JP4272947B2 - Discharge-type ozone gas generation method - Google Patents

Description

  The present invention relates to a discharge-type ozone gas generation method, and more particularly to an ozone gas generation method capable of obtaining a stable ozone yield.

  Ozone is used for sterilization of water, purification of drainage, deodorization, decolorization, etc., as well as removal of semiconductor photoresist, etc. due to its high oxidizing ability. Application to fields such as pretreatment for plant and plant disease control, etc. are being promoted, and in various directions, its application has been intensively pursued.

The following three methods are typical methods for producing ozone.
(1) Method of generating ozone by irradiating oxygen to ultraviolet rays
(2) Method of generating ozone by electrolysis of water
(3) Method of generating ozone by discharge in oxygen

  First, the first method of irradiating ultraviolet rays is a phenomenon in which ozone is generated in the stratosphere. In the atmosphere, an ultraviolet lamp is turned on to irradiate and absorb ultraviolet rays into oxygen molecules, thereby causing oxygen molecules in the atmosphere to irradiate. It is a simple method and is widely used as a germicidal lamp. However, in order to mass-produce high-concentration ozone gas, a high-energy ultraviolet irradiation device is required, There is a problem.

  Next, the second method based on electrolysis of water is to generate ozone water and oxygen on the anode side by supplying a direct current between electrodes arranged with a solid electric field film interposed therebetween, thereby generating ozone water. However, the generated ozone concentration is low, and it cannot be applied to a field requiring high concentration ozone.

Next, in the third discharge method, ozone is generated by discharging oxygen molecules in an oxygen stream, and ozone is generated by the following reaction.
O ₂ + e → O ₂ ⁺ + 2e -------- (a): ionization reaction
O ₂ + e → 2O + e --------- (b): dissociation reaction
O ₂ + O → O ₃ ------------- (c): Ozone formation reaction In the ionization reaction of (a) above, two electrons are collided by one electron colliding with an oxygen molecule. It is a phenomenon called “electron avalanche” that is generated, and is a reaction caused by electrons having an energy of 12.2 electron volts (eV) or more, which is a condition for continuing discharge. The dissociation reaction (b) is a reaction that occurs with electrons having an energy of about 5 to 8 eV, which is lower in energy than the ionization reaction, and there are many electrons having an energy of 12.2 eV or more in the discharge space. Therefore, dissociated oxygen is sufficiently generated by the reaction (b), and ozone is quickly generated by the reaction (c).

  Here, when a dielectric such as glass is placed between metal electrodes to which a high voltage is applied and oxygen is circulated between the electrodes to cause a discharge, a large current does not flow between the electrodes. There is no intense flashing and roaring, and a quiet discharge (silent discharge) is performed. Since this silent discharge takes a wide discharge space, it is suitable for mass production of ozone. In recent years, a large amount of ozone is produced by forming electrodes in a parallel laminated structure and narrowing the electrode interval to 0.1 to 0.2 mm. Has been put to practical use as a device for generating

  By the way, in the generation of ozone by the silent discharge method, as is apparent from the reaction formulas (a) to (c), oxygen molecules are involved in all reaction steps. Although it can be said that a raw material gas having a high oxygen concentration is preferable, as shown in FIG. 1 showing the relationship between the generated ozone concentration and the operation time when various raw material gases are used, the high purity oxygen gas of Six-Nine (99 .9999%) (curve “a” in the figure), the ozone generation amount decreases with the passage of operating time, and the function as an ozone generator (ozonizer) cannot be continued. is there.

The cause is considered as follows. That is, the reaction between the discharge electrodes of the ozonizer can be expressed by the following reaction formula.
O ₂ + e → e + O ₂ * ----------------- (1)
O ₂ * + e → e + O + O * ----------------- (2)
O + O ₂ → O ₃ ----------------- (3)
O ₃ + O ₂ * → O + 2O ₂ ----------------- (4)
O ₃ + O * → 2O ₂ ------------------ (5)
In the above reaction formula, O ₂ * and O * are reactive oxygen molecules and active oxygen atoms rich in reactivity. Reaction formulas (1) to (3) are ozone generation reactions, and reaction formulas (4) and (5) are ozone decomposition reactions. When the ozonizer is continuously operated for a long period of time, reactive oxygen molecules and active oxygen atoms rich in reactivity are adsorbed and accumulated on the electrode surface, and this is generated by the discharge and the above formulas (4) and (5). It is thought that ozone is decomposed into oxygen by the reaction of the formula.

