JP2005145762A - Method for generating ozone gas by electric discharge - Google Patents
Method for generating ozone gas by electric discharge Download PDFInfo
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- JP2005145762A JP2005145762A JP2003386387A JP2003386387A JP2005145762A JP 2005145762 A JP2005145762 A JP 2005145762A JP 2003386387 A JP2003386387 A JP 2003386387A JP 2003386387 A JP2003386387 A JP 2003386387A JP 2005145762 A JP2005145762 A JP 2005145762A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 239000001307 helium Substances 0.000 claims abstract description 13
- 229910052734 helium Inorganic materials 0.000 claims abstract description 13
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 10
- 229910052743 krypton Inorganic materials 0.000 claims abstract description 8
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052754 neon Inorganic materials 0.000 claims abstract description 8
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 230000008859 change Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000002411 adverse Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000036962 time dependent Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001364 causal effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
本発明は、放電式オゾンガス生成方法に関するものであり、特に、高収量でかつ経時的な濃度変化が殆どなくて極めて安定したオゾン収量の得られるオゾンガス生成方法に関するものである。 The present invention relates to a discharge-type ozone gas generation method, and more particularly, to an ozone gas generation method that provides a highly stable ozone yield with high yield and little change in concentration over time.
オゾンは、その高い酸化能のため、上水の殺菌や排水の浄化，脱臭，脱色等の他、半導体のフォトレジスト除去等に利用されており、更に、近年では、水溶液として食品の品質保持のための前処理や植物の病虫害防除等の分野への応用が進められており、各方面において、鋭意その応用が図られている。 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.
オゾンの製造方法としては、（１）酸素に紫外線を照射してオゾンを生成する方法、（２）水の電気分解によってオゾンを生成する方法、（３）酸素中で放電によりオゾンを生成する方法の三方法が代表的なものとして知られるが、それらのうちで高濃度オゾンガスを量産するのに適しているとされる後者の酸素中で放電によりオゾンを生成する方法に含まれるものであって、酸素含有原料ガスを放電式オゾナイザーに供給してオゾンガスを生成させる放電式オゾンガス生成方法に基づく新規な製造方法につき、本出願人は先に特願２００３−２８１７３１により提案した。 As a manufacturing method of ozone, (1) a method of generating ozone by irradiating oxygen to ultraviolet rays, (2) a method of generating ozone by electrolysis of water, and (3) a method of generating ozone by discharge in oxygen These three methods are known as typical ones. Among them, the latter method, which is suitable for mass production of high-concentration ozone gas, is included in the method of generating ozone by discharge in oxygen. The present applicant previously proposed in Japanese Patent Application No. 2003-281731 a novel manufacturing method based on a discharge-type ozone gas generation method in which an oxygen-containing source gas is supplied to a discharge-type ozonizer to generate ozone gas.
上記提案に係る先願発明は、高純度酸素ガスを用いた放電式オゾン生成方法における経時的なオゾン生成量の低下を防止すること、後工程で悪影響を与える不純物をも生成させないで安定して高いオゾン収量の得られる放電式オゾン生成法を提供することの２つの目的を同時に達成するために成されたものであって、従ってこの発明は、原料ガスとして高純度酸素ガス中にネオン（Ｎｅ），クリプトン（Ｋｒ），キセノン（Ｘｅ）の一種以上を合計で３．０ｖｏｌ．％以下、又は、水素を２．０ｖｏｌ．％以下のいずれか一方又は双方を添加してなる混合ガスを用いてなることを構成の特徴とするものである。 The prior invention related to the above-mentioned proposal is to prevent a decrease in ozone generation over time in a discharge-type ozone generation method using high-purity oxygen gas, and stably without generating impurities that adversely affect the subsequent process. The present invention has been made to simultaneously achieve the two objectives of providing a discharge-type ozone generation method capable of obtaining a high ozone yield. Accordingly, the present invention provides neon (Ne) in high-purity oxygen gas as a raw material gas. ), One or more of krypton (Kr) and xenon (Xe) in a total of 3.0 vol. % Or less, or hydrogen at 2.0 vol. % Or less, or a mixed gas obtained by adding one or both of the following.
