JP4110071B2 - Ozone generator and ozone generation method - Google Patents

Description

  The present invention relates to a discharge-type ozone generator and an ozone generation method. More specifically, the present invention relates to a discharge type ozone generator and an ozone generation method for mixing nitrogen into a raw material gas.

  As a means for generating high-concentration ozone in a discharge-type ozone generator using oxygen gas as a raw material, a technique for continuously supplying a small amount of nitrogen is known (see, for example, Patent Documents 1 and 2). Such nitrogen supply is necessary for stably generating high-concentration ozone, and it is very preferable that the nitrogen supply amount is continuously constant in order to keep the concentration of generated ozone high.

  On the other hand, as a nitrogen supply method, an intermittent supply method other than the continuous supply method can be considered (for example, refer to Patent Document 3). However, although this conventional example is not a continuous method for nominal purposes, only an intermittent supply method has been proposed as a supply method having the same effect as the continuous method. This is also clear from the fact that the example of intermittent supply is not specifically described in Patent Document 3.

  Generally, it is more preferable that the amount of nitrogen that can be contained in the ozone-containing gas generated by the ozone generator is smaller. For example, nitrogen oxide formed by reaction of nitrogen with oxygen or the like may have adverse effects such as corrosion.

However, as described in Patent Documents 1 and 2, it is more preferable that nitrogen of a certain amount or more is contained in order to stably generate high-concentration ozone.
JP-A-1-282104 JP-A-1-298003 JP 2001-172005 A

  In other words, reducing the nitrogen content to make the resulting ozone-containing gas more favorable prevents the generation of stable high-concentration ozone, while ensuring the generation of stable high-concentration ozone. Therefore, maintaining the nitrogen content to some extent makes the properties of the generated ozone-containing gas less favorable. That is, these are contradictory conditions.

  The present invention makes good use of keeping the amount of nitrogen, which is a seemingly contradictory condition as described above, as much as possible and maintaining the amount of nitrogen for stably generating high-concentration ozone. It is an object of the present invention to provide an ozone generator and an ozone generation method that stably generate high-concentration ozone while keeping the amount of ozone low.

In order to achieve the above object, in the present invention, in an ozone generator for generating ozone by supplying high-purity oxygen to a discharge ozone generator, variable nitrogen supply means for supplying nitrogen to the ozone generator; Measuring means for measuring the amount of ozone generated by the ozone generator, ozone amount control means for controlling the variable nitrogen supply means in accordance with the amount of ozone measured by the measuring means, and discharge output control for varying the discharge output And an ozone generator comprising the means. At this time, when the measured ozone amount reaches a predetermined value, the ozone amount control unit supplies the predetermined nitrogen supply by the variable nitrogen supply unit and the discharge according to the ozone amount measured by the measurement unit. A signal for varying the discharge output may be transmitted to the output control means .

Further, in the present invention, in an ozone generation method for generating ozone by supplying high purity oxygen to a discharge type ozone generator, the amount of ozone generated by the ozone generator is measured, and the measured amount of ozone is a predetermined value. when it is, have rows nitrogen supply of a predetermined amount, it is possible to provide an ozone generator wherein the varying the discharge power in accordance with the measured amount of ozone.

  Here, supplying nitrogen may mean that oxygen, which is a raw material of ozone, is supplied to the discharge ozone generator at the same time as nitrogen is supplied. Therefore, nitrogen may be supplied and mixed in advance in oxygen, and supplied to the discharge ozone generator as mixed oxygen. Further, oxygen and nitrogen may be separately supplied to the discharge type ozone generator and mixed in the discharge type ozone generator. The variable oxygen supply means may include a variable oxygen supply device, more specifically, a gas variable flow rate supply device. Examples thereof include a gas controller and a mass flow controller (MFC). The measuring means for measuring the amount of ozone may include a measuring device for measuring the amount of ozone, such as a so-called ozone monitor (OM). The ozone amount control means may include a general control device, and in particular, may include a device that controls the input ozone amount. In the above, the measured ozone amount may be a predetermined value, or may be a value obtained each time depending on various conditions. At this time, the ozone amount may be an absolute amount of ozone, or may be a relative amount of ozone (for example, ozone concentration). Further, since the ozone amount may change with time, the ozone amount is more preferably the ozone amount per unit time. Generally, in a mixed gas with oxygen, in a region where the amount of nitrogen is relatively small, the amount of ozone tends to increase as the nitrogen concentration increases. Therefore, when the amount of ozone is less than a certain value, a predetermined amount of nitrogen Supply may be made. The predetermined amount of nitrogen can be appropriately selected by an ozone generator, but can be expressed by a relative value to oxygen. As for the nitrogen concentration which is this relative value, for example, the lower limit may be 0.001% by volume or more, preferably 0.01% by volume or more, more preferably 0.05% by volume or more. For example, the upper limit may be 10% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less.

  More specifically, the following is provided.