Therefore, several measures have been proposed for long-term stable operation of the ozonizer. The first method uses, as a raw material gas, a mixed gas obtained by adding 1 to 10 vol.% Of high-purity nitrogen, argon or helium having a purity of 99.99 vol. This method is used (see Patent Document 1). The second method is a method in which a mixed gas obtained by adding air or nitrogen gas to high-purity oxygen gas obtained by gasifying liquid oxygen is used as a raw material gas (see Patent Document 2). The third method is a method of using a mixed gas obtained by adding carbon dioxide gas to oxygen gas as a raw material gas (see Patent Document 3).

In addition, there is a method in which the ozone generated by the discharge type ozonizer is used as it is by sending it to the place of use. A practical method is also known in which ozone gas is desorbed from silica gel and supplied as high-concentration ozone gas when used (for example, Patent Document 4).
Japanese Examined Patent Publication No. 6-21010 (see claims) JP 2001-172005 A (refer to claims) JP 2002-121011 A (refer to the claims) Japanese Patent Laid-Open No. 10-196893 (refer to claims and examples)

First, the method described in Patent Document 1 is not clear about the cause of the above-described decrease phenomenon of the ozone generation reaction, but this decrease phenomenon is remarkable when high-purity oxygen is used as a source gas. There is a feeling that it does not occur when liquid oxygen is used as a raw material, and attention is paid to nitrogen, argon and helium, which are impurities contained in liquid oxygen, and this is positively added.
On the other hand, in the method described in Patent Document 2, by adding nitrogen gas, it is said that the phenomenon of lowering the ozone generation amount is suppressed by causing the following reaction.
N ₂ + e → 2N * + e ----------------- (6)
N * + O ₂ → NO + O ---------------- (7)
NO + O ₂ * → NO ₂ + O ----------------- (8)
NO + O * → NO ₂ + O ----------------- (9)
That is, as shown in the above formulas (6) to (9), when nitrogen is fed between the discharge electrodes, the nitrogen atoms are excited by the discharge (the above formula (6)), and this reacts with the oxygen molecules to give NO. In addition, the NO reacts with the active oxygen molecules and active oxygen atoms to generate NO ₂ (the above formulas (8) to (9)). In this way, the active oxygen molecules and active oxygen atoms that act on the ozone decomposition reaction are consumed by nitrogen, and more than the reaction of ozone with active oxygen molecules and active oxygen atoms, NO and active oxygen molecules and active oxygen atoms Since the reaction rate is faster, the addition of nitrogen gas has the effect of decomposing the active oxygen molecules and active oxygen atoms adsorbed on the electrode surface, thereby suppressing the decomposition reaction of ozone. Is.

However, nitrogen oxide (NOx) is contained in the generated ozone gas. When the generated ozone is adsorbed on an adsorbent such as silica gel and concentrated and stored, NOx is adsorbed on the adsorbent. In addition to being concentrated, it causes the adsorbent to deteriorate at an early stage and also causes ozone decomposition due to the reaction of NO ₂ + O ₃ → NO ₃ + O ₂ . In addition, when water is present, nitric acid is produced, and even stainless steel pipes can be corroded. Therefore, considering the concentration of ozone and the degree of freedom of the reaction system in the subsequent process, the presence of NOx is extremely harmful. It can be said.

  In addition, in view of the above-mentioned problem of NOx generation, the method described in Patent Document 3 adds carbon dioxide to high-purity oxygen and uses it as a raw material gas. In the case of concentration, it is inevitable that carbon dioxide is also adsorbed at the same time. Therefore, it is inevitable that carbon dioxide will accompany the desorbed ozone gas during desorption. When ozone containing carbon dioxide is used, carbon dioxide may be adsorbed on the surface of electronic components, and carbon may be deposited in the reduction process. In the electronic technology field that forms micro-sized circuits, The deposition of conductive carbon may be a fatal defect.

  The present invention has been made in view of the above-mentioned various problems, and has as its first object to prevent a decrease in ozone generation over time in a discharge-type ozone generation method using high-purity oxygen gas. Furthermore, it is a second object to provide a discharge type ozone generation method that can stably obtain a high ozone yield without generating any impurities that have an adverse effect.

