JP4135186B2 - Ozone gas generator and ozone-dissolved water production device - Google Patents

Ozone gas generator and ozone-dissolved water production device Download PDF

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JP4135186B2
JP4135186B2 JP2003076310A JP2003076310A JP4135186B2 JP 4135186 B2 JP4135186 B2 JP 4135186B2 JP 2003076310 A JP2003076310 A JP 2003076310A JP 2003076310 A JP2003076310 A JP 2003076310A JP 4135186 B2 JP4135186 B2 JP 4135186B2
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ozone
gas
hydrogen
dissolved water
concentration
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JP2004285374A (en
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博志 森田
洋 黒部
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Kurita Water Industries Ltd
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Kurita Water Industries Ltd
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  • Treatment Of Water By Oxidation Or Reduction (AREA)
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Description

【0001】
【発明の属する技術分野】
本発明は、オゾンガス発生装置及びオゾン溶解水製造装置に関する。さらに詳しくは、本発明は、電解式オゾン発生装置の隔膜の劣化の状態を正確に把握して、適切な時期に隔膜を交換することを可能とするとともに、オゾンガス系及びオゾン溶解水系における水素ガスによる事故を防止することができるオゾンガス発生装置及びオゾン溶解水製造装置に関する。
【0002】
【従来の技術】
オゾンの用途は、従来の殺菌、漂白に留まらず、有機物分解などの水処理や、超純水などの純度が保証された水にオゾンを溶解して調製するオゾン溶解水による洗浄分野などにも広がりをみせている。
オゾン発生の手段としては、高純度酸素、濃度を高めた酸素、空気中の酸素などを原料として、放電エネルギーを与えてその一部をオゾンに転換する放電方式と、純水を原料として特殊な触媒と適当な電解条件によって陽極側からオゾンと酸素ガスの混合ガスを取り出す電解方式がある。両方式には、それぞれに長所と短所があり、使い分けられている。
電解方式は、純水と電気さえあればよいこと、比較的高濃度で高純度のオゾンガスを得やすいことなどの特徴によって、洗浄用のオゾン溶解水の製造装置などに多く使われている。手軽な方法であるが、オゾン発生と同時に、陰極側では副生成物として水素ガスが発生することも特徴となっている。
電解式オゾン発生器は、陰・陽両極の間を固体高分子隔膜が仕切る構造になっている。実用的な固体高分子隔膜として、耐オゾン性を有するポリテトラフルオロエチレンを基体とするイオン交換膜が採用されている。ポリテトラフルオロエチレンを基体とするイオン交換膜は、この用途に使用し得る事実上唯一の膜であるが、ポリテトラフルオロエチレン固有のガス透過性のために、水素ガスの陽極側への混入と、オゾンと酸素ガスの陰極側への混入が避けられないという問題点を有する。これらのガス成分が混合し、爆発条件を満たすガスになると、そこに静電気など何らかの着火源が加わった場合に爆発を起こすという事態も想定され、その事例も認められている。
これに対して、現状の危険回避策は、イオン交換膜の経年劣化や異常によるガス透過性の上昇を見越して、定期的に膜交換を実施することが一般的手段となっている。しかし、膜品質や電解セル組立施行技術などのばらつきにより、対極側ガスの混入量増加の進行もばらつき、単純な定期交換だけでは危険を回避できない場合もあった。また、定期交換の頻度を増やすことは、安全面では望ましいが、無駄が多くなり、手間とコスト増大の面から限界があることはいうまでもない。
他のイオン交換膜劣化に対する危険回避手段として、膜によって仕切られている陰・陽両極間の電圧をモニターする方法が提案され、一部実用化されている。オゾンを実質的に発生させない低電流電解条件下では、膜間電圧は膜の劣化指標として運用できるが、通常のオゾン発生条件である所定電流電解条件下では、膜の劣化を膜間電圧で見極めることは困難であるという問題点があった。特に生産ラインで連続運転することが求められる場合、頻繁に低電流電解を実施するわけはにいかず、使いやすい監視手段とは言えなかった。
