JP7024916B1 - Ozone supply device and ozone supply method - Google Patents

Abstract

It is an object of the present disclosure to provide an ozone supply device and an ozone supply method capable of suppressing a decrease in ozone generation efficiency. The ozone supply device (100) of the present disclosure generates an ozoneified gas containing ozone from a raw material gas supply unit (1) that supplies a raw material gas containing oxygen and nitrogen, and a supply gas composed of the raw material gas and the return gas. The ozone generating section (2), the suction / desorption section (3) that adsorbs the ozone contained in the ozone-forming gas and discharges the returned gas, and the suction / desorption section (3) that absorbs and desorbs the ozone-forming gas generated by the ozone generating section (2). The pipe (4), the ozone generating section (2), and the suction / desorption section (3) that supply the return gas supplied to 3) and discharged from the suction / desorption section (3) together with the raw material gas to the ozone generating section (2). ), And a control unit (5) that controls the nitrogen concentration of the supply gas based on the information in the circulation circuit.

Description

The present disclosure relates to an ozone supply device and an ozone supply method.

Ozone is used as a powerful oxidant in a wide range of fields such as water environment purification or semiconductor cleaning, and with the recent increase in environmental awareness, the demand for high-concentration and highly efficient ozone supply technology has increased. There is. Since the upper limit of the generated ozone concentration in the ozone generation part of the ozone supply device is about 20%, the ozone adsorption phenomenon is used to store ozone and intermittently use high-concentration ozone gas. Attention is being paid to the technology and equipment supplied to.

In the ozone storage technology, oxygen and nitrogen are supplied to the ozone generation part, and ozone is selectively adsorbed to the adsorbent from the ozone-containing ozone gas generated in the ozone generation part, and most of the oxygen is discharged. do. An oxygen recycling technique is disclosed in which oxygen and nitrogen are supplied to an ozone generation unit and the discharged oxygen and nitrogen are used again as a gas for ozone generation (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-65620

However, in the technique described in Patent Document 1, since the amount of nitrogen contained in the gas supplied to the ozone generator together with oxygen is a predetermined amount, the gas in the ozone supply device increases with the lapse of the operating time of the ozone generator. The concentration of nitrogen contained in the ozone is not suitable for ozone generation, and there is a problem that the ozone generation efficiency is lowered.

The present disclosure has been made to solve the above-mentioned problems, and an object of the present disclosure is to provide an ozone supply device and an ozone supply method capable of suppressing a decrease in ozone generation efficiency.

The ozone supply device according to the present disclosure includes a raw material gas supply unit that supplies a raw material gas containing oxygen and nitrogen, an ozone generation unit that generates an ozone-containing gas containing ozone from a supply gas consisting of the raw material gas and the return gas. The suction / desorption section that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas, and the raw material gas supply section are not included. Control to control the nitrogen concentration of the supply gas based on the information in the circulation circuit including the piping that supplies the return gas discharged from the source gas to the ozone generation part, the ozone generation part, and the suction / desorption part, and the information in the circulation circuit. It is equipped with a part.

The ozone supply method according to the present disclosure includes a step of supplying a supply gas including a raw material gas and a return gas supplied from the raw material gas supply unit to the ozone generation unit, and an ozone-containing gas containing ozone from the supply gas by the ozone generation unit. The step of adsorbing the ozone contained in the ozone-ized gas to the suction / desorption part and the step of discharging the return gas from the suction / desorption part, and the step of discharging the return gas from the suction / desorption part, and the raw material gas supply part are not included and are generated in the ozone generation part. Information in the circulation circuit including the pipe, ozone generating part, and the suction / desorption part that supplies the ozone-ized gas to the suction / desorption part and supplies the return gas discharged from the suction / desorption part together with the raw material gas to the ozone generating part. Based on the above, the control unit has a step of controlling the nitrogen concentration of the supply gas.

According to the present disclosure, it is possible to suppress a decrease in ozone generation efficiency.

The block diagram which shows the ozone supply apparatus which concerns on Embodiment 1. The flow diagram which shows the operation of the control part of the ozone supply device which concerns on Embodiment 1. FIG. The figure which shows the gas circuit in the adsorption process of the ozone supply device which concerns on Embodiment 1. FIG. The figure which shows the gas circuit in the supply process of the ozone supply apparatus which concerns on Embodiment 1. FIG. The block diagram which shows the ozone supply device which is a comparative example. A characteristic diagram showing the nitrogen component concentration of the ozone supply device as a comparative example. The characteristic figure which shows the nitrogen component concentration of the ozone supply device which concerns on Embodiment 1. FIG. The flow diagram which shows the operation of the control part of the ozone supply device which concerns on Embodiment 1. FIG. The block diagram which shows the ozone supply apparatus which concerns on Embodiment 1. The block diagram which shows the ozone supply apparatus which concerns on Embodiment 1. The block diagram which shows the ozone supply apparatus which concerns on Embodiment 1. The block diagram which shows the ozone supply apparatus which concerns on Embodiment 2.

Preferred embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. The present disclosure is not limited to the following description, and may be appropriately modified without departing from the gist of the present disclosure. Further, in the present specification and the drawings, components having substantially the same function are designated by the same reference numerals, so that duplicate description will be omitted. In addition, in the drawing, the figure which shows the structure of a device and the shape of a member shows only the schematic structure and shape of a device and a member. The relative size and relative position of each member shown in each drawing do not necessarily accurately represent the magnitude relationship and the positional relationship between the actual members.

Embodiment 1.
FIG. 1 is a configuration diagram showing an ozone supply device 100a according to the first embodiment. The ozone supply device 100a includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90. The ozone supply device 100a further includes a nitrogen component concentration measuring unit 6. The details will be described below.

Here, the gas supplied from the raw material gas supply unit 1 is referred to as a raw material gas, and the gas discharged from the ozone generation unit 2 is referred to as an ozoneified gas. Further, the gas discharged from the suction / desorption portion 3 is referred to as a return gas. A supply gas consisting of a raw material gas supplied from the raw material gas supply unit 1 and a return gas discharged from the suction / desorption unit 3 is supplied to the ozone generation unit 2. The raw material gas, ozonizing gas, return gas and supply gas may be collectively referred to as gas.

Further, in the pipe 4 of FIG. 1, the point A is the point where the raw material gas and the return gas meet, the point B is between the ozone generation part 2 and the suction / desorption part 3, and the point C is the suction / desorption part 3 and the nitrogen. Between the component concentration measuring unit 6 and the point D, the point D indicates between the nitrogen removing unit 8 and the point A.

The raw material gas supply unit 1 supplies a raw material gas containing oxygen and nitrogen. The raw material gas supply unit 1 has an oxygen source 10 as a raw material gas source and a nitrogen addition unit 12. The nitrogen addition unit 12 has a nitrogen source 11 and a flow rate adjusting unit 13. The flow rate adjusting unit 13 controls the flow rate of the nitrogen to be added, and for example, a mass flow controller, a flow rate adjusting valve, or the like may be used. Controlling the diversion of added nitrogen also includes controlling not adding nitrogen. As the oxygen source 10 and the nitrogen source 11, for example, a cylinder or a PSA (Pressure Swing Adsorption) device or the like may be used. In the ozone supply device 100a, the purity of oxygen and nitrogen supplied from the oxygen source 10 and the nitrogen source 11 is preferably 99% or more, respectively.

The ozone generation unit 2 is a device that generates ozone gas containing ozone by using a supply gas composed of a raw material gas supplied from the raw material gas supply unit 1 and a return gas discharged from the suction / desorption unit 3. As the ozone generator 2, for example, a silent discharge type ozone generator driven by an AC high voltage may be used.

The suction / desorption unit 3 selectively adsorbs ozone contained in the ozone-forming gas generated by the ozone generation unit 2 by an adsorbent (not shown in FIG. 1) filled therein, and discharges the return gas. It is a device. As the adsorbent, one that preferentially adsorbs ozone contained in the ozone-forming gas, for example, silica gel may be used. Due to the adsorption characteristics of the adsorbent, the ozone concentration on the surface of the adsorbent is higher than the ozone concentration in the ozonizing gas. The suction / desorption unit 3 concentrates ozone so as to increase the ozone concentration of the ozone-forming gas, and generates concentrated ozone. Although not shown in FIG. 1, in order to desorb the concentrated ozone adsorbed by the adsorbent of the adsorption / desorption portion 3 from the adsorbent, the ozone supply device 100a injects a gas for desorption of ozone into the adsorption / desorption portion 3. A desorbable gas injection unit is provided. The desorption gas is, for example, oxygen.