これにより、上記先願発明においては前述のオゾン生成量の経時的減少が抑制され、かつ、後工程で悪影響を及ぼす不純物の生成も防止されるとする所期の目的が達成されるに至ったのである。しかしてこの先願発明に基づく実用装置を供するべく本発明者等によって実用化のための研究及び検討を鋭意重ねてきたが、生成したオゾンを例えば半導体のフォトレジスト除去等の高精密処理作業に応用するような場合において、放電式オゾナイザーでのオゾン発生効率を高められたとしても、生成オゾン濃度が経時的に僅かでも漸減するようなことがあったのでは処理工程に悪影響を与えて好ましくないものであり、生成オゾン濃度が時間の経過にも影響されること無く略一定に安定した状態に保持される装置の提供が関連の作業現場において強く要求される事実を知見するに及んで、それらの要望に十分応え得るものとして高収量でかつ経時的な濃度変化が殆どなくて極めて安定したオゾン収量の得られるオゾンガス生成方法である本発明をここに完成するに至ったのである。 As a result, the above-described prior invention has achieved the intended purpose of suppressing the time-dependent decrease in the amount of ozone generated as described above and preventing the generation of impurities that adversely affect the subsequent process. It is. In order to provide a practical device based on the invention of the prior application, the present inventors have intensively studied and studied for practical use, but applied the generated ozone to high-precision processing work such as, for example, removal of a semiconductor photoresist. In such a case, even if the ozone generation efficiency in the discharge type ozonizer is increased, if the generated ozone concentration gradually decreases even with time, the treatment process is adversely affected, which is not preferable. In order to discover the fact that it is strongly required to provide a device in which the generated ozone concentration is maintained in a substantially constant and stable state without being affected by the passage of time, This is a method of generating ozone gas that can meet the demands sufficiently, with a high yield and a very stable ozone yield with little change in concentration over time. Akira is to have accomplished here.
ところで、オゾン濃度の経時的な低下を抑えるためとして、オゾンガス配管における金属不純物を低減する方法が提案されている（特許文献１参照）。また、オゾン発生器でのオゾンの発生効率を高めることが可能なオゾンの供給方法及び装置が提案されている（特許文献２参照）。
先ず、上記特許文献１に記載の方法は、オゾン発生器によりオゾンガスを発生させ、且つそのオゾンガスをステンレス鋼配管により供給する際に、高純度酸素ガスに窒素ガス、ヘリウムガス、アルゴンガス、二酸化炭素ガスおよび一酸化炭素ガスの一種以上を合計で、０．０２５％以上添加した混合ガスを原料ガスとして用い、且つ原料ガス中の窒素ガス濃度を１．０％未満に制限するものであって、このように窒素ガス濃度を１．０％未満にし、ヘリウムガス、アルゴンガス、二酸化炭素ガスおよび一酸化炭素ガスの一種以上を合計で、０．０２５％以上添加することによって、ステンレス鋼配管からの金属酸化物の発生を抑えながら、オゾン濃度の経時的な低下を防止し得ることが開示されている。 First, in the method described in Patent Document 1, when ozone gas is generated by an ozone generator and the ozone gas is supplied through a stainless steel pipe, nitrogen gas, helium gas, argon gas, carbon dioxide is added to high-purity oxygen gas. A total of one or more of gas and carbon monoxide gas, using a mixed gas added 0.025% or more as a raw material gas, and limiting the nitrogen gas concentration in the raw material gas to less than 1.0%, Thus, by making the nitrogen gas concentration less than 1.0% and adding one or more of helium gas, argon gas, carbon dioxide gas and carbon monoxide gas in a total of 0.025% or more, It is disclosed that the ozone concentration can be prevented from decreasing over time while suppressing the generation of metal oxides.
この特許文献１によれば、高純度酸素ガス中の添加ガスである窒素がオゾン濃度の安定性の維持に寄与していることが一応明示されてはいるが、このオゾン濃度安定性に関しては連続する１時間におけるオゾン濃度変動量が１２０ｇ／ｍ3±１０％未満か否かの比較で評価したものであって、窒素濃度とオゾン濃度変動量との因果関係には何等触れるところがなくて、所謂、定性的評価を単に明らかにしているに過ぎないものである。 According to Patent Document 1, it is clarified that nitrogen, which is an additive gas in high-purity oxygen gas, contributes to maintaining the stability of ozone concentration. It is evaluated by comparing whether or not the ozone concentration fluctuation amount in one hour is less than 120 g / m 3 ± 10%, and there is no point in touching the causal relationship between the nitrogen concentration and the ozone concentration fluctuation amount, so-called , It merely reveals the qualitative assessment.