In order to achieve the above two objects at the same time, the present invention provides a high-purity oxygen gas containing at least one of neon (Ne), krypton (Kr), and xenon (Xe) in a total of 500 ppm to 3.0 vol. A gas obtained by adding at least one of 10 ppm to 2.0 vol.% Hydrogen is used as a raw material gas . As a result, the decrease in the amount of ozone generated with time is suppressed, and the generation of impurities that adversely affect the subsequent process is also prevented. Note that the addition of Ne, Kr, and Xe exceeding 3.0% not only saturates the effect of suppressing the decrease in the amount of ozone generated with time, but also has an effect obtained when using expensive additive gas. It will not be.

The addition amount of these gases, Ne, Kr, for Xe is particularly preferred range is from 0.1 to 0.5%. On the other hand, the hydrogen, the preferred range especially is 50ppm~1.0%. Moreover, what mixed 0.5% or less of 1 or more types of argon (Ar) or helium (He) in the said mixed gas can also be used.

  It is also a preferred method to supply a reaction product gas containing ozone to an ozone storage container filled with silica gel so that the ozone gas is adsorbed to the silica gel and stored. In this case, the Ne, Kr, Xe, hydrogen supplied to the silica gel packed bed together with ozone, or Ar, He added together with them are difficult to be adsorbed by the ozone-adsorbing silica gel. It becomes possible to obtain ozone gas having a concentration.

  According to the discharge-type ozone generation method of the present invention, since a mixed gas obtained by adding a predetermined amount of one or more of Ne, Kr, Xe or hydrogen to high-purity oxygen gas is used as a raw material gas, only high-purity oxygen gas is used. Compared with the conventional method using NO as a raw material gas, it is possible to generate ozone with a high yield over a long period of time.

Among these gases, in the case of Ne, Kr, and Xe, an expensive rare gas can be obtained by setting the total amount of addition to 500 ppm to 3.0%, preferably 0.1 to 0.5%. Since the maximum effect can be exerted by minimizing the amount of use and the like, it is possible to relatively reduce the ozone generation cost and increase the generation amount. When hydrogen is added alone or in combination, hydrogen is added to pure oxygen by adjusting the hydrogen addition amount to 10 ppm to 2.0%, preferably 50 ppm to 1.0%. However, there is no risk of explosion, and there is no problem in the high-pressure gas safety law, and it is possible to safely improve the ozone generation efficiency. In addition, since there is no need to generate or add a gas that adversely affects subsequent processes such as nitrogen oxide and carbon dioxide, there is also an effect of increasing the versatility of the generated ozone gas.

  Further, since it is possible to use Ar or He contained in liquid oxygen together with Ne, Kr, Xe or hydrogen, highly purified oxygen gas from which Ar or He has been removed is used as high purity oxygen gas. There is no need, and there is an advantage that Ar and He contained in about 1000 to 2000 ppm in oxygen gas used as high-purity oxygen gas at an industrial level can be used as an active ingredient.

  In addition, when the reaction product gas containing ozone generated by the ozonizer is adsorbed on silica gel and concentrated and stored, the additive gas used in the present invention is difficult to be adsorbed on the silica gel for ozone adsorption. Not only does this increase the amount of ozone adsorbed on the silica gel per hit, but there is no deterioration of the silica gel due to the adsorption of other gas components, so it can be said that it is an optimal raw material gas system for adsorption concentration and storage using silica gel.

  In addition, when condensed and stored on silica gel is used after desorption, it is adsorbed with ozone, and at the time of desorption, it is desorbed with ozone and the gas accompanying ozone becomes a rare gas. Supplying ozone will not cause any problems. In particular, there is no problem of nitrogen oxide generation by the conventional addition of nitrogen, acidification of the generated gas by the addition of carbon dioxide gas, or precipitation of carbon by reduction, and it is not contracted for the use of the generated ozone gas. A secondary effect of providing versatility to the use of ozone is also expected.

Hereinafter, the present invention will be described in detail based on examples.
Using a commercially available silent discharge type ozonizer, various mixed gases obtained by adding Xe, Kr, Ne, nitrogen, and hydrogen to high-purity oxygen gas (99.9999%) are used as a raw material gas, and the raw material gas is set to 2.0. The time-dependent change of the generated ozone concentration (g / m ³ , ppm) when supplied at a flow rate of liter / min was measured. The result is shown in the graph of FIG. In the same figure, (a) is the case of high-purity oxygen only, (b) is obtained by adding 3000 ppm (0.3%) of Xe to high-purity oxygen, and (c) is adding 3000 ppm of Kr to high-purity oxygen. (D) is obtained by adding 3000 ppm of Ne to high purity oxygen, (e) is obtained by adding 3000 ppm of nitrogen to high purity oxygen, and (f) is obtained by adding 44 ppm of hydrogen to high purity oxygen. Is. The operation was performed with the pressure inside the ozonizer set to 0.05 MPa.