安全確保のために最も重要なことは、オゾンガス中に水素ガスが混入しない状態を保つことである。最悪でも、爆発限界(空気−水素ガス系では4容量%)未満を維持しなければならない。生産物であるオゾンガス中の水素ガスを監視することが最も直接的で確実であるが、オゾン雰囲気に耐える実用的な水素ガスモニターと検知器は現状では存在せず、このために上述の電圧測定に頼らざるを得ないという状況にあった。
【0003】
【発明が解決しようとする課題】
本発明は、電解式オゾン発生装置の隔膜の劣化の状態を正確に把握して、適切な時期に隔膜を交換することを可能とするとともに、オゾンガス系及びオゾン溶解水系における水素ガスによる事故を防止することができるオゾンガス発生装置及びオゾン溶解水製造装置を提供することを目的としてなされたものである。
【0004】
【課題を解決するための手段】
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、オゾンガス発生装置の陽極室から排出されたオゾン含有ガス中のオゾンをオゾン分解装置を用いて分解し、オゾン分解装置を経たガス中の水素ガス濃度を水素計測装置を用いて測定することにより、オゾンガス発生装置の隔膜の劣化の状態と、オゾンと酸素ガスの混合ガスへの水素ガスの混入状態を的確に把握することができ、オゾンガス発生装置の陰極室から排出された水素含有ガス中のオゾン又は酸素ガス濃度を計測装置を用いて測定することにより、オゾンガス発生装置の隔膜の劣化の状態を把握することができ、さらに、オゾンガス発生装置とガス溶解装置とを備えたオゾン溶解水製造装置に、上記のガス計測装置を付設することにより、オゾン溶解水製造装置とオゾン溶解水使用装置を安全に運転し得ることを見いだし、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
(1)隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置において、前記排出されたオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を測定する水素計測装置とを設けてなることを特徴とするオゾンガス発生装置、
(2)第1項記載のオゾンガス発生装置と、該オゾンガス発生装置から排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなることを特徴とするオゾン溶解水製造装置、及び、
)隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置と、該排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなるオゾン溶解水製造装置において、ガス溶解装置から排出された余剰のオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を検出する水素計測装置とを設けてなることを特徴とするオゾン溶解水製造装置、
を提供するものである。
さらに、本発明の好ましい態様として、
)オゾン分解装置が、活性炭充填塔、触媒充填塔又は紫外線照射装置である第1項記載のオゾンガス発生装置、
)水素計測装置が、測定した水素ガス濃度に応じて警報を発する第1項記載のオゾンガス発生装置、
)水素計測装置と電解装置の間にインターロックシステムが構成され、測定された水素ガス濃度が所定の閾値に達したとき、電解装置の運転が停止される第1項記載のオゾンガス発生装置、及び、
)水素ガス濃度の所定の閾値が、水素ガスの爆発限界濃度以下の値である第項記載のオゾンガス発生装置、
を挙げることができる。
【0005】
【発明の実施の形態】
本発明のオゾンガス発生装置の第一の態様は、隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置において、前記排出されたオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を測定する水素計測装置とを設けてなるオゾンガス発生装置である。
図1は、本発明のオゾンガス発生装置の一態様の説明図である。イオン交換膜1で区画して、一方の側を陰極室2、他方の側を陽極室3とした電解装置4に、純水が供給され、電解される。純水の電解により、陰極室では水素ガスが発生し、陽極室ではオゾンと酸素ガスの混合ガスが発生する。オゾンと酸素ガスの混合ガスとして排出されるオゾン含有ガスは、オゾン分解装置5においてガス中のオゾンが分解されたのち、水素計測装置6に送られてガス中の水素ガス濃度が測定される。
本発明装置に使用するオゾン分解装置に特に制限はなく、例えば、活性炭充填塔、オゾン分解触媒充填塔、紫外線照射装置などを挙げることができる。微量の水素ガスを含有するオゾンと酸素ガスの混合ガスは、オゾン分解装置を経由することにより、混合ガス中のオゾンが分解されて微量の水素ガスを含有する酸素ガスとなるので、水素計測装置は、オゾンによる劣化や妨害を受けず、誤計測がなく安定して水素ガス濃度を測定することができる。
【0006】