The pipe 4 is a gas circuit that supplies the ozone-forming gas generated by the ozone generating section 2 to the suction / desorption section 3 and supplies the return gas discharged from the suction / desorption section 3 together with the raw material gas to the ozone generating section 2. be. Since ozone-containing gas containing ozone flows in the gas circuit of the pipe 4, it is desirable to use a corrosion-resistant material for the portion in contact with the gas. Further, it is desirable that the inside of the pipe 4 has a structure having a small pressure loss. Here, the ozone generation unit 2, the suction / desorption unit 3, and the pipe 4 are collectively referred to as a circulation circuit.

The booster blower 7 is provided between the suction / desorption unit 3 and the nitrogen component concentration measuring unit 6 in the pipe 4. The step-up blower 7 is a device that boosts the return gas and circulates the return gas in the pipe 4 at a required flow rate.

The nitrogen component concentration measuring unit 6 is a device for measuring the nitrogen component concentration of the returned gas. Here, the "nitrogen component" refers to nitrogen contained in the gas. That is, the nitrogen component concentration measuring unit 6 measures the nitrogen concentration contained in the returned gas . The nitrogen component concentration measuring unit 6 is installed between, for example, the boosted blower 7 and the point A where the returned gas and the raw material gas meet in order to measure the nitrogen component concentration of the returned gas boosted by the boosted blower 7. Just do it. The nitrogen component concentration measuring unit 6 may be provided between the ozone generating unit 2 and the adsorption / desorption unit 3 to measure the nitrogen component concentration of the ozone-forming gas, or may be provided between the point A and the ozone generating unit 2. The nitrogen component concentration of the supply gas may be measured.

The control unit 5 is a device that controls the nitrogen concentration of the supply gas based on the information in the circulation circuit. When the nitrogen component concentration measured by the nitrogen component concentration measuring unit 6 is larger than the predetermined first value, the nitrogen concentration of the supply gas is controlled to be reduced, and the nitrogen component concentration measuring unit 6 measures the nitrogen component concentration. When the nitrogen component concentration is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased. Here, the information in the circulation circuit includes the nitrogen component concentration of the returned gas, the nitrogen component concentration of the ozone-ized gas, the nitrogen component concentration of the supply gas, the information related to the ozone concentration of the ozone-ized gas, and the operation of the ozone generating unit. Information based on at least one of the elapsed times. The estimated nitrogen component concentration in the circulation circuit may be calculated based on the information in the circulation circuit, and the calculated nitrogen component concentration estimation value may be compared with the first value and the second value. When the information in the circulation circuit is, for example, the nitrogen component concentration in the circulation circuit and the information in the circulation circuit is measured by the nitrogen component concentration measuring unit 6, the nitrogen in the circulation circuit calculated by the control unit 5 The component concentration estimated value agrees with the measured value measured by the nitrogen component concentration measuring unit 6.

The predetermined first value and the second value are nitrogen component concentrations predetermined so that the ozone generation efficiency becomes an appropriate value. In the ozone supply device 100a, since the nitrogen component concentration measuring unit 6 measures the nitrogen component concentration of the returned gas, the first value and the second value are predetermined nitrogen component concentrations of the returned gas. .. The predetermined nitrogen component concentration of the return gas may be manually input by the operator. The control unit 5 is configured by, for example, a microcomputer or the like, and controls by installing a predetermined control program. The nitrogen component concentration referred to when the control unit 5 controls the nitrogen concentration of the supply gas, the nitrogen component concentration of the ozone-forming gas, the nitrogen component concentration of the supply gas, the information related to the ozone concentration of the ozone-forming gas, and ozone. The operation elapsed time of the generation unit may be manually input by the operator to the control unit 5, or the control unit 5 may receive signal information transmitted from a device in the circulation circuit.

When the measured value of the nitrogen component concentration is larger than the predetermined first value, the control unit 5 instructs the nitrogen removing unit 8 to remove nitrogen from the returned gas, increases the amount of nitrogen removed, and adds nitrogen. At least one of an instruction to reduce the amount of nitrogen added to the raw material gas and an instruction to stop the addition of nitrogen to the nitrogen addition part 12 is given to the part 12 to reduce the nitrogen concentration of the supply gas.

On the other hand, when the measured value of the nitrogen component concentration is smaller than the predetermined second value, the control unit 5 instructs the nitrogen removing unit 8 to reduce the amount of nitrogen removed from the returned gas, and the nitrogen removing unit 8 is instructed to reduce the amount of nitrogen removed. At least one of an instruction to stop the removal of nitrogen, an instruction to add nitrogen to the raw material gas to the nitrogen addition part, and an instruction to increase the amount of nitrogen added is given to increase the nitrogen concentration of the supply gas. The operations of the nitrogen removing unit 8 and the nitrogen adding unit 12 will be described later.

The nitrogen removing unit 8 is a device that removes nitrogen contained in the gas. The ozone supply device 100a removes nitrogen contained in the returned gas. Examples of the nitrogen removing method in the nitrogen removing unit 8 include a method of removing nitrogen in the returned gas using a nitrogen adsorbent (not shown in FIG. 1) that selectively adsorbs nitrogen.

Further, the nitrogen removing unit 8 adjusts the temperature of the nitrogen adsorbent in the nitrogen removing unit 8 by the first temperature adjusting unit 14. The first temperature control unit 14 lowers the temperature of the adsorbent when the nitrogen adsorbent of the nitrogen removing unit 8 adsorbs nitrogen, and raises the temperature of the adsorbent when the nitrogen adsorbent desorbs nitrogen. do. The first temperature control unit 14 is, for example, a constant temperature bath, a refrigerator, a chiller, or the like.

When the control unit 5 instructs the nitrogen removal unit 8 to remove the nitrogen concentration of the supply gas, the first temperature control unit 14 adjusts the temperature of the nitrogen adsorbent to reduce the amount of nitrogen removed from the return gas. Adjust. That is, the control unit 5 adjusts the temperature of the first temperature control unit 14, and the nitrogen removal unit 8 transfers nitrogen from the returned gas when the measured value of the nitrogen component concentration is larger than the predetermined first value. The amount of nitrogen removed is increased to reduce the nitrogen concentration of the supply gas. Further, when the measured value of the nitrogen component concentration is smaller than the predetermined second value, the nitrogen removing unit 8 reduces the amount of nitrogen removed from the returned gas and increases the nitrogen concentration of the supply gas.

Further, in the ozone supply device 100a, the nitrogen removing unit 8 does not go through the pipe 4 via the nitrogen removing unit 8 selected when removing nitrogen and the nitrogen removing unit 8 selected when not removing nitrogen. It has a pipe 4 (not shown in FIG. 1) via a bypass circuit, and is selected to be via a nitrogen removing unit 8 or a bypass circuit based on an instruction from the control unit 5. When the measured value of the nitrogen component concentration is larger than the predetermined first value, the control unit 5 selects the pipe 4 via the nitrogen removing unit 8 and starts removing nitrogen from the returned gas. Further, when the measured value of the nitrogen component concentration is smaller than the second value determined in advance, the control unit 5 selects the pipe 4 via the bypass circuit and stops the removal of nitrogen from the return gas.

On the other hand, when the control unit 5 instructs the nitrogen addition unit 12 to increase the nitrogen concentration of the supply gas, the nitrogen addition unit 12 adjusts the flow rate adjustment unit 13 to add the nitrogen supplied from the nitrogen source 11 to the raw material gas. To control. That is, when the measured value of the nitrogen component concentration is larger than the predetermined first value, the nitrogen addition unit 12 reduces the amount of nitrogen added to reduce the nitrogen concentration of the supply gas. Further, when the measured value of the nitrogen component concentration is larger than the predetermined first value, the nitrogen addition unit 12 stops the addition of nitrogen. Further, when the measured value of the nitrogen component concentration is larger than the predetermined first value, the nitrogen addition unit 12 intermittently opens the valve installed in the flow rate adjusting unit 13 to supply nitrogen from the nitrogen source 11. The amount of nitrogen added may be controlled. The timing at which the flow rate adjusting unit 13 opens the valve intermittently and the time during which the valve continues to open may be a program installed in the nitrogen adding unit 12 in advance or an instruction from the control unit 5. Further, when the measured value of the nitrogen component concentration is smaller than the predetermined second value and the addition of nitrogen to the raw material gas is stopped, the nitrogen addition unit 12 adds nitrogen to the raw material gas. To start. When the measured value of the nitrogen component concentration is smaller than the predetermined second value, the nitrogen addition unit 12 increases the amount of nitrogen added to increase the nitrogen concentration of the supply gas.