(1) In an ozone generator for supplying high-purity oxygen to a discharge type ozone generator to generate ozone, variable nitrogen supply means for supplying nitrogen to the ozone generator, and an amount of ozone generated by the ozone generator measuring means for measuring comprises an ozone amount controlling means for controlling the variable nitrogen supply means according to the amount of ozone was measured by the measuring means, a discharge output control means for varying the discharge power, and the ozone amount controlling means Controls the variable nitrogen supply means to supply a predetermined amount of nitrogen when the measured ozone amount reaches a predetermined value, and controls the discharge output control means according to the ozone amount measured by the measurement means. An ozone generator characterized by transmitting a signal for changing a discharge output .

(2) The ozone amount control means transmits a signal for changing a discharge output to the discharge output control means when the nitrogen supply is performed by the variable nitrogen supply means. Ozone generator.

(3) The ozone generator according to (1) or (2) above , wherein the variable nitrogen supply means performs intermittent supply of nitrogen .

(4) The variable nitrogen supply means continues the nitrogen supply for a predetermined time or until the amount of ozone measured by the measurement means reaches a second predetermined value, and then stops the nitrogen supply, and the measured ozone. The ozone generator according to any one of (1) to (3), wherein the nitrogen supply is not performed until the nitrogen supply is started again according to the amount .

( 5 ) Furthermore, a generated gas distribution unit that distributes the generated ozone-containing gas is provided, the distribution unit according to the amount of ozone measured by the measurement unit and / or the nitrogen supply performed by the variable nitrogen supply unit. The ozone generator according to any one of (1) to ( 4 ), wherein the generated ozone-containing gas is divided into a high nitrogen-containing gas and a low nitrogen-containing gas.

( 6 ) The ozone generator according to any one of (1) to ( 5 ), wherein the high-purity oxygen is 99.995% or more of high-purity oxygen.

(7) the high-purity oxygen, ozone generator according to any of that nitrogen gas as an impurity is less high purity oxygen 20ppm from above (1), wherein the (5).

(8) the high purity oxygen, ozone generator according to (7), which is a 9 3% or more of the high purity oxygen.

( 9 ) In an ozone generation method for generating ozone by supplying high-purity oxygen to a discharge ozone generator, a step of measuring the amount of ozone generated by the ozone generator, and an amount of ozone measured in the step are predetermined. Ozone generation comprising: supplying a predetermined amount of nitrogen when a value is reached; and varying the discharge output in accordance with the amount of ozone measured in the step of measuring the amount of ozone Method.

( 10 ) The ozone generation method according to ( 9 ), wherein the discharge output is simultaneously varied in the step of supplying the predetermined amount of nitrogen.

( 11 ) The ozone generation method according to ( 9 ) or (10), wherein nitrogen supply is not performed except for the step of supplying the predetermined amount of nitrogen.

( 12 ) From the above ( 9 ) to ( 11 ) , the step of supplying the predetermined amount of nitrogen is continued for a predetermined time and / or until the measured ozone amount reaches a second predetermined value. The ozone generation method according to any one of the above.

( 13 ) From the above ( 9 ), further comprising a step of distributing the generated ozone-containing gas into a high nitrogen-containing gas and a low nitrogen-containing gas according to the step of supplying the predetermined amount of nitrogen. The ozone generation method according to any one of ( 12 ).

  In the ozone generator or the ozone generation method as described above, the supply of the predetermined amount of nitrogen can change the concentration of the nitrogen at a predetermined cycle or time interval. That is, when the amount of ozone reaches a predetermined value, nitrogen is supplied at a certain nitrogen concentration (hereinafter referred to as “first nitrogen concentration”), and nitrogen is supplied at a concentration gradually lower than the first nitrogen concentration. Then, while confirming that the measured ozone amount is decreasing with time, when the measured ozone amount finally reaches a predetermined value, nitrogen may be supplied again at the first nitrogen concentration. At this time, the concentration of nitrogen can be adjusted by variable nitrogen supply means (including a variable nitrogen supply device). The lower limit of the so-called one cycle or time interval at this time can be appropriately defined by the ozone generator, but is, for example, 10 seconds or longer, preferably 60 seconds or longer, more preferably 150 seconds or longer. May be. On the other hand, the upper limit can be appropriately determined similarly by the ozone generator, but is, for example, 1800 seconds or less, preferably 600 seconds or less, and more preferably 300 seconds or less. The change in the nitrogen concentration over time may be a sine or cosine curve, or may be a stepped change, but can be appropriately selected so that the generated ozone concentration is high and constant. When the nitrogen concentration is changed in such a cycle or the like, it is possible to significantly reduce the amount of nitrogen (the total amount through one cycle, etc.) compared to the case where nitrogen of a constant concentration is continuously supplied.

  The intermittent supply described above refers to a supply including at least a period during which the supply of nitrogen is stopped, unlike the case of the variable supply described above. At this time, the lower limit of the ratio (TN / TB) between the time for supplying nitrogen (TN) and the time for not supplying nitrogen (TB) can be appropriately determined by the ozone generator, but for example 0.15 As described above, preferably, it may be 0.17 or more, more preferably 0.20 or more, and the upper limit can be similarly appropriately determined by the ozone generator, for example, 1.50 or less, preferably May be 0.75 or less, more preferably 0.50 or less. Such an intermittent ratio can be defined by the total concentration of nitrogen per cycle, and the lower limit thereof can be appropriately defined by the ozone generator. For example, 0.003 volume % Or more, preferably 0.004% by volume or more, more preferably 0.006% by volume or more, and the upper limit can be appropriately determined by the ozone generator as well. % Or less, preferably 0.014% by volume or less, more preferably 0.013% by volume or less.