一方、上記特許文献２に記載の方法は、オゾンを含有する酸素ガスを吸着剤に吸着させる吸着工程と、吸着剤から脱着させたオゾンを掃気ガスに同伴させてオゾン使用先に供給する脱着工程とを交互に繰返して高濃度のオゾンを供給するものにおいて、オゾン発生器に導入するオゾン原料ガス中の二酸化炭素濃度を１０ｐｐｍ〜１０％の範囲に制御するものであって、これによって所定濃度範囲で二酸化炭素をオゾン原料ガス中に添加することでオゾンの発生効率を向上させ得る点が明示されている。しかしながら、この特許文献２では二酸化炭素の添加がオゾン発生効率の向上に寄与することが定性的評価として開示されているだけであって、二酸化炭素ガス濃度とオゾン濃度変動量との関係については特許文献１と同じく一切触れていないことは明らかである。 On the other hand, the method described in Patent Document 2 includes an adsorption step in which an oxygen gas containing ozone is adsorbed on an adsorbent, and a desorption step in which ozone desorbed from the adsorbent is accompanied by a scavenging gas and supplied to an ozone usage destination. In which high concentration of ozone is repeatedly supplied, the concentration of carbon dioxide in the ozone raw material gas introduced into the ozone generator is controlled within a range of 10 ppm to 10%, thereby providing a predetermined concentration range. It is clearly shown that the efficiency of ozone generation can be improved by adding carbon dioxide to the ozone source gas. However, this Patent Document 2 merely discloses as a qualitative evaluation that the addition of carbon dioxide contributes to the improvement of ozone generation efficiency, and the relationship between the carbon dioxide gas concentration and the ozone concentration variation is patented. It is clear that it is not touched at all as in Reference 1.
本発明は、上記したように特に経時的な濃度変化が殆どなくて極めて安定したオゾン収量の得られるオゾンガス生成方法を提供するべくなされたものであって、加えて、高純度酸素ガスを用いた放電式オゾン生成方法における経時的なオゾン生成量の低下を防止すること、悪影響を与える如何なる不純物をも生成させることなく安定して高いオゾン収量の得られる放電式オゾン生成法を提供することを主要な目的とするものである。 As described above, the present invention has been made to provide an ozone gas generation method that can obtain an extremely stable ozone yield with little change in concentration over time. In addition, a high-purity oxygen gas is used. The main objective is to provide a discharge-type ozone generation method that can prevent a decrease in ozone generation over time in a discharge-type ozone generation method and that can stably obtain a high ozone yield without generating any adverse impurities. Purpose.
本発明は、上記目的を同時に達成するために、酸素含有原料ガスを放電式オゾナイザーに供給してオゾンガスを生成させる放電式オゾンガス生成方法において、原料ガスとして、高純度酸素ガス中に、水素、メタンの一種以上を合計で５〜２００ｐｐｍ、且つ窒素ガスを５〜１５０ｐｐｍ又は二酸化炭素ガスを１〜１０ｖｏｌ．％添加してなる混合ガスを用いることを特徴とする。これにより、前述のオゾン生成量の経時的減少が抑制され、且つ、後工程で悪影響を及ぼす不純物の生成も防止されることになる。更に、窒素ガス又は二酸化炭素ガスを所定濃度範囲に添加することで、経時的な濃度変化が殆どなくて極めて安定したオゾン収量が保持される。 In order to achieve the above-mentioned object at the same time, the present invention provides a discharge-type ozone gas generation method in which an oxygen-containing source gas is supplied to a discharge-type ozonizer to generate ozone gas. 5 to 200 ppm in total, 5 to 150 ppm of nitrogen gas, or 1 to 10 vol. % Mixed gas is used. Thereby, the time-dependent decrease in the amount of ozone generated is suppressed, and the generation of impurities that adversely affect the subsequent process is also prevented. Furthermore, by adding nitrogen gas or carbon dioxide gas to a predetermined concentration range, there is almost no change in concentration over time, and an extremely stable ozone yield is maintained.
又、本発明は、前項における前記混合ガス中に、アルゴン、ヘリウム、ネオン、クリプトン、キセノンの一種以上を合計で５０００ｐｐｍ以下含有させてなることも好ましいものである。これにより、工業レベルで高純度ガスとして用いられている酸素ガスを原料ガスに活用させることが可能である。 In the present invention, it is also preferable that the mixed gas in the preceding item contains at least 5000 ppm in total of at least one of argon, helium, neon, krypton, and xenon. Thereby, oxygen gas used as high purity gas at an industrial level can be used as a raw material gas.