FIG. 2 is a flow chart showing the operation of the control unit 5 of the ozone supply device 100a according to the first embodiment. First, the control unit 5 receives the nitrogen component concentration, which is information in the circulation circuit, from the nitrogen component concentration measuring unit 6 (step ST1). Then, the control unit 5 determines whether or not the nitrogen component concentration measured by the nitrogen component concentration measuring unit 6 is larger than the predetermined first value (step ST2). In step ST2, when the nitrogen component concentration measured by the nitrogen component concentration measuring unit 6 is larger than the predetermined first value (YES), the control unit 5 controls to reduce the nitrogen concentration of the supply gas (step). ST3), for example, the nitrogen removing unit 8 is controlled to remove nitrogen in the gas. Then, the control unit 5 ends the control.

If NO is determined in step ST2, the control unit 5 determines whether or not the measured nitrogen component concentration is smaller than the predetermined second value (step ST4). In step ST4, when the measured nitrogen component concentration is smaller than the predetermined second value (YES), the control unit 5 controls to increase the nitrogen concentration of the supply gas (step ST5), for example, nitrogen addition. Part 12 is controlled to increase the amount of nitrogen added to the raw material gas. Then, the control unit 5 ends the control.

A predetermined value used for determining to decrease the nitrogen component concentration of the supply gas, that is, a predetermined value used for determining to increase the nitrogen component concentration of the supply gas, with the value used in step ST2 as the first value. The value used in step ST4 is set as the second value. By setting the first value to be larger than the second value, if NO is determined in step ST4, the ozone supply device 100a operates within the predetermined range of the first value and the second value. Since it can be determined that the control is performed, the control unit 5 ends the control.

In FIG. 2, the order of step ST2 and step ST4 is arbitrary and may be simultaneous. Further, the first value and the second value may be the same, and the nitrogen component concentration measured by the nitrogen component concentration measuring unit 6 may be compared with a predetermined value. If the measured nitrogen component concentration is higher than the predetermined value, the process proceeds to step ST3. If the measured nitrogen component concentration is smaller than the predetermined value, the process proceeds to step ST5. When the measured nitrogen component concentration is the same as the predetermined value, the treatment is terminated.

Next, the operation of the ozone supply device 100a, that is, the ozone supply method will be described. FIG. 3 is a diagram showing a gas circuit in the adsorption step of the ozone supply device 100a according to the first embodiment. The adsorption step is the circuit shown in bold in FIG. Further, FIG. 4 is a diagram showing a gas circuit in the supply process of the ozone supply device 100a according to the first embodiment. The supply process is the gas circuit shown in bold in FIG. In the ozone supply device 100a, a series of operations of the adsorption process and the supply process is referred to as one cycle.

First, the adsorption process will be described with reference to FIG. In the adsorption step, a supply gas supplied from the raw material gas supply unit 1 and composed of a raw material gas containing oxygen and nitrogen and a return gas is supplied to the ozone generation unit 2, and the ozone generation unit 2 supplies ozone from the supply gas. The step of generating the containing ozone gas, the step of adsorbing the ozone contained in the ozone-ized gas to the suction / desorption unit 3, and the step of discharging the return gas from the suction / desorption unit 3, and the process of generating the ozone gas were generated by the ozone generation unit 2. A circulation including a pipe 4, an ozone generating section 2, and an suction / desorption section 3 that supplies the ozone-ized gas to the suction / desorption section 3 and supplies the return gas discharged from the suction / desorption section 3 together with the raw material gas to the ozone generating section 2. It has a step of controlling the nitrogen concentration of the supply gas by the control unit 5 based on the information in the circuit. In the ozone supply device 100a, the nitrogen component concentration of the returned gas is measured by the nitrogen component concentration measuring unit 6. Further, when the nitrogen removing unit 8 operates based on the instruction of the control unit 5, the nitrogen adsorbed by the nitrogen adsorbent is discharged to the outside from the exhaust circuit 9.

In the adsorption step, when the amount of ozone adsorbed on the adsorbent of the adsorption / desorption portion 3 reaches the amount of ozone required for the ozone supply target (not shown in FIG. 3), the adsorbent of the adsorption / desorption portion 3 is used. When the ozone supply device 100a satisfies the preset conditions, such as when the adsorption of ozone has elapsed for a certain period of time, or when an operation transition signal instructing the transition from the adsorption process to the supply process is input from the outside, ozone The supply device 100a shifts to the supply process.

Next, the supply process will be described with reference to FIG. In the supply step, the ozone adsorbed by the adsorbent of the adsorption / desorption unit 3 is desorbed from the adsorbent and supplied to the ozone supply target (not shown in FIG. 4). When the amount of ozone desorbed from the adsorbent of the adsorption / desorption unit 3 reaches the amount of ozone required for the supply target, or when an operation transition signal instructing the transition from the supply process to the adsorption process is input from the outside, etc. When the ozone supply device 100a satisfies the preset conditions, the ozone supply device 100a shifts to the adsorption step of the next cycle.

Next, the configuration of the ozone supply device 101 will be described by comparing the ozone supply device 100a with the ozone supply device 101 which is a comparative example. FIG. 5 is a configuration diagram showing an ozone supply device 101 as a comparative example. In FIG. 5, the configuration with the same reference numerals as those in FIG. 1 corresponds to or corresponds to the configuration of the ozone supply device 100a, and therefore detailed description thereof will be omitted. The ozone supply device 101 differs from the ozone supply device 100a in that it does not include a control unit 5, a nitrogen component concentration measurement unit 6, a nitrogen removal unit 8, a nitrogen addition unit 12, an exhaust circuit 9, and a first temperature control unit 14. ..

Next, the operation of the ozone supply device 101 will be described. The ozone supply device 101 has an adsorption step and a supply step, similarly to the ozone supply device 100a.

The operation of the ozone supply device 101 differs from the operation of the ozone supply device 100a in that the ozone supply device 101 has a constant amount of nitrogen added to the raw material gas. That is, the nitrogen concentration of the raw material gas is constant regardless of the nitrogen component concentration of the returned gas. In the raw material gas supplied from the raw material gas supply unit 1, when the amount of nitrogen added to oxygen is constant, ozone is generated from oxygen by the ozone generation unit 2, and ozone is selectively used as the adsorbent of the adsorption / desorption unit 3. The concentration of the nitrogen component of the returned gas continues to increase with the passage of the operating time of the ozone supply device 101. With the passage of the operating time of the ozone generator, there is a problem that the concentration of nitrogen contained in the gas in the ozone supply device increases and the ozone generation efficiency decreases.

Further, the raw material gas supply unit 1 of the ozone supply device 101 adds nitrogen to the raw material gas only at the start of operation of the ozone supply device 101, and then does not add nitrogen, that is, the raw material gas containing only oxygen. When supplied, in the ozone supply device 101, the nitrogen concentration of the returned gas continues to decrease with the passage of the operating time of the ozone supply device 101. With the passage of operating time of the ozone generator, the concentration of nitrogen contained in the gas in the ozone supply device decreases, and it occurs when the ozone zero phenomenon, that is, when high-purity oxygen gas is used as the raw material for ozone generation. There was a problem that the ozone generation efficiency dropped sharply.

Next, the nitrogen component concentrations at the points A to D of the pipe 4 of the ozone supply device 100a and the ozone supply device 101 will be described. FIG. 6 is a characteristic diagram showing the nitrogen component concentration of the ozone supply device 101 as a comparative example, and FIG. 7 is a characteristic diagram showing the nitrogen component concentration of the ozone supply device 100a according to the first embodiment. In FIGS. 6 and 7, the vertical axis is the concentration of nitrogen component contained in the gas, and the horizontal axis points A1 to D1, points A2 to D2, and points A3 are points A to points in FIGS. 1 and 5, respectively. It corresponds to D.

First, the nitrogen component concentration at each point of the ozone supply device 101 will be described with reference to FIG. As described above, the ozone supply device 101 has a constant amount of nitrogen added to oxygen as a raw material gas. At the point A1, the nitrogen component concentration is C ₀ , but since ozone is selectively adsorbed by the adsorbent of the adsorption / desorption portion 3, the nitrogen component concentration contained in the gas is C between the points B1 and the point C1. _Increases from ₀ to C1. Assuming that the nitrogen component concentration of the raw material gas is lower than the nitrogen component concentration of the return gas, then at point A2, the nitrogen component concentration decreases from C ₁ to C ₂ due to the mixing of the raw material gas and the return gas. At this time, the nitrogen component concentration of the supply gas does not decrease to _C0 , which is the nitrogen component concentration of the raw material gas.