  Further, the predetermined time for continuing the above-described started nitrogen supply can be defined as an absolute time, and the lower limit thereof can be appropriately defined by the ozone generator, for example, 20 seconds or more. Preferably, it is 24 seconds or longer, more preferably 28 seconds or longer. On the other hand, the upper limit can be appropriately determined similarly by the ozone generator, but is, for example, 120 seconds or shorter, preferably 100 seconds or shorter, and more preferably 90 seconds or shorter.

  Further, the second predetermined value of the ozone amount may be larger than the predetermined value of the ozone amount when the nitrogen supply is started. This second predetermined value may also be a predetermined value, or may be a value obtained each time according to various conditions. Continuing the nitrogen supply may include supplying a predetermined concentration of nitrogen at a constant level, or may include supplying the nitrogen with varying concentrations. However, when the nitrogen supply is stopped, the nitrogen supply is not performed until the nitrogen supply is resumed. When the nitrogen supply is started again, it may include a case where the ozone concentration measured as described above becomes a predetermined value.

  The above-mentioned discharge output control means may include a general discharge output control device. For example, a discharge output controller or other general devices may be included. In general, the amount of ozone generated tends to decrease with time even if the nitrogen concentration is constant. On the other hand, when the discharge output is increased, the ozone generation amount tends to increase even if the nitrogen concentration is constant. This is because the decrease with time is probably due to the decomposition of ozone due to the temperature increase in the vicinity of the discharge electrode where ozone is generated. However, an increase in discharge output promotes the generation of ozone. However, if the discharge output is increased too much, there is a possibility that the ozone concentration is lowered due to the decomposition of ozone due to the increase in temperature. Therefore, if the degree of decrease in the ozone generation amount is small, the ozone generation amount can be kept constant by appropriately increasing the discharge output accordingly. That is, when the measured amount of ozone is decreasing with time, it is considered that performing control to increase the discharge output and keep the amount of ozone constant effectively works to stabilize the amount of generated ozone. Such control can be achieved by transmitting a signal for changing (increasing) the discharge output to the discharge output control means including the discharge output control device by the ozone amount control means including the ozone amount control device. .

  On the other hand, when the nitrogen supply is started, the ozone generation amount may fluctuate greatly, so that the discharge output can be controlled to be constant so as to keep the ozone generation amount constant. This control may be feedback control based on the amount of ozone measured, but if the change is abrupt, it can also be performed by reducing the discharge output by a predetermined amount, triggered by the start of nitrogen supply It is. Accordingly, the discharge output can be varied almost simultaneously with the start of the nitrogen supply or after a predetermined delay time has elapsed. This delay time can be in accordance with the inherent response speed of the ozone generator.

  The generated gas distribution means for distributing the generated ozone-containing gas may include a distribution device. Examples of such a sorter include a combination of a valve such as a three-way valve and piping, a flow controller, and the like. This distribution can be provided in front of the ozone amount measuring device that continues from the ozone generator, and can be distributed according to the measured value of the ozone amount measuring device. It is also possible to perform distribution according to the start, continuation, or stop of nitrogen supply.

  In the present invention, the raw material oxygen gas used is preferably high-purity oxygen gas, more preferably high-purity oxygen gas of 99.995% or more. Such high-purity oxygen gas can also be obtained by purifying ordinary oxygen gas and improving the purity to 99.995% or more. Moreover, it is preferable that the raw material oxygen gas is a high-purity oxygen gas in which nitrogen gas as an impurity is reduced to about 20 ppm or less. For example, oxygen gas obtained by reducing the amount of impurity nitrogen gas from oxygen gas obtained using a general oxygen gas generator to a concentration of about 20 ppm or less can be used. At this time, argon may be contained as a main impurity. For example, the purity of this high-purity oxygen gas is about 93%, the nitrogen gas contained is about 20 ppm or less, and the main impurity may be argon. Examples of such an oxygen gas generator include PSA and VSA, but are not limited thereto.

  In the present invention, since it is decided to provide an ozone generator having the above-described configuration or to provide an ozone generation method according to the above-described procedure, the nitrogen content is generated while generating high-concentration ozone. Thus, a gas containing ozone with less impurities such as nitrogen can be generated and supplied.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 is a block diagram of an ozone generator 10 that is an embodiment of the present invention. The raw material high-purity oxygen is supplied from the mass flow controller 12 to the discharge unit 14 which is an ozone generator by a predetermined amount, and ozone is generated. At this time, the pressure of the discharge part 14 is maintained by the orifice 18. The generated mixed gas of ozone and raw material oxygen passes through the ozone monitor 16 and the amount of ozone is grasped. Two stop valves 20 and 21 are used as a sorting device. When unnecessary gas mixture is discharged, the stop valve 20 is closed and the stop valve 21 is opened to be discharged to the ozonolysis device 23. Conversely, the necessary mixed gas is sent to the chamber and the processing tank 22 by opening the stop valve 20 and closing the stop valve 21. A mass flow controller 24, which is a supply device of nitrogen gas that can be mixed with raw material oxygen, is arranged in front of the discharge unit 14, and supplies nitrogen as necessary. The discharge unit 14 of the ozone generator 10 and the mass flow controller 24 for supplying nitrogen are controlled by the control unit 25 according to the result of the ozone monitor 16 and the like. The signal of the ozone monitor 16 is transmitted through the line 25a. A control signal is transmitted from the control unit 25 to the discharge unit 14 via the line 25b. Further, the mass flow controller 24 and the control unit 25 are connected by a line 25c to transmit and receive signals. Moreover, the control part 25 can transmit / receive a signal via the line | wire 25d between the stop valves 20 and 21 which are distribution apparatuses.