  As is clear from FIG. 1, all of Xe (b in the figure), Kr (same c), Ne (same d), nitrogen (same e) and hydrogen (same f) are only high-purity oxygen (same a). Compared to the above, it can be seen that it is effective in preventing a decrease in ozone concentration. In particular, Kr (c) and Ne (d) show the same performance as nitrogen (e) and can be said to be extremely effective additive gases. Hydrogen (f) is next to the top three components (nitrogen, Kr, Ne), and Xe (b) is next, but both are stable at a higher level than high-purity oxygen. is doing. Of these components, nitrogen has the problem of generating nitrogen oxides as described above, so in the present invention, four types of Xe, Kr, Ne and hydrogen excluding nitrogen can be stably operated for a long time. Selected as an effective additive gas component.

  Next, using the discharge type ozonizer, high purity oxygen gas having a purity of 99.9999% and nitrogen, carbon dioxide, Ne, Ar, Kr, He, Xe, and hydrogen were added to 500 ppm to 1%, respectively. An ozone generation test was performed using the raw material gas. FIG. 2 shows the test results as a graph of relative concentration comparison with respect to the ozone concentration generated when only high-purity oxygen is used as the source gas. As is clear from the figure, nitrogen, carbon dioxide, Ne, and Kr are at the same level, Xe is next, Ar, He, and hydrogen are next, and high-purity oxygen is the lowest. I understand that. From this fact, it can be seen that the addition of Ne, Ar, Kr, He, Xe and hydrogen of 500 ppm to 1% can obtain a high ozone generation rate as compared with high-purity oxygen alone. In addition, Ar and He have a relatively low effect of increasing the amount of ozone generated in the same rare gas group. Therefore, in the present invention, Ne, Kr, and Xe are positioned as highly effective additive rare gases. Since Ar and He are not harmful gases such as other nitrogen and carbon dioxide, there is no problem even if these Ar and He are contained together with Ne, Kr and Xe. In particular, high-purity oxygen obtained from an air liquefaction / separation apparatus generally contains about 1000 to 2000 ppm of Ar or He as impurities, and therefore it is not necessary to remove it. Hydrogen is a component that is not contained in high-purity oxygen, and is a component that needs to be positively added. Its effect on the ozone generation concentration is similar to that of Ar and He. Since it has the stability of long-time operation as shown, in the present invention, it is positioned as a highly effective additive gas like Ne, Kr, and Xe. In the graph of FIG. 2, the supply amount of the raw material gas to the ozonizer is 2.0 liters / minute, and the internal pressure is 0.05 MPa.

  Next, using the discharge type ozonizer, the change in the generated ozone concentration was measured by changing the amount of Ne added to high-purity oxygen having a purity of 99.9999%. The results are plotted in the graph of FIG. As is clear from the figure, the effect of increasing the ozone concentration appears with the addition of a small amount of Ne, which becomes remarkable when the Ne concentration is 500 ppm (0.05%) or more, reaches a peak at about 3000 ppm, and is added with 10,000 ppm (1%). But you can see that there is almost no change. From this fact, it can be said that the amount of Ne added is preferably 500 ppm or more, although there is an effect even if a small amount is added. In addition, it is preferable to keep the upper limit to 3% or less, and addition beyond this is ineffective in increasing the amount of ozone generated with respect to an increase in the amount added, and wastes expensive Ne gas. Therefore, in this invention, the preferable range of the addition amount of Ne was made into the range of 500 ppm-3%. This range is the same not only for Ne but also for Kr and Xe, as can be seen from the example of FIG. 2, and in the present invention, these gases are set to a total of 500 ppm (0.05%) to 3%. did. A particularly preferable range is 1000 to 5000 ppm (0.1 to 0.5%) as shown in FIG.