Then, when the supply gas is supplied to the ozone generation unit 2 and the ozone-ized gas generated by the ozone generation unit 2 is selectively adsorbed by the adsorbent of the adsorption / desorption unit 3, between the points B2 and C2. Then, the concentration of the nitrogen component contained in the gas increases from C ₂ to C _1' . After that, at point A3, the nitrogen component concentration decreases from C _1'to C _2'by mixing the raw material gas and the return gas, but the nitrogen component concentration of the mixed gas is the nitrogen component concentration of the raw material gas. It does not decrease to a certain C ₀ .

As described above, the nitrogen component concentration continues to increase with the lapse of the operating time of the ozone supply device 101. When the nitrogen component concentration increases, the ozone generation efficiency in the ozone generation unit 2 decreases, which causes an increase in the operating cost of the ozone supply device 101. Further, the ozone-forming gas discharged from the ozone generating unit 2 contains nitrogen oxides. Nitrogen oxides are generated in the discharge space of the ozone generation unit 2 due to the dissociation of nitrogen added to oxygen as a raw material gas. In addition to ozone, nitrogen oxides are also adsorbed and concentrated in the adsorbent of the adsorption / desorption portion 3, which causes poisoning or deterioration of the adsorbent, resulting in deterioration of the adsorbent's adsorption capacity over time. There is concern about corrosion deterioration of the adsorption / desorption portion 3.

Further, as described above, when the raw material gas supply unit 1 stops adding nitrogen to the raw material gas after a certain period of time, the nitrogen component concentration continues to decrease with the lapse of the operating time of the ozone supply device 101. Further, even when the raw material gas supply unit 1 does not add nitrogen to the raw material gas, that is, when the raw material gas supply unit 1 has only the oxygen source 10, the nitrogen component concentration increases with the lapse of the operating time of the ozone supply device 101. It keeps decreasing. When the nitrogen component concentration decreases, the ozone generation efficiency in the ozone generation unit 2 sharply decreases due to the ozone zero phenomenon, which causes an increase in the operating cost of the ozone supply device 101.

On the other hand, in the ozone supply device 100a, as shown in FIG. 7, even if the nitrogen component concentration rises to C _1'from the point B2 to the point C2, the information is related to the nitrogen component concentration of the returned gas. Since the control unit 5 controls to reduce the nitrogen concentration of the supplied gas based on the nitrogen component concentration of the returned gas, the nitrogen removing unit 8 between the points C2 and the point D2 has a C ₀ equivalent to the nitrogen concentration of the raw material gas. Up to, the nitrogen concentration can be reduced. Further, although not shown in FIG. 7, when the nitrogen component concentration is C ₀ or less, the nitrogen addition unit 12 increases the amount of nitrogen added to the raw material gas, and C is equivalent to the nitrogen concentration of the raw material gas. You can raise it to ₀ .

As described above, the ozone supply device 100a generates ozone that generates ozone-containing ozone gas from the raw material gas supply unit 1 that supplies the raw material gas containing oxygen and nitrogen and the supply gas consisting of the raw material gas and the return gas. The suction / desorption unit 3 that adsorbs ozone contained in the ozone-forming gas and discharges the returned gas, and supplies the ozone-forming gas generated by the ozone generation unit 2 to the suction / desorption unit 3. The nitrogen concentration of the supply gas based on the information in the circulation circuit including the pipe 4, the ozone generation part 2, and the suction / desorption part 3 that supplies the return gas discharged from the source gas together with the raw material gas to the ozone generation part 2. A control unit 5 for controlling the gas is provided.

With the above configuration, the ozone supply device 100a controls the nitrogen concentration of the supply gas based on the information in the circulation circuit, so that the decrease in ozone generation efficiency can be suppressed.

Further, since the ozone supply device 100a controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

The information in the circulation circuit may be information related to the nitrogen component concentration of the returned gas. Then, the control unit 5 calculates the nitrogen component concentration estimated value of the returned gas based on the information related to the nitrogen component concentration of the returned gas, and the calculated nitrogen component concentration estimated value is higher than the predetermined first value. If it is large, control is performed to reduce the nitrogen concentration of the supply gas, and if the calculated nitrogen component concentration estimated value is smaller than the predetermined second value, control is performed to increase the nitrogen concentration of the supply gas. May be good. Here, the information related to the nitrogen component concentration of the returned gas includes the nitrogen component concentration of the returned gas, the nitrogen component concentration of the ozone-ized gas, the nitrogen component concentration of the supply gas, the information related to the ozone concentration of the ozone-ized gas, and Information based on at least one of the elapsed operating times of the ozone generating unit. The predetermined first value and second value are the nitrogen component concentrations of the return gas determined in advance so that the ozone generation efficiency becomes an appropriate value. The predetermined nitrogen component concentration of the return gas may be calculated from the nitrogen component concentration of the supply gas at which the ozone generation efficiency is an appropriate value.

When the information related to the nitrogen component concentration of the return gas is, for example, the nitrogen component concentration of the return gas and the nitrogen component concentration of the return gas is measured by the nitrogen component concentration measuring unit 6, the return is calculated by the control unit 5. The estimated nitrogen component concentration of the gas agrees with the measured value measured by the nitrogen component concentration measuring unit 6.

Here, an ozone supply device 100b will be described as an example of controlling the nitrogen concentration of the supply gas based on the information related to the nitrogen component concentration of the return gas. FIG. 8 is a flow chart showing the operation of the control unit 5 of the ozone supply device 100b according to the first embodiment. Similar to the ozone supply device 100a, the ozone supply device 100b includes a raw material gas supply unit 1, an ozone generation unit 2, an adsorption / desorption unit 3, a pipe 4, a control unit 5, a nitrogen component concentration measurement unit 6, a step-up blower 7, and nitrogen removal. A unit 8, an exhaust circuit 9, and an ozone exhaust circuit 90 are provided.

First, the control unit 5 receives the nitrogen component concentration, which is information related to the nitrogen component concentration of the returned gas, from the nitrogen component concentration measuring unit 6 (step ST10). Then, the control unit 5 calculates the estimated nitrogen component concentration of the returned gas based on the information related to the nitrogen component concentration of the returned gas (step ST11). In the ozone supply device 100b, as described above, the calculated nitrogen component concentration estimated value and the nitrogen component concentration measured by the nitrogen component concentration measuring unit 6 match.

Then, the control unit 5 determines whether or not the calculated nitrogen component concentration estimated value is larger than the predetermined first value (step ST12). In step ST12, when the estimated nitrogen component concentration is larger than the predetermined first value (YES), the control unit 5 controls to reduce the nitrogen concentration of the supply gas (step ST13), for example, the nitrogen removal unit. No. 8 is controlled to remove nitrogen in the gas. Then, the control unit 5 ends the control.

If NO is determined in step ST12, the control unit 5 determines whether or not the calculated nitrogen component concentration estimated value is smaller than the predetermined second value (step ST14). In step ST14, when the estimated nitrogen component concentration is smaller than the predetermined second value (YES), the control unit 5 controls to increase the nitrogen concentration of the supply gas (step ST15), for example, the nitrogen addition unit. No. 12 is controlled to increase the amount of nitrogen added to the raw material gas. Then, the control unit 5 ends the control.

A predetermined value used for determining to decrease the nitrogen component concentration of the supply gas, that is, a predetermined value used for determining to increase the nitrogen component concentration of the supply gas, with the value used in step ST12 as the first value. The value used in step ST14 is set as the second value. By setting the first value to be larger than the second value, if NO is determined in step ST14, the ozone supply device 100b operates within the predetermined range of the first value and the second value. Since it can be determined that the control is performed, the control unit 5 ends the control.

As described above, since the ozone supply device 100b controls the nitrogen concentration of the supply gas based on the information related to the nitrogen component concentration of the return gas, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 100b controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

Hereinafter, a modification in which the control unit 5 calculates an estimated value of the nitrogen component concentration of the return gas based on the information related to the nitrogen component concentration of the return gas and controls the nitrogen concentration of the supply gas will be described.

<Modification example 1>
Next, a modification 1 in the first embodiment is shown. FIG. 9 is a block diagram showing the ozone supply device 100c according to the first embodiment. The ozone supply device 100c includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90. The ozone generation unit 2 of the ozone supply device 100c further has a detection unit 15. In FIG. 9, the configuration with the same reference numerals as those in FIG. 1 indicates the same or corresponding configuration as the configuration of the ozone supply device 100a, and therefore detailed description thereof will be omitted. The details will be described below.