本発明の放電式オゾン生成方法によると、水素、メタンの１種以上を所定量添加した混合ガスを原料ガスとして使用しているので、高純度酸素ガスのみを原料ガスとして使用する従来法に比して、高い収量で安定したオゾンの生成を長時間にわたって行うことが可能となる。水素、メタンの１種以上を添加する場合は、２００ｐｐｍ添加で生成オゾン濃度が最大になり、それ以上の添加は生成オゾン濃度が変わらなく影響を与えない。また、５ｐｐｍ程度添加する場合においても比較的高い生成オゾン濃度が得られ、それ以下では生成オゾン量が顕著に減ることが明らかである。 According to the discharge type ozone generation method of the present invention, since a mixed gas in which a predetermined amount of one or more of hydrogen and methane is added is used as a raw material gas, it is compared with the conventional method using only a high purity oxygen gas as a raw material gas. Thus, it is possible to stably generate ozone with a high yield over a long period of time. When one or more of hydrogen and methane are added, the concentration of generated ozone is maximized by addition of 200 ppm, and the addition of more than that does not affect the concentration of generated ozone. Further, even when about 5 ppm is added, a relatively high generated ozone concentration is obtained, and it is clear that the amount of generated ozone is significantly reduced below that.
また、水素、メタンの一種以上に窒素ガスを５〜１５０ｐｐｍ又は二酸化炭素ガスを１〜１０ｖｏｌ．％添加してなることで、更に高い収量のオゾンを得ることができ、且つオゾン濃度の経時的な変化も殆どなくなる。 Moreover, 5 to 150 ppm of nitrogen gas or 1 to 10 vol. % Addition of ozone makes it possible to obtain a higher yield of ozone, and there is almost no change in ozone concentration over time.
更に本発明の放電式オゾン生成方法によると、水素、メタン、窒素、二酸化炭素ガスと共に、液体酸素中に含有されているアルゴンやヘリウムを併用することができるので、高純度酸素ガスとしてアルゴンやヘリウムを除去した高度精製酸素ガスを用いる必要はなく、工業レベルで高純度酸素ガスとして用いられている酸素ガス中に１０００〜２０００ｐｐｍ程度含有されているアルゴンやヘリウムも有効成分として活用し得る工業上の利点がある。 Furthermore, according to the discharge type ozone generation method of the present invention, since argon and helium contained in liquid oxygen can be used together with hydrogen, methane, nitrogen and carbon dioxide gas, argon or helium can be used as high purity oxygen gas. It is not necessary to use highly purified oxygen gas from which oxygen has been removed. Industrially, argon or helium contained in an oxygen gas used as high-purity oxygen gas at an industrial level of about 1000 to 2000 ppm can also be used as an active ingredient. There are advantages.
また、アルゴンやヘリウムと同じ希ガスであるネオン、クリプトン、キセノンを併用することもできる。尚、アルゴン、ヘリウム、ネオン、クリプトン、キセノンを積極的に添加する場合は、その一種以上を合計で５０００ｐｐｍ以下とすることが望ましい。それ以上の添加は、水素、メタン、窒素、二酸化炭素ガスの共存下ではオゾン収量を大きく変化させなく経済的などの点で不利となるからである。 Further, neon, krypton, and xenon, which are the same noble gases as argon and helium, can be used in combination. In addition, when argon, helium, neon, krypton, and xenon are positively added, it is desirable that one or more of them be 5000 ppm or less in total. Addition beyond that is disadvantageous at any economical point in the presence of hydrogen, methane, nitrogen and carbon dioxide gas without significantly changing the ozone yield.
以下に、実施例に基づいて本発明を詳細に説明する。
市販の無声放電式オゾナイザーを用いて、高純度酸素ガス（９９．９９９９％）に、メタン、窒素、水素を夫々添加した各種混合ガスを原料ガスとし、該原料ガスを４．０リットル／分の流量で供給したときの生成オゾン濃度（ｇ／ｍ３，ｐｐｍ）の経時変化を測定した。その結果を図１のグラフに示す。
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 methane, nitrogen, and hydrogen to high-purity oxygen gas (99.9999%) are used as a raw material gas, and the raw material gas is supplied at 4.0 liters / minute. The change over time of the generated ozone concentration (g / m 3 , ppm) when supplied at a flow rate was measured. The result is shown in the graph of FIG.