  More specifically, as mass flow controllers 12 and 24, SEC-4500MC-O2-20SLM and UFC-1661-N2-5SCCM manufactured by STEC Co., Ltd. can be used, respectively. Moreover, the ozone generating unit GR-RD22 by Sumitomo Precision Industries, Ltd. can be used for the discharge part 14. FIG. As the ozone monitor 16, EG-600W manufactured by Sugawara Jitsugyo Co., Ltd. can be used. All of the pipes connecting these parts can use 1/4 "(Φ6.35 x 3.95) PFA tubes. Also, 1/4" (Φ 6.35 x 4.35) can be used for the pipes. When using a SUS316L EP-treated product, an ozone generation unit GR-RD20 manufactured by Sumitomo Precision Industry Co., Ltd. can be used for the discharge unit 14, and the ozone monitor 16 is an EG-600M manufactured by Sugawara Jitsugyo Co., Ltd. Can be used. At about 300 mm from the oxygen mass flow controller 12 and about 100 mm from the nitrogen mass flow controller 24, the pipes merge at the junction 13 and connect to the discharge section 14 at about 1,000 mm from the junction 13. May be. The distance from the discharge unit 14 to the ozone monitor 16 may be about 1,000 mm. In such an apparatus, for example, the oxygen gas flow rate may be set to about 5 L / min.

  FIG. 2 shows a typical change in ozone amount over time when ozone is generated by the ozone generator as shown in FIG. The vertical axis is the ozone concentration, measured by the ozone monitor 16, and the horizontal axis is time. After flowing a gas mixture of raw material oxygen and necessary nitrogen at a constant ratio, the discharge starts ( The time from 0 second) is shown. As can be seen from the figure, ozone begins to be generated as soon as the discharge is started, and its amount gradually increases. After showing peak 30 after about 10 seconds, the amount of ozone gradually decreases, and if the amount of mixed nitrogen is large, the generation of ozone at a high concentration is maintained as shown by the broken flat line 34, and the amount of mixed nitrogen is slightly small. A slightly high concentration of ozone is maintained as indicated by a solid flat line 32. On the other hand, if the amount of mixed nitrogen is extremely small, the amount of ozone generated decreases as indicated by the broken line 36 that gradually decreases, becomes unstable, and the amount fluctuates as indicated by the branched broken line 36. That is, it is suggested that in a region where the amount of nitrogen is extremely small, a certain amount of ozone generation can be maintained depending on conditions.

  FIG. 3 is a schematic graph showing the relationship between the ozone generation amount after several tens of seconds in which the ozone generation amount in FIG. 2 is relatively constant and the nitrogen concentration at that time. In this graph, the ozone concentration rises with the nitrogen concentration, particularly in the region 38 where the nitrogen concentration is low, but this is a very unstable region, and in practice it is not necessarily represented by a single line. It is not an area that can be expressed. In the relatively stable region 40, the ozone concentration is high and stable, and the ozone concentration is slightly increased while the nitrogen concentration is increased. FIG. 4 shows a graph of the relationship between the actually measured ozone concentration and the nitrogen concentration. In this figure, the nitrogen concentration of about 0.05% or more corresponds to the region 40 in FIG.

  FIG. 5 is a diagram in which the nitrogen concentration 42 to be mixed and the ozone concentration 44 to be generated are plotted with respect to time. As can be seen from this figure, nitrogen is intermittently introduced. This graph does not particularly correct the delay in the arrival time of the mixed nitrogen. However, since the flow rate of the mixed gas is about 5 L / min, it is theoretically considered to be about 0.5 seconds until the mixed gas whose nitrogen supply has started reaches the ozone monitor 16. Therefore, this delay does not cause a large change in the shape of the graph.

  As can be seen from FIG. 5, when the nitrogen supply is started, the ozone concentration rapidly rises with a slight delay, and the high ozone concentration is maintained substantially flat while the nitrogen supply is continued and for several seconds thereafter. Thereafter, the ozone concentration gradually decreases, but a certain level of ozone concentration is maintained. If nitrogen is supplied again when the ozone concentration drops to a predetermined value, the ozone concentration rapidly increases as described above, and the high ozone concentration is maintained substantially flat during the nitrogen supply and for several seconds thereafter. be able to. Thereafter, the ozone concentration gradually decreases, but a certain level of ozone concentration is maintained. In this way, the effect of the nitrogen concentration on the amount of ozone generated becomes clear, and even after the supply of nitrogen is stopped, a higher ozone concentration can be maintained relatively stably than when no nitrogen is supplied from the beginning. You can see that

  FIG. 6 is a graph schematically showing the relationship between the ozone concentration and the discharge output. It can be seen from this figure that the ozone concentration increases relatively linearly when the discharge output is increased. FIG. 7 schematically shows the state of the ozone concentration 48 when the discharge output 46 is increased in a pulse manner as in the intermittent supply of the nitrogen concentration in FIG. As can be seen from this figure, the ozone concentration 48 increases immediately when the discharge output 46 is increased, and decreases immediately when the discharge output 46 is decreased. That is, it can be seen that the behavior is different from the case of intermittent nitrogen.