In the ozone supply device 100c, the information related to the nitrogen component concentration of the returned gas is the nitrogen component concentration of the supply gas. In the ozone supply device 100c, the nitrogen component concentration of the supply gas is estimated based on the emission intensity of nitrogen detected by the detection unit 15.

The detection unit 15 of the ozone generation unit 2 detects an emission spectrum derived from nitrogen in the discharge space of the ozone generation unit 2, for example, the second positive system of nitrogen molecules, the NO-γ band, or the like. The nitrogen component concentration of the supplied gas is estimated based on the spectrum detection intensity, that is, the emission intensity. For the detection unit 15, for example, a semiconductor light receiving element, for example, a photodiode or the like is used. Further, in the detection unit 15, the spectrum detection by the light receiving element becomes easy by applying the band bus filter.

In the ozone supply device 100c, when the estimated nitrogen component concentration of the return gas calculated from the nitrogen component concentration of the supply gas estimated based on the emission intensity of nitrogen is larger than the predetermined first value, the supply gas When the nitrogen component concentration of the supply gas is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased. In the ozone supply device 100c, when the nitrogen component concentration of the supply gas estimated based on the emission intensity of nitrogen is larger than the predetermined first value, the nitrogen concentration of the supply gas is controlled to be reduced, and the supply gas is controlled. When the nitrogen component concentration of the above is smaller than the predetermined second value, the nitrogen concentration of the supply gas may be controlled to be increased.

As described above, since the ozone supply device 100c controls the nitrogen concentration of the supply gas based on the nitrogen concentration of the supply gas, it is possible to suppress a decrease in the ozone generation efficiency.

Further, since the ozone supply device 100c controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

In the ozone supply device 100c, an example of estimating the nitrogen concentration of the supply gas based on the emission intensity of nitrogen is shown. However, if the emission intensity of nitrogen is predetermined and the emission intensity is high, the nitrogen removing unit 8 is used. An instruction to remove nitrogen from the return gas may be transmitted, and if the predetermined emission intensity is low, the nitrogen addition unit 12 may be instructed to add nitrogen to the raw material gas. That is, as shown in the ozone supply device 100a, the nitrogen concentration of the supply gas may be controlled based on the emission intensity of nitrogen, which is information in the circulation circuit.

<Modification 2>
Next, a modification 2 of the first embodiment is shown. FIG. 10 is a block diagram showing the ozone supply device 100d according to the first embodiment. The ozone supply device 100d includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90. The ozone supply device 100d further includes an ozone concentration measuring unit 16. In FIG. 10, the configuration with the same reference numerals as those in FIG. 1 indicates the same or corresponding configuration as the configuration of the ozone supply device 100a, and therefore detailed description thereof will be omitted. The details will be described below.

In the ozone supply device 100d, the information related to the nitrogen component concentration of the returned gas is the information related to the ozone concentration of the ozone-ized gas. In the ozone supply device 100d, the nitrogen component concentration of the ozone-forming gas is estimated based on the ozone concentration measured by the ozone concentration measuring unit 16.

The ozone concentration measuring unit 16 measures the ozone concentration of the ozone-forming gas. The ozone concentration measuring unit 16 is installed, for example, between the ozone generating unit 2 and the adsorption / desorption unit 3 in order to measure the ozone concentration of the ozone-forming gas discharged from the ozone generating unit 2.

The control unit 5 estimates the nitrogen component concentration of the returned gas based on the ozone concentration. Since the ozone concentration decreases whether the nitrogen component concentration is too high or too low, the control unit 5 estimates, for example, assuming that the nitrogen component concentration is too high. It may be estimated assuming that it is too low. When the calculated nitrogen component concentration estimation value of the return gas is larger than the predetermined first value, the control unit 5 controls to reduce the nitrogen concentration of the supply gas, and the nitrogen component concentration of the supply gas becomes high. If it is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased.

The control unit 5 may instruct the nitrogen removing unit 8 to remove nitrogen or the nitrogen adding unit 12 to add nitrogen based on the ozone concentration.

However, if the nitrogen component concentration is too high or too low, the ozone concentration will decrease. That is, when the ozone concentration of the ozone-forming gas decreases, it is difficult to determine whether the cause is a high or low nitrogen component concentration. Therefore, in the ozone supply device 100d, for example, the following control is performed.

First, as a control example 1, the control unit operates the preset control unit 5, for example, the control unit so as to perform the opposite operation when the ozone concentration is not recovered with respect to the addition or removal of nitrogen. 5 is controlled. Specifically, when the ozone concentration decreases below a predetermined value, the nitrogen is first controlled to be removed. Then, after a certain period of time, if the ozone concentration of the ozone-forming gas does not recover, the control is switched to the addition of nitrogen.

That is, the nitrogen component concentration estimated value of the returned gas is calculated based on the information related to the nitrogen component concentration of the returned gas, and if the calculated nitrogen component concentration estimated value is larger or smaller than the predetermined value, it is set in advance. The control unit 5 is controlled, and if the calculated nitrogen component concentration estimated value is continuously large or small, the control opposite to the operation of the controlled unit 5 is performed.

Further, as a control example 2, it is determined whether the nitrogen component concentration is high or low by storing the operation of the control unit 5. For example, in the case where the ozone supply device 100d is operated for removing nitrogen without adding nitrogen for a certain period of time, if the ozone concentration of the ozone-forming gas is reduced, it can be determined that the amount of nitrogen in the supply gas is insufficient.

As described above, since the ozone supply device 100d controls the nitrogen concentration of the supply gas based on the information related to the ozone concentration of the ozone-forming gas, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 100d controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

<Modification 3>
Next, a modification 3 in the first embodiment will be shown. FIG. 11 is a block diagram showing the ozone supply device 100e according to the first embodiment. The ozone supply device 100e includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90. The ozone supply device 100e further includes an ozone concentration measuring unit 16a and an ozone concentration measuring unit 16b. In FIG. 11, the configurations with the same reference numerals as those in FIG. 1 indicate the same or corresponding configurations as the configurations of the ozone supply device 100a, and therefore detailed description thereof will be omitted. The details will be described below.

In the ozone supply device 100e, the information related to the nitrogen component concentration of the returned gas is the information related to the ozone concentration of the ozone-ized gas. In the ozone supply device 100e, the information related to the ozone concentration of the ozone-ized gas is the amount of ozone adsorbed on the adsorbent of the desorption unit 3 acquired from the desorption unit 3.

The control unit 5 estimates the nitrogen component concentration of the returned gas based on the amount of ozone adsorbed. When the calculated nitrogen component concentration estimation value of the return gas is larger than the predetermined first value, the control unit 5 controls to reduce the nitrogen concentration of the supply gas, and the nitrogen component concentration of the supply gas becomes high. If it is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased.

When the ozone adsorption amount is smaller than the predetermined ozone adsorption amount based on the ozone adsorption amount, the control unit 5 instructs the nitrogen removing unit 8 to remove nitrogen from the gas, or gives the nitrogen addition unit 12 the raw material gas. May be instructed to add nitrogen to the water.

As a method of measuring the amount of ozone adsorbed by the suction / desorption unit 3, for example, an ozone concentration measuring unit 16a is installed between the ozone generation unit 2 and the suction / desorption unit 3, and the suction / desorption unit 3 and the booster blower 7 are used. A method of installing an ozone concentration measuring unit 16b between them and measuring the amount of ozone adsorbed on the adsorbent of the adsorption / desorption unit 3 can be mentioned. By installing the ozone concentration measuring unit 16 before and after the desorption unit 3, the change in the ozone concentration in the desorption unit 3 can be measured, and the amount of ozone adsorbed by the adsorbent in the desorption unit 3 is estimated. can do.

Similar to the ozone supply device 100d, in the ozone supply device 100e, when the ozone adsorption amount of the adsorption / desorption portion 3 decreases, it is difficult to determine whether the cause is a high nitrogen component concentration or a low nitrogen component concentration. Therefore, even in the ozone supply device 100e, the nitrogen concentration of the supply gas may be controlled by performing the control as in the control example 1 or 2 described above.

As described above, since the ozone supply device 100e controls the nitrogen concentration of the supply gas based on the information related to the ozone concentration of the ozone-forming gas, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 100e controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

<Modification example 4>
Next, a modification 4 in the first embodiment is shown. The ozone supply device 100f includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90. The ozone supply device 100f further includes an ozone concentration measuring unit 16.