同図において、（ａ）は高純度酸素のみの場合（比較例１）であり、（ｂ）は高純度酸素に水素を１０ｐｐｍ添加したもの（比較例２）、（ｃ）は高純度酸素にメタンを５ｐｐｍ添加したもの（比較例３）、（ｄ）は高純度酸素に窒素を３０ｐｐｍ添加したもの（比較例４）、（ｅ）は高純度酸素に二酸化炭素ガスを２vol.％添加したもの（比較例５）である。又、（ｆ）は高純度酸素に二酸化炭素ガスを２vol.％、及びメタンを５ｐｐｍ添加したもの（実施例１）であり、(g)
は高純度酸素に二酸化炭素ガスを２vol.％、及び水素を１０ｐｐｍ添加したもの（実施例２）、(h) は高純度酸素に窒素を３０ｐｐｍ、及びメタンを５ｐｐｍ添加したもの（実施例３）、(i)
は高純度酸素に窒素を３０ｐｐｍ、及び水素を１０ｐｐｍ添加したもの（実施例４）である。尚、オゾナイザー内の圧力は、０．１５ＭＰａに設定して運転を行った。
In the figure, (a) is the case of high-purity oxygen only (Comparative Example 1), (b) is the one obtained by adding 10 ppm of hydrogen to high-purity oxygen (Comparative Example 2), and (c) is the high-purity oxygen. Methane added 5 ppm (Comparative Example 3), (d) high purity oxygen added 30 ppm nitrogen (Comparative Example 4), (e) carbon dioxide gas added 2 vol.% To high purity oxygen (Comparative Example 5). In addition, (f) is obtained by adding 2 vol.% Of carbon dioxide gas and 5 ppm of methane to high purity oxygen (Example 1), (g)
Is a high purity oxygen to which 2 vol.% Of carbon dioxide gas and 10 ppm of hydrogen are added (Example 2). (H) is a high purity oxygen to which 30 ppm of nitrogen and 5 ppm of methane are added (Example 3). , (I)
Is one obtained by adding 30 ppm of nitrogen and 10 ppm of hydrogen to high purity oxygen (Example 4). The operation was performed with the pressure inside the ozonizer set to 0.15 MPa.
水素添加の比較例２（ｂ）、メタン添加の比較例３（ｃ）は、高純度酸素のみの比較例１（ａ）に比して、高いオゾン収量が得られるが、１０時間経過後のオゾン濃度は５０ｇ／ｍ3程度となって、５０％程度の濃度低下が示される。又、窒素添加の比較例４（ｄ）、二酸化炭素ガス添加の比較例５（ｅ）は、更に高いオゾン収量が得られるが、１０時間経過後のオゾン濃度は１００〜１１０ｇ／ｍ３程度となって、１０〜２５％程度の濃度低下が示される。 Comparative Example 2 (b) with hydrogenation and Comparative Example 3 (c) with methane addition have higher ozone yields than Comparative Example 1 (a) with only high-purity oxygen, but after 10 hours have elapsed. The ozone concentration is about 50 g / m 3, indicating a decrease in concentration of about 50%. Further, Comparative Example 4 (d) with addition of nitrogen and Comparative Example 5 (e) with addition of carbon dioxide gas provide a higher ozone yield, but the ozone concentration after 10 hours is about 100 to 110 g / m 3. Thus, a concentration decrease of about 10 to 25% is shown.
一方、高純度酸素に二酸化炭素ガスを２vol.％、及びメタンを５ｐｐｍ添加した実施例１（ｆ）については、比較例５（ｅ）と同等の程度の高いオゾン収量が得られ、且つ、１０時間経過後のオゾン濃度は１３５ｇ／ｍ３程度であって、これは４％程度の濃度低下を呈すに過ぎなくて、経時的な濃度変化が極めて小さいことを示している。 On the other hand, in Example 1 (f) in which 2 vol.% Of carbon dioxide gas and 5 ppm of methane were added to high purity oxygen, a high ozone yield equivalent to that in Comparative Example 5 (e) was obtained, and 10 The ozone concentration after the lapse of time is about 135 g / m 3 , which shows only a decrease in concentration of about 4%, indicating that the change in concentration over time is extremely small.