  Next, a change in the generated ozone concentration was measured by changing the amount of hydrogen added to high purity oxygen having a purity of 99.9999% using the discharge type ozonizer. The results are plotted in the graph of FIG. As is clear from the figure, the effect of increasing the ozone concentration appears with the addition of a small amount of hydrogen, which becomes noticeable when the hydrogen concentration is 50 ppm (0.005%) or more, reaches a peak at about 200 ppm, and reaches 1000 ppm (0.1 %) It can be seen that there is almost no change even when added. From this, it can be said that the addition amount of hydrogen is effective even when a very small amount of several ppm is added, but it is preferably 10 ppm or more, and particularly preferably 50 ppm or more. In addition, as an upper limit, it is indispensable to restrain to 4% or less of the explosion limit value of hydrogen, and it is preferable to restrain to 2% or less from the viewpoint of the high-pressure gas safety law. Addition beyond this is ineffective in increasing the amount of ozone produced with respect to the increase in the amount added, and there is a risk of meaningless hydrogenation. Therefore, in the present invention, the amount of hydrogen added is 2.0% or less, preferably 10 ppm or more, and more preferably 50 ppm or more. In terms of effectiveness, even when 1% addition in FIG. Therefore, the upper limit is preferably 1%. When other Ne, Kr, or Xe and hydrogen are used in combination, hydrogen in the above range and Ne, Kr, or Xe in the above range can be used in combination.

  As described above, in the present invention, in addition to Ne, Kr, Xe, and hydrogen, Ar and He are allowed to be contained. However, these components are generally about 1000 to 2000 ppm as impurities in oxygen. Is included as described above. Further, even when positively added, it is preferable that the total amount of both is 0.5% or less. Addition beyond this is not meaningful in the presence of Ne, Kr, Xe or hydrogen.

  Next, the increase and stabilization of the ozone generation concentration by adding these gases will be considered. As shown in FIG. 1 above, Ne, Kr, Xe, hydrogen used in the present invention, and those added with conventionally known nitrogen, etc., are used as raw material gases. As compared with the case of the above, high ozone yield and yield stability are obtained. The effect of preventing the decrease in yield due to the presence of nitrogen is as described above, but the theory does not apply to the rare gases Ne, Kr, and Xe as they are. These gases do not generate reaction products with active oxygen molecules or active oxygen atoms even by discharge. However, these atoms are relatively high in electrical conductivity, that is, the outermost electrons enter and exit in a short time in the discharge field, and the light generated at that time is assumed to contribute to ozone generation. Is done. In particular, Ne is an atom having a high conductivity as used as a neon sign. Therefore, as can be seen from FIG. 1, it does not simply prevent the decrease in the amount of ozone generated compared to pure oxygen. A higher yield than that obtained using pure oxygen was obtained from the beginning, and it is presumed that the light generated by Ne actively contributes to ozone generation. On the other hand, as in the case of nitrogen, hydrogen reacts with active oxygen molecules and active oxygen atoms adsorbed on the discharge electrode surface to generate water, and the active oxygen molecules and active oxygen atoms on the discharge electrode surface are generated. Presumed to prevent deposition due to adsorption.

  The ozone generated by the discharge type ozonizer can be used as it is, but as disclosed in Japanese Patent Application Laid-Open No. 10-196893 (patent document 4) previously filed by the applicant. There is a method in which the reaction product gas containing the generated ozone gas is saturated and adsorbed on silica gel, concentrated and stored in the state of gas ozone, and in use, it is desorbed from the silica gel and used as high-concentration ozone gas of several tens% or 90% . This method is extremely promising because it enables storage of ozone and use in high-concentration ozone. However, when a mixed gas added with nitrogen disclosed in the conventional method is used in this method, The by-product nitrogen oxide (NO2) has a molecular weight of 46 and is very close to the molecular weight of ozone 48. Therefore, such nitrogen oxide is also adsorbed to silica gel together with ozone, and as a result, the amount of ozone adsorbed relatively decreases. At the same time, the adsorbent may be deteriorated. This phenomenon has a similar problem even when a mixed gas in which carbon dioxide gas is added instead of nitrogen is used, since the molecular weight of carbon dioxide gas is 44 and approximates that of ozone. On the other hand, in the present invention, no by-product reactant is present, and Ne is 20.2, Kr is 83.8, Xe is 131.3, and hydrogen is 2 with respect to the molecular weight of ozone 48. These gases are hardly adsorbed on silica gel designed for ozone adsorption, and the adsorption characteristics of silica gel are not deteriorated. In particular, since hydrogen is a gas that is extremely difficult to be adsorbed, as is used as a carrier gas for gas analysis, it is not adsorbed by silica gel and does not hinder the adsorption of ozone gas. Further, when adsorbed ozone is desorbed and used, there is almost no adsorption of gases other than ozone, so that it can be desorbed as high-concentration ozone gas. Also from this point, it can be said that the additive gas used in the present invention is a very effective additive gas. Incidentally, the molecular weights of Ar and He that can be used together with the above four gases are 40 and 4, respectively, and the adsorption amount to silica gel is small compared to the nitrogen oxide and carbon dioxide gas. There is no problem at all. Particularly, since He is used as a carrier gas for gas analysis like hydrogen and is a gas that is extremely difficult to be adsorbed, it does not deteriorate the ozone adsorption characteristics of silica gel.

