求項1から請求項4のいずれか1項に記載のオゾン供給装置。 - 前記吸着塔内の温度を測定する温度計と前記吸着剤の温度を調節する温度調節装置とを備え、
前記制御部は、前記待機状態における前記吸着剤の温度を、前記吸着における前記吸着剤の温度以下の温度にする請求項1から請求項5のいずれか1項に記載のオゾン供給装置。 - 前記供給対象と前記制御部との間で信号の授受を行うための通信部を設け、前記供給対象でオゾン要求が発生した場合、
前記制御部は、前記オゾン要求を受信し、前記減圧装置および前記ガス流を制御し、前記供給対象に前記オゾン化ガスを供給する請求項1から請求項6のいずれか1項に記載のオゾン供給装置。 - 前記待機部を複数並列に備え、1つまたは複数の前記供給対象に対して前記濃縮したオゾン化ガスを供給する請求項1から請求項7のいずれか1項に記載のオゾン供給装置。
- オゾン供給間隔またはオゾン供給時間のうち少なくとも一方を記憶する記憶部を備え、
前記制御部は、前記記憶部に蓄積されたオゾン供給データを用いて次回のオゾン供給時期を推定し、前記オゾン供給時期の直前に前記吸着および前記濃縮が完了するように前記オゾン発生器および前記ガス流を制御する請求項1から請求項8のいずれか1項に記載のオゾン供給装置。 - 前記吸着塔および前記待機部の両方またはいずれか一方の内壁面は、オゾン分解を抑制する処理を施した請求項1から請求項9のいずれか1項に記載のオゾン供給装置。
- 前記オゾン供給部は、液体供給部と気液混合装置とを備え、
前記濃縮した前記オゾン化ガスを、前記気液混合装置を用いて液体に溶解させてオゾン溶液を生成し、前記オゾン溶液を前記供給対象に供給する請求項1から請求項10のいずれか1項に記載のオゾン供給装置。 - オゾン発生器と、内部に吸着剤が充填された吸着塔と、オゾン化ガスを待機させる待機部と、減圧装置と、前記オゾン化ガスを供給するオゾン供給部と、前記吸着剤を冷却する低温冷媒循環器と、を備えたオゾン供給装置を用い、
前記オゾン発生器で発生したオゾン化ガスを、前記吸着塔に導入し、冷却された前記吸着剤に前記オゾン化ガスを吸着する吸着工程と、
前記減圧装置で前記吸着塔を減圧して前記吸着塔内のガス中オゾン純度を高める濃縮工程と、
濃縮された高純度オゾン化ガスを減圧された前記吸着塔および前記待機部の内部に封じ切り、待機する待機工程と、
前記高純度オゾン化ガスを供給する供給工程と、
を備えたオゾン供給方法。
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