  FIG. 8 schematically shows the relationship between the amount of nitrogen added to the raw material oxygen and the amount of nitrogen oxide in the ozone mixed gas to be generated. As can be seen from this figure, in the invention of the present application, the concentration of the nitrogen oxides in the mixed ozone gas to be reduced as much as possible increases almost in proportion to the amount of added nitrogen.

  FIG. 9 is a graph relating to the quantitative determination of nitric oxide that is generally performed. The vertical axis represents the nitrate ion concentration in the water through which the nitrogen oxide-containing mixed gas is vented, and the horizontal axis represents the time during which the nitrogen oxide-containing mixed gas is vented (that is, the amount of the gas mixture to be vented). Therefore, in order to obtain the time change of the concentration of nitric oxide with this method, aeration is performed with a predetermined time (for example, 10 seconds) as a unit time, and the average nitric oxide amount per unit time is determined from the nitrate ion concentration at that time. Can be requested.

  FIG. 10 shows the time change of the ozone concentration 52 when nitrogen is added in a pulsed manner 50 at the start of discharge. At this time, nitrogen is made to flow for about 30 seconds in a pulsed manner, the supply of nitrogen is stopped, waits for about 150 seconds, and a cycle in which nitrogen is made to flow again for about 30 seconds is repeated. Although the ozone concentration 52 varies in a sawtooth shape, a relatively high ozone concentration can be maintained even while nitrogen is not supplied. On the other hand, it is considered that the nitrogen concentration is extremely low during the nitrogen supply stop period, and therefore the nitrogen oxide concentration is also considered to be extremely low (see FIG. 8).

  FIG. 11 shows the time variation of the generated ozone concentration 58 when the nitrogen supply is performed in a pulse form 54 as in FIG. 10 and the discharge output 56 is performed in a sawtooth shape. Similar to FIG. 10, a cycle of flowing nitrogen for about 60 seconds, stopping the nitrogen supply, waiting for about 900 seconds, and again flowing nitrogen for about 60 seconds again is repeated. In addition, the discharge output 56 is gradually increased so that the ozone concentration becomes constant when the nitrogen supply is stopped, and the discharge power is rapidly reduced when nitrogen is resupplied. In this way, the ozone concentration 58 is constant and stable although it causes fluctuations (decrease, increase, or a combination thereof) due to a rapid change at the start of nitrogen supply.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the following examples, the oxygen gas used is high-purity oxygen gas. Specifically, it is a high purity oxygen gas of 99.995% or more. Particularly in the following experimental examples, 99.9999% high-purity oxygen gas was used. It should be noted that ordinary oxygen gas can be purified and used as a high purity oxygen gas of 99.995% or more, and such oxygen gas is usually used in general semiconductor factories. It is also possible to use a gas in which an oxygen gas generator is used and the nitrogen gas is reduced to 20 ppm or less. As such an oxygen gas generator, for example, PSA and VSA are conceivable. The oxygen purity at this time is about 93%, but most of the remainder is argon gas. Therefore, it is considered that nitrogen oxides are generated like nitrogen and are not easily affected by corrosion. This is because argon is a rare gas.

[Experimental Example 1] The following experiment was performed in the ozone generator 10 of FIG. The flow rate of oxygen gas, which is a raw material gas of ozone, was supplied at 5 L / min. When the concentration of the generated ozone measured by the ozone monitor is the concentration (Hi), the nitrogen addition is switched to zero, and when the concentration is the concentration (Lo), the nitrogen addition is switched to a predetermined nitrogen concentration (here, 0.1%), This operation was repeated. The concentration (Hi) at this time is 200 g / m ³ (N), and the concentration (Lo) is 180 g / m ³ (N). The time change of the ozone concentration and the nitrogen gas flow rate at this time is shown in FIG. As can be seen from FIG. 12, the ozone concentration fluctuates in a sawtooth shape as in FIGS. Here, the nitrogen gas flow rate is not variably controlled according to the time, but is controlled by switching according to the upper limit and the lower limit of the ozone concentration. As a result, the average nitrogen addition (0.1%) time is about 0. 0. While the time was 4 minutes, the time for stopping (or not adding) nitrogen addition was about 2.4 minutes. If the ratio was taken, the time of nitrogen addition stop (or no addition) was about 6 times the time of nitrogen addition (0.1%). Therefore, when considering one cycle as a whole, the average nitrogen addition concentration was about 0.014%.