また、高純度酸素に二酸化炭素ガスを２vol.％、及び水素を１０ｐｐｍ添加してなる実施例２(g) は、実施例１と同程度若しくはやや高いオゾン収量が得られ、且つ、１０時間経過後のオゾン濃度は１４０ｇ／ｍ３程度であって、この例の場合も４％程度の濃度低下を呈すに過ぎなくて、経時的な濃度変化が極めて小さいことを示している。 In addition, Example 2 (g) obtained by adding 2 vol.% Of carbon dioxide gas and 10 ppm of hydrogen to high-purity oxygen provides an ozone yield that is similar to or slightly higher than Example 1, and 10 hours have passed. The ozone concentration afterwards is about 140 g / m 3 , and in this example, the concentration decrease is only about 4%, indicating that the concentration change with time is very small.
更に、高純度酸素に窒素を３０ｐｐｍ、及びメタンを５ｐｐｍ添加した実施例３(h) については、より高いオゾン収量が得られ、且つ、１０時間経過後のオゾン濃度は１６５ｇ／ｍ３程度であって、これは３％程度の濃度低下を呈すに過ぎなくて、経時的な濃度変化が極めて小さいことを示している。 Furthermore, for Example 3 (h) in which nitrogen was added to high purity oxygen at 30 ppm and methane at 5 ppm, a higher ozone yield was obtained, and the ozone concentration after 10 hours was about 165 g / m 3. This shows only a decrease in concentration of about 3% and indicates that the change in concentration over time is extremely small.
また、高純度酸素に窒素を３０ｐｐｍ、及び水素を１０ｐｐｍ添加してなる実施例４(i) は実施例３同様の高いオゾン収量が得られ、且つ、１０時間経過後のオゾン濃度は１７０ｇ／ｍ３程度であって、これも３％程度の濃度低下を呈すに過ぎなくて、経時的な濃度変化が極めて小さいことを示している。 Further, Example 4 (i) obtained by adding 30 ppm of nitrogen and 10 ppm of hydrogen to high-purity oxygen provides the same high ozone yield as that of Example 3, and the ozone concentration after 10 hours is 170 g / m. be about 3, which may not only Teisu a density reduction of about 3% concentration over time changes indicates that very small.
以上述べた通り、本発明では二酸化炭素とメタン、二酸化炭素と水素、窒素とメタン及び窒素と水素の４種を安定した高い収量が得られる添加ガス成分としている。尚、水素、メタンの一種以上を合計で５ｐｐｍ以下、且つ窒素ガスを５ｐｐｍ以下又は二酸化炭素ガスを１ｖｏｌ．％以下の少量添加した場合は、オゾン収量が極端に減じて好ましくなく、一方、水素、メタンの一種以上を合計で２００ｐｐｍ以上、且つ窒素ガスを１５０ｐｐｍ以上又は二酸化炭素ガスを１０ｖｏｌ．％以上の多量添加した場合は、オゾン収量がそれ程高くならなくて経済性等の点で不利であり好ましくない。 As described above, in the present invention, four kinds of carbon dioxide and methane, carbon dioxide and hydrogen, nitrogen and methane, and nitrogen and hydrogen are used as additive gas components that provide a stable and high yield. One or more of hydrogen and methane are added in total to 5 ppm or less, nitrogen gas is 5 ppm or less, or carbon dioxide gas is 1 vol. When a small amount of less than 10% is added, the ozone yield is extremely reduced, which is not preferable. On the other hand, one or more of hydrogen and methane are combined in a total of 200 ppm or more, nitrogen gas is 150 ppm or more, or carbon dioxide gas is 10 vol. When a large amount of at least% is added, the ozone yield is not so high, which is disadvantageous in terms of economy and the like.
又前述の通り、本発明では、水素、メタンの一種以上と、窒素又は二酸化炭素ガスの他に、アルゴン、ヘリウム、ネオン、クリプトン、キセノンの一種以上の含有を許容しているが、これらの成分は、熱伝導性の大きいガスであるため、オゾナイザー内の余剰な熱を排除する効果があり、オゾンの分解を抑制する働きが見込まれる。しかし、積極的に添加する場合においても、それらの合計で５０００ｐｐｍ以下となすのが望ましい。これ以上の添加は、水素、メタンの一種以上と、窒素又は二酸化炭素ガスの存在下ではオゾン収量を変化させることはなく、却って高価なガスを浪費することになって余り意味がない。 As described above, in the present invention, one or more of hydrogen, methane and nitrogen or carbon dioxide gas are allowed to contain one or more of argon, helium, neon, krypton, and xenon. Is a gas having a high thermal conductivity, and therefore has the effect of eliminating excess heat in the ozonizer, and is expected to function to suppress the decomposition of ozone. However, even when positively added, it is desirable that the total amount thereof is 5000 ppm or less. Addition beyond this does not change the ozone yield in the presence of one or more of hydrogen, methane, and nitrogen or carbon dioxide gas, but rather wastes expensive gas.