In the ozone supply device 100f, the information related to the nitrogen component concentration of the returned gas is the information related to the ozone concentration of the ozone-ized gas. In the ozone supply device 100f, the information related to the ozone concentration of the ozone gas is a measured value or a set value of the discharge power at the time of generating the ozone gas, which is received from the ozone generation unit 2. At this time, the ozone generating unit 2 has a feedback control for bringing the ozone concentration of the generated ozone-forming gas closer to a set value based on the information of the ozone concentration measured by the ozone concentration measuring unit 16.

The control unit 5 estimates the nitrogen component concentration of the return gas based on the information of the discharge power measured or set by the ozone generation unit 2. When the calculated nitrogen component concentration estimation value of the return gas is larger than the predetermined first value, the control unit 5 controls to reduce the nitrogen concentration of the supply gas, and the nitrogen component concentration of the supply gas becomes high. If it is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased.

Based on the information on the discharge power measured or set by the ozone generation unit 2, the control unit 5 instructs the nitrogen removal unit 8 to remove nitrogen from the gas or nitrogen when the discharge power is higher than a predetermined value. The addition unit 12 may be instructed to increase the amount of nitrogen added to the raw material gas.

Similar to the ozone supply device 100d, when the discharge power of the ozone supply device 100f is higher than a predetermined value, it is difficult to determine whether the cause is the high or low nitrogen component concentration of the supply gas. Therefore, even in the ozone supply device 100f, the nitrogen concentration of the supply gas may be controlled by performing the control as in the control example 1 or 2 described above.

As described above, since the ozone supply device 100f controls the nitrogen concentration of the supply gas based on the information related to the ozone concentration of the ozone-forming gas, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 100f controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

In the modified example 4, the ozone generation efficiency can be calculated based on the information of the ozone concentration acquired by the ozone concentration measuring unit 16 and the information of the discharge power acquired by the ozone generating unit 2. The nitrogen component concentration of the supply gas may be estimated using the ozone generation efficiency as information related to the ozone concentration of the ozone-forming gas.

<Modification 5>
Next, a modification 5 in the first embodiment is shown. The ozone supply device 100g includes a raw material gas supply unit 1, an ozone generation unit 2, an absorption / desorption unit 3, a pipe 4, a control unit 5, a booster blower 7, a nitrogen removal unit 8, an exhaust circuit 9, and an ozone discharge circuit 90.

Information related to the nitrogen component concentration of the returned gas may be used as the operating status of the ozone generating unit 2. In the ozone supply device 100g, the information related to the nitrogen component concentration of the returned gas is the information on the discharge time from the start of the adsorption process of the ozone generation unit 2, that is, the elapsed discharge time, received from the ozone generation unit 2 by the control unit 5. Is.

The control unit 5 estimates the nitrogen component concentration of the returned gas based on the elapsed discharge time of the ozone generation unit 2. When the calculated nitrogen component concentration estimation value of the return gas is larger than the predetermined first value, the control unit 5 controls to reduce the nitrogen concentration of the supply gas, and the nitrogen component concentration of the supply gas becomes high. If it is smaller than the predetermined second value, the nitrogen concentration of the supply gas is controlled to be increased.

The control unit 5 may give an instruction to remove nitrogen from the gas or an instruction to add nitrogen to the raw material gas to the nitrogen addition unit 12 based on the elapsed discharge time of the ozone generation unit 2. At this time, whether to remove nitrogen from the gas or add nitrogen to the raw material gas may be determined by performing the control as in Control Example 1 or 2 described above, and the nitrogen concentration of the supply gas may be controlled.

As described above, since the ozone supply device 100g controls the nitrogen concentration of the supply gas based on the information related to the ozone concentration of the ozone-forming gas, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 100g controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

In addition, in the modification 2 to 5, an example in which the determination of whether to increase or decrease the nitrogen concentration of the supply gas is performed by the control example 1 or 2 is shown, but the ozone supply device 100a to 100g (hereinafter collectively referred to as a group) is shown. The configuration of "ozone supply device 100") may be combined to make a comprehensive judgment based on a plurality of measured values.

In the first embodiment, in the ozone supply device 100a of FIG. 1, the nitrogen component concentration measuring unit 6 is installed between the booster blower 7 and the confluence point A, but the ozone generating unit 2 and the adsorption / desorption unit 2 are installed. A second nitrogen component concentration measuring unit 6 may be installed on the pipe 4 between the third and the third. By installing a nitrogen component concentration measuring unit before and after the adsorption / desorption unit 3, it is possible to measure the change in the nitrogen component concentration in the adsorption / desorption unit 3, and the amount of nitrogen adsorbed by the adsorbent in the adsorption / desorption unit 3 can be measured. Can be estimated. By estimating the amount of nitrogen adsorbed by the adsorbent in the suction / desorption unit 3, the change in the nitrogen concentration of the returned gas can be predicted in advance, and the control unit 5 controls to increase or decrease the nitrogen concentration of the supply gas. It can be used as information for doing.

Further, in the first embodiment, an oxygen concentration measuring unit for measuring the oxygen concentration of at least one of the return gas, the ozonizing gas, and the supply gas may be further provided. The control unit 5 may control the nitrogen concentration of the supply gas based on the measured value of the oxygen concentration measured by the oxygen concentration measuring unit. Alternatively, the control unit 5 may estimate the concentration of at least one of the nitrogen components of the return gas, the ozone-ized gas, and the supply gas based on the measured value of the oxygen concentration measured by the oxygen concentration measuring unit.

Further, in the first embodiment, as a method for removing oxygen in the nitrogen removing unit 8, an oxygen adsorbent that selectively adsorbs oxygen is used to adsorb oxygen in the returned gas and exhaust the unadsorbed nitrogen. A method may be used in which oxygen discharged from the circuit 9 to the outside of the pipe 4 and oxygen adsorbed on the oxygen adsorbent is discharged again as a return gas.

Embodiment 2.
FIG. 12 is a block diagram showing the ozone supply device 200 according to the second embodiment. The ozone supply device 200 controls to increase or decrease the nitrogen concentration of the supplied gas based on the information in the circulation circuit, and also controls to reduce the nitrogen oxide concentration in the gas based on the information in the circulation circuit. Therefore, it is different from the ozone supply device 100. The ozone supply device 200 includes a nitrogen oxide removing unit 17, a second temperature control unit 18, and a purge circuit 19 in addition to the configuration of the ozone supply device 100.

In the ozone supply device 200, the nitrogen oxide removing unit 17 is installed on the pipe 4 between the ozone generating unit 2 and the suction / desorption unit 3. The nitrogen oxide removing unit 17 is a device that removes nitrogen oxides generated in the ozone generating unit 2. Examples of the method for removing nitrogen oxides in the nitrogen oxide removing unit 17 include a method using an adsorbent (hereinafter referred to as “NOx adsorbent”) that selectively adsorbs nitrogen oxides. The NOx adsorbent preferably has a change in adsorption performance due to a temperature change, and particularly preferably has a large change in the amount of nitrogen oxide adsorbed in the range of −30 ° C. or higher and 40 ° C. or lower. Further, as the NOx adsorbent, one capable of desorbing the adsorbed nitrogen oxide by gas purging of the raw material gas by the purge circuit 19 (described later) is preferable. The nitrogen oxide desorbed from the NOx adsorbent by the raw material gas is discharged from the nitrogen oxide exhaust circuit 91. As the NOx adsorbent, for example, silica gel may be used.

The nitrogen component concentration measuring unit 6 measures the nitrogen concentration and the nitrogen oxide concentration contained in the returned gas. When the nitrogen oxide measured by the nitrogen component concentration measuring unit 6 is larger than a predetermined value, the control unit 5 sends an instruction to remove the nitrogen oxide from the ozone-ized gas to the nitrogen oxide removing unit 17. do.

The second temperature control unit 18 is a device that controls the temperature of the nitrogen oxide removing unit 17. Examples of the second temperature control unit 18 include a constant temperature bath, a refrigerator, a chiller, and the like. The second temperature control unit 18 preferably has a function of raising the temperature to a temperature higher than the sublimation temperature of N ₂ O ₅ . Further, the second temperature control unit 18 may have a function of adjusting the temperature of the suction / desorption unit 3.

The purge circuit 19 is a circuit for supplying the raw material gas to the nitrogen oxide removing unit 17, and is a gas circuit connected from the raw material gas supply unit 1 to the nitrogen oxide removing unit 17. The purge circuit 19 preferably has a flow rate adjusting unit for adjusting the purge flow rate to the nitrogen oxide removing unit 17.