[Experimental Example 2] The following experiment was performed in the ozone generator 10 of FIG. The flow rate of oxygen gas, which is a raw material gas of ozone, was supplied at 5 L / min. When the concentration of the generated ozone measured by the ozone monitor is the concentration (Hi), the nitrogen addition is switched to zero, and when the concentration is the concentration (Lo), the nitrogen addition is switched to a predetermined nitrogen concentration (here, 0.01%), This operation was repeated. The concentration (Hi) at this time is 200 g / m ³ (N), and the concentration (Lo) is 180 g / m ³ (N). The time change of the ozone concentration and the nitrogen gas flow rate at this time is shown in FIG. As can be seen from FIG. 13, the ozone concentration fluctuates in a sawtooth shape as in FIGS. 5 and 10. Here, the nitrogen gas flow rate is not variably controlled according to the time, but is controlled by switching according to the upper limit and the lower limit of the ozone concentration. As a result, the average nitrogen addition (0.01%) time is about 1. The time for stopping nitrogen addition (or no addition) was about 6.6 minutes compared to 4 minutes. If the ratio is taken, the time for stopping nitrogen addition (or no addition) was about 4.7 times the time for nitrogen addition (0.01%). Therefore, when considering one period as a whole, the average nitrogen addition concentration was about 0.00175%. Compared to the case of FIG. 12, although it takes time to rise in the ozone concentration from the start of nitrogen supply, the rate of decrease when it was not added was moderate, and it was possible to operate without any additive for a relatively long time. .

[Experimental Example 3] The following experiment was performed in the ozone generator 10 of FIG. The flow rate of oxygen gas, which is a raw material gas of ozone, was supplied at 5 L / min. Nitrogen addition is switched to 0.005% when the concentration of generated ozone measured by the ozone monitor is concentration (Hi), and nitrogen addition is performed at a predetermined nitrogen concentration (here, 0.1%) at the concentration (Lo). This operation was repeated. The concentration (Hi) at this time is 200 g / m ³ (N), and the concentration (Lo) is 180 g / m ³ (N). FIG. 14 shows temporal changes in the ozone concentration and the nitrogen gas flow rate at this time. As can be seen from FIG. 14, the ozone concentration fluctuates in a sawtooth shape as in FIGS. 5 and 10. Here, the nitrogen gas flow rate is not variably controlled according to the time, but is controlled by switching according to the upper limit and the lower limit of the ozone concentration. As a result, the average nitrogen addition (0.1%) time is about 0. 0. While the time was 3 minutes, the time when the nitrogen addition was extremely reduced was about 5.0 minutes. If the ratio was taken, the time for low nitrogen addition (0.005%) was about 17 times the time for nitrogen addition (0.1%). Therefore, when considering one cycle as a whole, the average nitrogen addition concentration was about 0.01%. In this case, it can be seen that the operation time in the low addition state can be relatively long.

[Experimental Example 4] The following experiment was performed in the ozone generator 10 of FIG. The flow rate of oxygen gas, which is a raw material gas of ozone, was supplied at 5 L / min. At this time, the discharge output was subjected to feedback control independently with respect to the discharge output so that the measured ozone concentration was a set concentration of 210 g / m ³ (N). However, when the discharge output approaches 100% by this feedback control, nitrogen addition is performed at a predetermined nitrogen concentration (in this case, 0.01%), and at the same time, the discharge output is reduced according to the above feedback, and the discharge output is added with nitrogen. Nitrogen addition was switched to zero when it dropped to near stable discharge output. Subsequently, when the decrease in ozone concentration, which seems to be caused by no addition of nitrogen, was started, the discharge output was increased by the above-described feedback control, and the ozone concentration was made constant. This was repeated thereafter. FIG. 15 shows changes over time in ozone concentration, nitrogen gas flow rate, and discharge output at this time. As can be seen from FIG. 15, the ozone concentration changes relatively constant as in FIG. 11. Here, the nitrogen gas flow rate is not variably controlled with time, but is controlled by switching with the upper and lower limits of the discharge output (switching between ON and OFF). As a result, the average nitrogen addition (0. (01%) was about 7 minutes, while the time for stopping nitrogen addition (or no addition) was about 14 minutes. If the ratio was taken, the time of nitrogen addition stop (or no addition) was about twice the time of nitrogen addition (0.01%). Therefore, when considering one period as a whole, the average nitrogen addition concentration was about 0.003%.

[Experimental Example 5] The following experiment was performed in the ozone generator 10 of FIG. The flow rate of oxygen gas, which is a raw material gas of ozone, was supplied at 5 L / min. At this time, the discharge output was subjected to feedback control independently with respect to the discharge output so that the measured ozone concentration was a set concentration of 210 g / m ³ (N). However, when the discharge output is close to 100% by this feedback control, nitrogen addition is performed at a predetermined nitrogen concentration (here, 0.1%), and at the same time, the discharge output is reduced according to the feedback described above, and the discharge output is added with nitrogen. Nitrogen addition was switched to zero when it dropped to near stable discharge output. Subsequently, when the decrease in ozone concentration, which seems to be caused by no addition of nitrogen, was started, the discharge output was increased by the above-described feedback control, and the ozone concentration was made constant. This was repeated thereafter. FIG. 16 shows changes over time in ozone concentration, nitrogen gas flow rate, and discharge output at this time. As can be seen from FIG. 16, the ozone concentration changes relatively constant as in FIG. Here, the nitrogen gas flow rate is not variably controlled over time, but is controlled by switching according to the upper limit and lower limit of the discharge output. As a result, the average nitrogen addition time (0.1%) is about The time for stopping (or adding no) nitrogen was about 14.5 minutes compared to 1 minute. If the ratio was taken, the time of nitrogen addition stop (or no addition) was about 14.5 times the time of nitrogen addition (0.1%). Therefore, when considering one period as a whole, the average nitrogen addition concentration was about 0.0065%. Thus, it became possible to lengthen the non-addition time up to 14 minutes.