  Furthermore, even when ozone is concentrated and stored by the silica gel adsorption method, it is inevitable that the additive gas and by-product gas are also adsorbed together with ozone, although there are differences depending on the type of additive gas and by-product gas. It is. Since carbon dioxide gas and nitrogen oxide accompanying the above-described conventional carbon dioxide gas and nitrogen as an additive gas are easily adsorbed in a large amount as compared with Ne, Kr and Xe used in the present invention as described above, At the time of desorption, these adsorbed gases are also released along with the ozone gas. However, since these carbon dioxide and nitrogen oxides have activity as acid gases, There are appropriate and unsuitable uses. On the other hand, among Ne, Kr, Xe, and hydrogen (plus Ar, He) used in the present invention, it may be considered that hydrogen and He are not adsorbed, but other Ne, Kr, Xe, and Ar are trace amounts. It is inevitable that it will be adsorbed. For this reason, at the time of desorption, these gas components also accompany ozone, but these are rare gases and usually do not react with other components, so these gases are mixed into ozone. Even if it is sent to the use system, there will be no problem. This has the effect of giving versatility to the use of ozone produced by the method of the present invention.

  In the above embodiment, six-nine (99.9999%) ultra-high purity oxygen gas is used, but industrially, the purity is 99.9% obtained as high-purity oxygen from an air liquefaction separator or the like. Needless to say, oxygen gas of a certain degree can be used in the present invention. In particular, a gas generally called high-purity oxygen gas contains Ar and He as impurities, and these impurity gases are gases allowed in the present invention as described above. It is not necessary to use the high-strength oxygen gas removed.

  As described above in detail, according to the discharge type ozone generation method of the present invention, a gas obtained by adding Ne, Kr, Xe, hydrogen or further Ar, He to a high purity oxygen gas is used as a raw material gas. All the gas accompanying the generated ozone gas becomes harmless gas, and the ozone gas generated by the present invention can be used in all industrial fields.

It is a chart which shows the relationship between the production | generation ozone concentration at the time of using various raw material gas, and driving | running time. It is a graph which shows the relative concentration ratio with respect to the high purity oxygen raw material of the production | generation ozone concentration at the time of using various raw material gas. It is a graph which shows the relationship between the addition amount of Ne with respect to high purity oxygen, and production | generation ozone concentration. It is a graph which shows the relationship between the addition amount of hydrogen with respect to high purity oxygen, and production | generation ozone concentration.

Claims (5)

In the discharge-type ozone gas generation method of supplying ozone-containing source gas to a discharge-type ozonizer to generate ozone gas,
Add at least one of neon, krypton, and xenon as a raw material gas in a total of 500 ppm to 3.0 vol.% And 10 ppm to 2.0 vol.% Hydrogen in high purity oxygen gas A discharge-type ozone gas generation method characterized by using a gas that has been discharged.   2. The discharge type ozone gas generation method according to claim 1, wherein the addition amount of one or more of neon, krypton, and xenon in the mixed gas is 0.1 to 0.5 vol.% In total.   The discharge-type ozone gas generation method according to claim 1 or 2, wherein an addition amount of hydrogen in the mixed gas is 50 ppm to 1.0 vol.%. The discharge type ozone gas generation method according to any one of claims 1 to 3 , wherein the mixed gas contains one or more of argon or helium at 0.5 vol.% Or less.   The reaction product gas containing ozone produced | generated using the said mixed gas is supplied to the ozone storage container filled with the silica gel, Ozone is made to adsorb | suck to the said silica gel, and it stores it. The discharge type ozone gas production method according to claim 1.

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