Next, the operation of the ozone supply device 200 will be described. The ozone supply device 200 has an adsorption step and a supply step similar to the ozone supply device 100. Further, the ozone supply device 200 has a removal step of desorbing and removing nitrogen oxides from the nitrogen oxide removing unit 17 between the desorption step and the adsorption step of the next cycle.

The operation of the control unit 5 in the adsorption process of the ozone supply device 200 will be described as being different from the ozone supply device 100. In the adsorption step of the ozone supply device 200, the nitrogen oxide removing unit 17 performs an operation of removing nitrogen oxides in the pipe 4 when the control unit 5 determines that the nitrogen oxide concentration in the gas is reduced. The nitrogen oxide removing unit 17 removes nitrogen oxides in the ozone-ized gas based on the instruction from the control unit 5 to reduce the nitrogen oxide concentration. Further, the nitrogen oxide removing unit 17 adjusts the amount of nitrogen oxides removed from the ozone-ized gas by adjusting the second temperature adjusting unit 18 based on the instruction from the control unit 5 to reduce the amount of nitrogen oxides. do.

Further, in the nitrogen oxide removing unit 17, when the nitrogen oxide removing amount in the nitrogen oxide removing unit 17 reaches a predetermined amount, the nitrogen oxide removing time in the nitrogen oxide removing unit 17 is predetermined. Desorption step and adsorption step of the next cycle when predetermined conditions are met, such as when the time is reached or the amount of ozone adsorbed on the adsorbent of the adsorption / desorption unit 3 is less than the predetermined amount. In the meantime, the process shifts to a removal step of desorbing and removing nitrogen oxides from the nitrogen oxide removing unit 17.

In the removal step of the ozone supply device 200, the nitrogen oxide adsorbed on the nitrogen oxide removing unit 17 in the adsorption step is removed. The nitrogen oxide removing unit 17 raises the temperature of the nitrogen oxide removing unit 17 by adjusting the second temperature adjusting unit 18. It is desirable that the temperature rise control of the second temperature control unit 18 is, for example, raised to a temperature higher than the sublimation temperature of N ₂ O ₅ .

As described above, since the ozone supply device 200 controls the nitrogen concentration of the supply gas based on the information related to the nitrogen component concentration, it is possible to suppress the decrease in the ozone generation efficiency.

Further, since the ozone supply device 200 controls the nitrogen concentration of the supply gas, it is possible to suppress an increase in operating cost and quality defects of the device as compared with the ozone supply device 101.

Further, since the ozone supply device 200 controls to reduce the nitrogen oxide concentration, the nitrogen oxides in the gas can be removed, and the increase in the operating cost and the quality defect of the ozone supply device 200 can be further suppressed.

Further, in the removal step of the ozone supply device 200, by raising the temperature of the NOx adsorbent above the sublimation temperature of _N2 O ₅ , the NOx adsorbent is adsorbed at room temperature and then solidified and immobilized on the NOx adsorbent. It is possible to promote the desorption of N ₂ O ₅ from the NOx adsorbent.

Further, in the removal step of the ozone supply device 200, by supplying the raw material gas to the nitrogen oxide removing unit 17 by the purge circuit 19, the desorption of nitrogen oxides can be promoted by the gas replacement action of the raw material gas.

Further, in the removal step of the ozone supply device 200, the nitrogen oxide removal performance of the nitrogen oxide removing unit 17 can be restored by removing the nitrogen oxide in the nitrogen oxide removing unit 17.

In the second embodiment, the suction / desorption portion 3 and the nitrogen oxide removing portion 17 may be integrated. That is, the adsorbent of the adsorption / desorption portion 3 may adsorb nitrogen oxides, or the nitrogen oxide removing portion 17 may be provided inside the adsorption / desorption portion 3. When the nitrogen oxide removing section 17 is provided inside the suction / desorption section 3, it is preferable that the nitrogen oxide removing section 17 is arranged on the side of the suction / desorption section 3 to which the ozoneified gas is supplied.

Further, in the second embodiment, as a method for removing nitrogen oxides in the nitrogen oxide removing unit 17, for example, a method of performing low temperature condensation by a refrigerator may be used. By providing the low temperature condensation mechanism in the pipe 4, nitrogen oxides can be removed by controlling the temperature of the second temperature control unit 18.

In the second embodiment, the nitrogen oxide removing portion 17 may be installed on the pipe 4 between the suction / desorption portion 3 and the point A to remove the nitrogen oxides in the return gas, or the nitrogen oxides may be oxidized. The substance removing unit 17 may be installed on the pipe 4 between the point A and the ozone generating unit 2 to remove nitrogen oxides in the supply gas.

In the present disclosure, in addition to the ozone generation unit 2, the adsorption / desorption unit 3, and the pipe 4, the circulation circuit includes a nitrogen component concentration measuring unit 6, a booster blower 7, a nitrogen removing unit 8, an exhaust circuit 9, and a first. The temperature control unit 14, the detection unit 15, and the ozone concentration measurement unit 16 may be included.

Further, in the present disclosure, within the scope of the invention, each embodiment can be freely combined, and each embodiment can be appropriately modified or omitted.

1 Raw material gas supply unit, 2 Ozone generation unit, 3 Desorption unit, 4 Piping, 5 Control unit,
6 Nitrogen component concentration measuring unit, 7 Booster blower, 8 Nitrogen removing unit, 9 Exhaust circuit,
10 Oxygen source, 11 Nitrogen source, 12 Nitrogen addition part, 13 Flow rate adjustment part,
14 1st temperature control unit, 15 detection unit, 16 ozone concentration measurement unit,
17 Nitrogen oxide remover, 18 Second temperature controller, 19 Purge circuit,
90 Ozone exhaust circuit, 91 Nitrogen oxide exhaust circuit, 100, 100a, 100c, 100d, 100e, 100f, 101, 200 Ozone supply device.

Claims (23)