  As described above, when nitrogen is supplied in a pulsed manner, there is a period when nitrogen supply is unnecessary or a period when only a very small amount of nitrogen is required, even if ozone is stably generated at a certain concentration. I understand that Therefore, when the distribution device is controlled so that the mixed gas of generated ozone is used only during the period when the nitrogen supply is stopped, the generated gas released from the stop valve 20 is extremely low in nitrogen or nitrogen oxides. It will be a thing. For example, in FIG. 15, only a part of... Is used from 2, 3 minutes to 10 minutes, from 20 minutes to 30 minutes, from 40 minutes to 50 minutes, and so on. Other than that, it is also possible to control by the control unit 25 so as to exhaust from the stop valve 21 to the outside of the system.

  As described above, according to the present invention, the total amount of nitrogen gas can be reduced by intermittently supplying nitrogen gas and controlling the ozone concentration. This is because the inventors have discovered and used a characteristic change in the amount of ozone generated that the ozone concentration does not decrease immediately after the supply of nitrogen gas is stopped. Specifically, the supply of nitrogen gas is resumed when the ozone concentration is lowered to some extent, and the ozone concentration is raised relatively quickly. Thereafter, when the ozone concentration reaches a predetermined concentration, the supply of nitrogen gas is stopped and the ozone concentration is gently lowered. And when ozone concentration falls to some extent, supply of nitrogen gas is restarted, and the process of raising ozone concentration early is repeated.

  Here, such a so-called intermittent operation may be complete ON / OFF control, but may also be selective control of high addition rate / low addition rate. Further, the nitrogen addition rate may be varied in an analog manner. For example, the control is to increase or decrease the addition rate continuously at a change rate like a sine curve.

  Furthermore, feedback control based on the discharge output is added, and the time during which nitrogen is not added or the time during which the addition rate is low can be extended. Specifically, it is as follows. In the case of the operation of simply supplying / stopping nitrogen gas, it is expected that there will be some change in ozone concentration. Therefore, in order to reduce the fluctuation, the time for stopping the supply of nitrogen gas may be shortened, but the effect of suppressing the generation of nitrogen oxides may be reduced. Therefore, in order to keep the ozone concentration constant and to make the nitrogen gas supply stop time as long as possible so as to further suppress the generation of nitrogen oxides, the amount of nitrogen to be supplied is variably feedback-controlled with respect to the ozone concentration. You can also

  Further, if the supply of nitrogen gas is stopped and the discharge concentration has a margin even if the ozone concentration starts to decrease, the ozone concentration can be kept constant in a high concentration state by increasing the output. If the discharge output becomes 100% and the output cannot be increased any further, it is considered that the ozone concentration gradually decreases. However, the ozone concentration can be rapidly increased by restarting the supply of nitrogen gas at this time. Therefore, the discharge output can be decreased simultaneously with the resumption of supply, so that the ozone concentration does not increase excessively.

  And when it becomes a predetermined discharge output, supply of nitrogen gas is stopped. When the ozone concentration decreases with time, the discharge output is increased accordingly as described above. Then, when there is little room for increase in the discharge output, the supply of nitrogen is resumed and the discharge output is reduced. By performing the cycle as described above, the ozone concentration can be kept stable at a high concentration, and the generation of nitrogen oxides can be reduced.

  In addition, in synchronization with the treatment process with ozone, nitrogen gas is sufficiently added to the ozone generator before the treatment, the ozone concentration is increased, and the supply of nitrogen is stopped during the treatment with ozone. It is also possible to reduce the influence of nitrogen oxides in the treatment. Further, when the supply of nitrogen is resumed, the influence of nitrogen can be reduced if the treatment is not performed.

  Thus, compared with the continuous supply of nitrogen gas, the intermittent supply control as in the present invention can significantly reduce the supply of nitrogen gas as a whole, and significantly reduce the amount of nitrogen oxide generated. Can do.