次いで、前記無声放電式オゾナイザーを用いて、高純度酸素ガス（９９．９９９９％）に対する窒素、水素、及びメタンの添加量を変化させた場合についての生成オゾン濃度の変化を測定した。その結果を図２のグラフに示す。同図において、（ａ）は高純度酸素に窒素を添加したもの（実験例１）であり、（ｂ）は高純度酸素に水素を添加したもの（実験例２）、（ｃ）は高純度酸素にメタンを添加したもの（実験例３）である。 Next, using the silent discharge type ozonizer, the change in the generated ozone concentration was measured when the amounts of nitrogen, hydrogen, and methane added to the high-purity oxygen gas (99.9999%) were changed. The result is shown in the graph of FIG. In the figure, (a) is a high purity oxygen added with nitrogen (Experimental Example 1), (b) is a high purity oxygen added with hydrogen (Experimental Example 2), and (c) is a high purity oxygen. It is what added methane to oxygen (Experimental example 3).
実験例１（ａ）の場合、５ｐｐｍ未満の窒素添加では生成されるオゾンは極めて少量であり、１０〜２０ｐｐｍの範囲で生成オゾン濃度が急峻に増して、それから後は緩やかに増加し、添加量が１５０ｐｐｍ以上になると生成オゾン濃度は殆ど変わらなくなる。 In the case of Experimental Example 1 (a), the amount of ozone generated is very small when nitrogen is added at less than 5 ppm, and the concentration of generated ozone increases sharply in the range of 10 to 20 ppm, and then gradually increases. When the concentration exceeds 150 ppm, the generated ozone concentration hardly changes.
実験例２（ｂ）の場合、２０ｐｐｍの水素添加で約８０ｇ／ｍ３のオゾンが発生し、添加量を増やして行くと生成オゾン濃度は緩やかに増加して２００ｐｐｍ近傍で最大値となり、その後、濃度は殆ど変わらなくなる。 In the case of Experimental Example 2 (b), ozone of about 80 g / m 3 is generated by hydrogen addition of 20 ppm, and when the addition amount is increased, the generated ozone concentration gradually increases and reaches a maximum value in the vicinity of 200 ppm. The concentration is almost unchanged.
実験例３（ｃ）の場合、５ｐｐｍ未満のメタン添加で約８０ｇ／ｍ３のオゾンが発生し、一旦、５０ｐｐｍ程度の添加で生成オゾン濃度が最大になり、その後、緩やかに減衰するものの、２００ｐｐｍ添加では、依然として８０ｇ／ｍ３以上のオゾンが発生する。 In the case of Experimental Example 3 (c), about 80 g / m 3 of ozone is generated by adding less than 5 ppm of methane, and once the addition of about 50 ppm, the generated ozone concentration becomes maximum, and then gradually attenuates, but 200 ppm In addition, ozone of 80 g / m 3 or more is still generated.
以上の説明により明らかであるが、請求項１に記載するガスの添加濃度の範囲として、窒素は５〜１５０ｐｐｍにし、水素及びメタンは可燃性ガスであるため高圧ガス保安法の観点からも２％未満にすることが望ましく、添加量をできるだけ減らす意味も含めて上限は２００ｐｐｍ、下限は生成オゾン量が顕著に大きくなる５ｐｐｍとするものである。 As is apparent from the above description, the range of the gas addition concentration described in claim 1 is 5 to 150 ppm for nitrogen, and hydrogen and methane are flammable gases, so 2% from the viewpoint of the high-pressure gas safety law. The upper limit is 200 ppm including the meaning of reducing the addition amount as much as possible, and the lower limit is 5 ppm at which the amount of generated ozone is remarkably increased.