A raw material gas supply unit that supplies raw material gas containing oxygen and nitrogen,
An ozone generation unit that generates ozone-containing gas from the supply gas consisting of the raw material gas and the return gas, and
An adsorption / desorption unit that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas.
The raw material gas supply unit is not included, the ozone gas generated by the ozone generation unit is supplied to the suction / desorption unit, and the return gas discharged from the suction / desorption unit is used together with the raw material gas to generate the ozone. A piping that supplies the unit, the ozone generation unit, and a circulation circuit that includes the suction / desorption unit.
A control unit that controls the nitrogen concentration of the supply gas based on the information in the circulation circuit,
Ozone supply device equipped with. The control unit calculates a nitrogen component concentration estimated value in the circulation circuit based on the information in the circulation circuit, and when the calculated nitrogen component concentration estimated value is larger than a predetermined first value, the control unit calculates the nitrogen component concentration estimated value. , Control to reduce the nitrogen concentration of the supply gas, and if the calculated estimated value of the nitrogen component concentration is smaller than a predetermined second value, control to increase the nitrogen concentration of the supply gas. conduct,
The ozone supply device according to claim 1. When reducing the nitrogen concentration of the supply gas, the control unit gives an instruction to remove nitrogen from the return gas, an instruction to increase the amount of nitrogen removed, an instruction to reduce the amount of nitrogen added to the raw material gas, and nitrogen. Take at least one of the instructions to stop the addition of
When increasing the nitrogen concentration of the supply gas, the control unit gives an instruction to reduce the amount of nitrogen removed from the return gas, an instruction to stop the removal of nitrogen, and an instruction to add nitrogen to the raw material gas. And at least one of the instructions to increase the amount of nitrogen added,
The ozone supply device according to claim 2. The information in the circulation circuit is at least one of the nitrogen component concentration of the return gas, the nitrogen component concentration of the supply gas, and the nitrogen component concentration of the ozonizing gas.
The ozone supply device according to any one of claims 1 to 3. Further comprising a nitrogen component concentration measuring unit for measuring the nitrogen component concentration of at least one of the return gas, the supply gas and the ozonizing gas.
The ozone supply device according to claim 4. Further, an oxygen concentration measuring unit for measuring the oxygen concentration of at least one of the return gas, the supply gas, and the ozonizing gas is provided.
The control unit estimates the nitrogen component concentration of at least one of the return gas, the supply gas, and the ozonization gas from the oxygen concentration.
The ozone supply device according to claim 4. The information in the circulation circuit is the nitrogen component concentration of the supply gas.
The ozone generation unit has a detection unit that detects the emission of nitrogen in the discharge space.
The control unit estimates the nitrogen component concentration of the supply gas from the emission intensity of nitrogen detected by the detection unit.
The ozone supply device according to any one of claims 1 to 3. The information in the circulation circuit is information related to the ozone concentration of the ozone-forming gas.
The ozone supply device according to any one of claims 1 to 3. Further, an ozone concentration measuring unit for measuring the ozone concentration of the ozone-forming gas generated by the ozone generating unit is provided.
The information related to the ozone concentration of the ozone-forming gas is the ozone concentration measured by the ozone concentration measuring unit.
The ozone supply device according to claim 8. The information related to the ozone concentration of the ozone-ized gas is the amount of the ozone adsorbed by the desorption portion.
The ozone supply device according to claim 8. The information related to the ozone concentration of the ozone-forming gas is the discharge power of the ozone generating unit.
The ozone supply device according to claim 8. The information related to the nitrogen component concentration of the returned gas is the elapsed discharge time of the ozone generating portion.
The ozone supply device according to any one of claims 1 to 3. Based on the information in the circulation circuit, at least one of the nitrogen removing part for removing nitrogen of at least one of the return gas, the ozoneting gas and the supply gas and the nitrogen oxide removing part for removing nitrogen oxides is further added. Prepare, prepare
The ozone supply device according to any one of claims 1 to 12. Further, at least one of a first temperature control unit for controlling the temperature of the nitrogen removing unit and a second temperature control unit for controlling the temperature of the nitrogen oxide removing unit is further provided.
The first temperature control unit adjusts the amount of nitrogen or oxygen adsorbed by the nitrogen removal unit.
The second temperature control unit adjusts the amount of nitrogen oxide adsorbed on the nitrogen oxide removal unit.
The ozone supply device according to claim 13. The process of supplying the supply gas, which is supplied from the raw material gas supply unit and consists of the raw material gas containing oxygen and nitrogen and the return gas, to the ozone generation unit.
A step of generating an ozone-containing gas containing ozone from the supply gas by the ozone generating unit, and
A step of adsorbing the ozone contained in the ozone-forming gas to the suction / desorption portion and discharging the return gas from the suction / desorption portion.
The raw material gas supply unit is not included, the ozone gas generated by the ozone generation unit is supplied to the suction / desorption unit, and the return gas discharged from the suction / desorption unit is used together with the raw material gas to generate the ozone. It has a step of controlling the nitrogen concentration of the supply gas by the control unit based on the information in the circulation circuit including the piping supplied to the unit, the ozone generation unit, and the suction / desorption unit.
Ozone supply method. A raw material gas supply unit that supplies raw material gas containing oxygen and nitrogen,
An ozone generation unit that generates ozone-containing gas from the supply gas consisting of the raw material gas and the return gas, and
An adsorption / desorption unit that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. And the circulation circuit including the suction / detachment part,
A control unit for controlling the nitrogen concentration of the supply gas based on the information in the circulation circuit is provided.
The control unit calculates a nitrogen component concentration estimated value in the circulation circuit based on the information in the circulation circuit, and when the calculated nitrogen component concentration estimated value is larger than a predetermined first value, the control unit calculates the nitrogen component concentration estimated value. , Control to reduce the nitrogen concentration of the supply gas, and if the calculated estimated value of the nitrogen component concentration is smaller than a predetermined second value, control to increase the nitrogen concentration of the supply gas. conduct
An ozone supply device characterized by that . A raw material gas supply unit that supplies raw material gas containing oxygen and nitrogen,
An ozone generation unit that generates ozone-containing gas from the supply gas consisting of the raw material gas and the return gas, and
An adsorption / desorption unit that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. And the circulation circuit including the suction / detachment part,
A control unit for controlling the nitrogen concentration of the supply gas based on the information in the circulation circuit is provided.
The information in the circulation circuit is the nitrogen component concentration of the supply gas.
The ozone generation unit has a detection unit that detects the emission of nitrogen in the discharge space.
The control unit estimates the nitrogen component concentration of the supply gas from the emission intensity of nitrogen detected by the detection unit.
An ozone supply device characterized by that . A raw material gas supply unit that supplies raw material gas containing oxygen and nitrogen,
An ozone generation unit that generates ozone-containing gas from the supply gas consisting of the raw material gas and the return gas, and
An adsorption / desorption unit that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. And the circulation circuit including the suction / detachment part,
A control unit for controlling the nitrogen concentration of the supply gas based on the information in the circulation circuit is provided.
The information related to the nitrogen component concentration of the returned gas is the elapsed discharge time of the ozone generating part.
An ozone supply device characterized by that . A raw material gas supply unit that supplies raw material gas containing oxygen and nitrogen,
An ozone generation unit that generates ozone-containing gas from the supply gas consisting of the raw material gas and the return gas, and
An adsorption / desorption unit that adsorbs the ozone contained in the ozone-ized gas and discharges the returned gas.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. And the circulation circuit including the suction / detachment part,
A control unit for controlling the nitrogen concentration of the supply gas based on the information in the circulation circuit is provided.
Based on the information in the circulation circuit, at least one of the nitrogen removing part for removing nitrogen of at least one of the return gas, the ozoneting gas and the supply gas and the nitrogen oxide removing part for removing nitrogen oxides is further added. Prepare
An ozone supply device characterized by that . The process of supplying the supply gas, which is supplied from the raw material gas supply unit and consists of the raw material gas containing oxygen and nitrogen and the return gas, to the ozone generation unit.
A step of generating an ozone-containing gas containing ozone from the supply gas by the ozone generating unit, and
A step of adsorbing the ozone contained in the ozone-forming gas to the suction / desorption portion and discharging the return gas from the suction / desorption portion.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. A step of controlling the nitrogen concentration of the supply gas by the control unit based on the information in the circulation circuit including the unit and the suction / desorption unit is provided.
The control unit calculates a nitrogen component concentration estimated value in the circulation circuit based on the information in the circulation circuit, and when the calculated nitrogen component concentration estimated value is larger than a predetermined first value, the control unit calculates the nitrogen component concentration estimated value. , Control to reduce the nitrogen concentration of the supply gas, and if the calculated estimated value of the nitrogen component concentration is smaller than a predetermined second value, control to increase the nitrogen concentration of the supply gas. conduct
Ozone supply method characterized by that . The process of supplying the supply gas, which is supplied from the raw material gas supply unit and consists of the raw material gas containing oxygen and nitrogen and the return gas, to the ozone generation unit.
A step of generating an ozone-containing gas containing ozone from the supply gas by the ozone generating unit, and
A step of adsorbing the ozone contained in the ozone-forming gas to the suction / desorption portion and discharging the return gas from the suction / desorption portion.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. A step of controlling the nitrogen concentration of the supply gas by the control unit based on the information in the circulation circuit including the unit and the suction / desorption unit is provided.
The information in the circulation circuit is the nitrogen component concentration of the supply gas.
The ozone generation unit has a detection unit that detects the emission of nitrogen in the discharge space.
The control unit estimates the nitrogen component concentration of the supply gas from the emission intensity of nitrogen detected by the detection unit.
Ozone supply method characterized by that . The process of supplying the supply gas, which is supplied from the raw material gas supply unit and consists of the raw material gas containing oxygen and nitrogen and the return gas, to the ozone generation unit.
A step of generating an ozone-containing gas containing ozone from the supply gas by the ozone generating unit, and
A step of adsorbing the ozone contained in the ozone-forming gas to the suction / desorption portion and discharging the return gas from the suction / desorption portion.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. A step of controlling the nitrogen concentration of the supply gas by the control unit based on the information in the circulation circuit including the unit and the suction / desorption unit is provided.
The information related to the nitrogen component concentration of the returned gas is the elapsed discharge time of the ozone generating part.
Ozone supply method characterized by that . The process of supplying the supply gas, which is supplied from the raw material gas supply unit and consists of the raw material gas containing oxygen and nitrogen and the return gas, to the ozone generation unit.
A step of generating an ozone-containing gas containing ozone from the supply gas by the ozone generating unit, and
A step of adsorbing the ozone contained in the ozone-forming gas to the suction / desorption portion and discharging the return gas from the suction / desorption portion.
A pipe that supplies the ozone-forming gas generated by the ozone generating section to the suction / desorption section, and supplies the return gas discharged from the suction / desorption section together with the raw material gas to the ozone generating section, the ozone generation. A step of controlling the nitrogen concentration of the supply gas by the control unit based on the information in the circulation circuit including the unit and the suction / desorption unit is provided.
Based on the information in the circulation circuit, at least one of the nitrogen removing part for removing nitrogen of at least one of the return gas, the ozoneting gas and the supply gas and the nitrogen oxide removing part for removing nitrogen oxides is further added. Prepare
Ozone supply method characterized by that .

Images