It is a block diagram of the ozone generator by the Example of this invention. It is a schematic diagram which shows the time change of the ozone generation amount after starting discharge in a general ozone generator. In a general ozone generator, it is a schematic diagram which shows the relationship between a nitrogen addition rate and ozone generation density | concentration. It is a graph which shows the relationship between the measured nitrogen addition rate and ozone generation concentration. It is a schematic diagram which shows the relationship between the nitrogen intermittent addition by the Example of this invention, and ozone concentration. In a general ozone generator, it is a schematic diagram which shows the relationship between discharge output and ozone concentration. It is a schematic diagram which shows the ozone density | concentration change when changing a discharge output in a pulse form. In a general ozone generator, it is a mimetic diagram showing the relation of the amount of generated nitric oxide to the amount of added nitrogen. It is a schematic diagram which shows the change of the nitrate ion used as a parameter | index when quantifying nitrogen oxides. It is a schematic diagram which shows the change of ozone concentration at the time of performing control of intermittent nitrogen addition by the Example of this invention. It is a schematic diagram which shows the change of the ozone concentration at the time of performing nitrogen intermittent addition control and discharge output control by the Example of this invention. It is a graph which shows the result of the change of ozone concentration when performing nitrogen intermittent addition control in the ozone generator by the Example of this invention. It is a graph which shows the result of the change of ozone concentration when performing nitrogen intermittent addition control in the ozone generator by the Example of this invention. It is a graph which shows the result of the change of ozone concentration when performing nitrogen concentration addition control in the ozone generator by the Example of this invention. It is a graph which shows the result of the change of ozone concentration when performing nitrogen intermittent addition control and discharge output control in the ozone generator by the Example of this invention. It is a graph which shows the result of the change of ozone concentration when performing nitrogen intermittent addition control and discharge output control in the ozone generator by the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Ozone generator 12 Mass flow controller 13 Junction point 14 Discharge part 16 Ozone monitor 18 Orifice 20 Stop valve 21 Stop valve 22 Treatment tank 23 Ozone decomposer 24 Mass flow controller 25 Control part 25a Line 25b Line 25c Line 25d Line 30 Peak 32 Nitrogen low Ozone concentration at the time of addition 34 Ozone concentration at the time of high nitrogen addition 36 Ozone concentration at the time of very small addition of nitrogen 38 Ozone concentration unstable region 40 Ozone concentration stable region 42 Nitrogen concentration 44 Ozone concentration 46 Discharge output 48 Ozone concentration 50 Nitrogen concentration 52 Ozone concentration 54 Nitrogen concentration 56 Discharge output 58 Ozone concentration

Claims (13)

In an ozone generator that generates ozone by supplying high-purity oxygen to a discharge-type ozone generator,
Variable nitrogen supply means for supplying nitrogen to the ozone generator;
Measuring means for measuring the amount of ozone generated by the ozone generator;
Ozone amount control means for controlling the variable nitrogen supply means according to the ozone amount measured by the measuring means;
Discharge output control means for changing the discharge output;
With
The ozone amount control means controls the variable nitrogen supply means to supply a predetermined amount of nitrogen when the measured ozone amount reaches a predetermined value, and the ozone amount control means according to the ozone amount measured by the measurement means. An ozone generator characterized by transmitting a signal for changing the discharge output to the discharge output control means . 2. The ozone generator according to claim 1 , wherein when the nitrogen supply is performed by the variable nitrogen supply unit, the ozone amount control unit transmits a signal for changing a discharge output to the discharge output control unit. . The ozone generator according to claim 1 or 2 , wherein the variable nitrogen supply means performs intermittent supply of nitrogen. The variable nitrogen supply means continues the nitrogen supply for a predetermined time or until the ozone amount measured by the measuring means reaches a second predetermined value, and then stops the nitrogen supply, and according to the measured ozone amount The ozone generator according to any one of claims 1 to 3, wherein the nitrogen supply is not performed until the nitrogen supply is started again. Furthermore, a generated gas distribution means for distributing the generated ozone-containing gas is provided,
The distribution means distributes the generated ozone-containing gas into a high nitrogen content gas and a low nitrogen content gas according to the amount of ozone measured by the measurement means and / or the nitrogen supply performed by the variable nitrogen supply means. The ozone generator according to any one of claims 1 to 4, wherein The ozone generator according to any one of claims 1 to 5 , wherein the high-purity oxygen is 99.995% or more of high-purity oxygen. The ozone generator according to any one of claims 1 to 5 , wherein the high-purity oxygen is high-purity oxygen in which nitrogen gas as an impurity is 20 ppm or less. The ozone generator according to claim 7 , wherein the high-purity oxygen is 93% or more high-purity oxygen. In an ozone generation method for generating ozone by supplying high purity oxygen to a discharge type ozone generator,
Measuring the amount of ozone generated by the ozone generator;
A step of supplying a predetermined amount of nitrogen when the amount of ozone measured in the step reaches a predetermined value;
Varying the discharge output in accordance with the amount of ozone measured in the step of measuring the amount of ozone. The ozone generation method according to claim 9 , wherein the discharge output is simultaneously changed in the step of supplying the predetermined amount of nitrogen. 11. The ozone generation method according to claim 9 , wherein nitrogen is not supplied except for the step of supplying the predetermined amount of nitrogen. Performing a nitrogen supply of the predetermined amount is a predetermined time and / or measuring the amount of ozone is until the second predetermined value, the ozone generation according to any one of claims 9, characterized in that it is allowed to continue 11 Method. Furthermore, depending on the stage of performing the nitrogen supply of the predetermined amount, generated according 12 claim 9, characterized in that it comprises an ozone-containing gas to step of distributing the nitrogen-rich gas and a nitrogen-low-containing gas Ozone generation method.

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