続いて、前記無声放電式オゾナイザーを用いて、高純度酸素ガス（９９．９９９９％）に対する二酸化炭素ガスの添加量を変化させた場合についての生成オゾン濃度の変化を測定した。その結果を図３のグラフに示す。同図に示される実験例４の場合は、１％未満の二酸化炭素ガス添加では、生成オゾン濃度が十分に得られなく、また、安定したオゾン収量が得られないため、１％以上の添加量が望ましい。また、１０％以上の添加は生成オゾン濃度に大きく影響を与えないため、却ってガスの無駄使いとなって好ましくない。以上の点から本発明は、二酸化炭素ガスの添加量として下限を１％とし、且つ、上限を１０％としたものである。 Subsequently, using the silent discharge type ozonizer, a change in the generated ozone concentration was measured when the amount of carbon dioxide gas added to the high-purity oxygen gas (99.9999%) was changed. The result is shown in the graph of FIG. In the case of Experimental Example 4 shown in the same figure, when the carbon dioxide gas addition is less than 1%, the generated ozone concentration cannot be sufficiently obtained, and a stable ozone yield cannot be obtained. Is desirable. Moreover, since addition of 10% or more does not greatly affect the generated ozone concentration, it is not preferable because it wastes gas. From the above points, the present invention sets the lower limit of the amount of carbon dioxide gas added to 1% and the upper limit to 10%.
尚、上記各実施例・実験例では、シックス−ナイン（９９．９９９９％）の超高純度酸素ガスを用いているが、工業的には、空気液化分離装置等から高純度酸素として得られる純度９９．９％程度の酸素ガスも、本発明で使用可能である事はいうまでもない。特に、一般に高純度酸素ガスと呼ばれるガス中には、不純物としてアルゴンやヘリウムが含まれており、これらの不純物ガスは、前述の通り、本発明では許容されているガスであるので、これらを積極的に除去した高重度酸素ガスを用いる必要はない。 In each of the above examples and experimental examples, six-nine (99.9999%) ultra-high purity oxygen gas is used, but industrially, the purity obtained as high-purity oxygen from an air liquefaction separation apparatus or the like. It goes without saying that oxygen gas of about 99.9% can also be used in the present invention. In particular, a gas generally called high-purity oxygen gas contains argon and helium 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.
以上に詳述した如く、本発明の放電式オゾン生成方法によると、高純度酸素ガスに、ネオン、クリプトン、キセノン、水素或いはメタン更にアルゴン、ヘリウムを添加したガスを原料ガスとして使用しているので、生成オゾンガスに随伴するガスは凡そ無害なガスとなり、あらゆる産業分野に、本発明で生成したオゾンガスを使用することができる。 As described in detail above, according to the discharge ozone generation method of the present invention, a gas obtained by adding neon, krypton, xenon, hydrogen, methane, argon, and helium to a high purity oxygen gas is used as a raw material gas. The gas accompanying the generated ozone gas is almost harmless, and the ozone gas generated by the present invention can be used in all industrial fields.
Claims (2)
原料ガスとして、高純度酸素ガス中に、水素、メタンの一種以上を合計で５〜２００ｐｐｍ、且つ窒素ガスを５〜１５０ｐｐｍ又は二酸化炭素ガスを１〜１０ｖｏｌ．％添加してなる混合ガスを用いることを特徴とする放電式オゾンガス生成方法。 In the discharge-type ozone gas generation method of supplying ozone-containing source gas to a discharge-type ozonizer to generate ozone gas,
As a raw material gas, in a high purity oxygen gas, a total of one or more of hydrogen and methane is 5 to 200 ppm, nitrogen gas is 5 to 150 ppm, or carbon dioxide gas is 1 to 10 vol. A discharge-type ozone gas generation method characterized by using a mixed gas obtained by adding%.
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| JP2009298669A (en) * | 2008-06-16 | 2009-12-24 | Sumitomo Precision Prod Co Ltd | Method of producing ozone and ozone generator |
| EP3725739A1 (en) * | 2019-04-16 | 2020-10-21 | SUEZ Groupe | Ozone generation method and ozone generation device |
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| JP2009298669A (en) * | 2008-06-16 | 2009-12-24 | Sumitomo Precision Prod Co Ltd | Method of producing ozone and ozone generator |
| EP3725739A1 (en) * | 2019-04-16 | 2020-10-21 | SUEZ Groupe | Ozone generation method and ozone generation device |
| WO2020212435A1 (en) * | 2019-04-16 | 2020-10-22 | Suez Groupe | Ozone generation method and ozone generation device |
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