測定された水素ガス濃度は、記録計等に出力して、陰極室側から陽極室側への水素ガスの移動量を把握し、電解装置の隔膜として用いているイオン交換膜の劣化の状態を判断することができる。また、水素ガス濃度が所定の値に達したとき、ライトの点滅やブザーなどにより、水素計測装置から警報を発することができる。さらに、水素計測装置にあらかじめ水素ガスの爆発限界濃度以下の閾値を設定しておき、水素計測装置と電解装置の間にインターロックシステムを構成し、水素ガス濃度が閾値に達したとき、自動的に電解装置の運転を停止し、高濃度の水素ガスによる事故を未然に防止することができる。
図1に示す態様のオゾンガス発生装置においては、陽極側から排出されるオゾン含有ガスの一部をバイパスして、オゾン分解装置及び水素計測装置に通気しているが、オゾン利用部においてオゾン含有ガスを使用しない時間帯がある場合は、陽極室から排出されるオゾン含有ガスの全量をオゾン分解装置及び水素計測装置に通気することもできる。
【0007】
図2は、本発明のオゾンガス発生装置の他の態様の説明図である。イオン交換膜1で区画して、一方の側を陰極室2、他方の側を陽極室3とした電解装置4に、純水が供給され、電解される。純水の電解により、陰極室では水素ガスが発生し、陽極室ではオゾンと酸素ガスの混合ガスが発生する。陰極から排出される水素含有ガスは、オゾン又は酸素計測装置7に送られて、ガス中のオゾン濃度又は酸素ガス濃度が測定される。
測定されたオゾン濃度又は酸素ガス濃度は、記録計に出力して、陽極室側から陰極室側へのオゾン又は酸素ガスの移動量を把握し、電解装置の隔膜として用いているイオン交換膜の劣化の状態を判断することができる。また、オゾン又は酸素計測装置にあらかじめオゾン又は酸素ガスの濃度の閾値を設定しておき、オゾン又は酸素ガスの濃度が所定の値に達したとき、ライトの点滅やブザーなどにより、警報を発することができる。
本発明において、陰極室から排出される水素含有ガスの処理方法に特に制限はなく、例えば、アルミナ担体に白金を担持させた酸化触媒に空気の存在下で接触させ、低温で酸化させて水に変換することができる。
【0008】
本発明のオゾン溶解水製造装置の第一の態様は、本発明のオゾンガス発生装置と、該オゾンガス発生装置から排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなるオゾン溶解水製造装置である。図3は、本発明のオゾン溶解水製造装置の一態様の説明図である。本態様のオゾン溶解水製造装置においては、電解装置4の陽極室3から排出されるオゾンと酸素ガスの混合ガスが、オゾン分解装置5においてガス中のオゾンが分解されたのち、水素計測装置6に送られてガス中の水素ガス濃度が測定される本発明のオゾンガス発生装置、又は、電解装置4の陰極室2から排出される水素含有ガスが、オゾン又は酸素計測装置7に送られてガス中のオゾン濃度又は酸素ガス濃度が測定される本発明のオゾンガス発生装置と、オゾン含有ガスを水に溶解させるガス溶解装置8が備えられている。
純水の電解によりオゾン含有ガスを発生させると、水素ガスの発生モル数は、オゾンと酸素ガスの合計発生モル数の2モル倍以上である。本態様のオゾン溶解水製造装置を用い、陽極室から排出されるオゾン含有ガス中の水素ガス濃度を測定し、必要に応じて、水素計測装置と電解装置のインターロックシステムを構成することにより、オゾン溶解水製造装置において、水素ガス濃度が上昇し、不測の事故が発生することを未然に防止することができる。
【0009】
本発明のオゾン溶解水製造装置の第二の態様は、隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置と、該排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなるオゾン溶解水製造装置において、ガス溶解装置から排出された余剰のオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を検出する水素計測装置とを設けてなるオゾン溶解水製造装置である。
図4は、本発明のオゾン溶解水製造装置の他の態様の説明図である。イオン交換膜1で区画して、一方の側を陰極室2、他方の側を陽極室3とした電解装置4に、純水が供給され、電解される。純水の電解により、陰極室では水素ガスが発生し、陽極室ではオゾンと酸素ガスの混合ガスが発生する。オゾンと酸素ガスの混合ガスとして排出されるオゾン含有ガスは、ガス溶解装置8に送られ、オゾン含有ガスがガス溶解装置に供給される水に溶解してオゾン溶解水が調製される。本態様のオゾン溶解水製造装置においては、ガス溶解装置8から排出される排ガスがオゾン分解装置5に導かれ、排ガス中に残存するオゾンが分解されたのち、水素計測装置6に送られてガス中の水素ガス濃度が測定される。
【0010】
本発明のオゾン溶解水製造装置に使用するオゾン分解装置に特に制限はなく、例えば、活性炭充填塔、オゾン分解触媒充填塔、紫外線照射装置などを挙げることができる。微量の水素ガスを含有するオゾンと酸素ガスの混合ガスからなる排ガスは、オゾン分解装置を経由することにより、排ガス中のオゾンが分解されて微量の水素ガスを含有する酸素ガスとなるので、水素計測装置は、オゾンによる劣化や妨害を受けることなく安定して水素ガス濃度を測定することができる。測定された水素ガス濃度は、記録計に出力して、陰極室側から陽極室側への水素ガスの移動量を把握し、電解装置の隔膜として用いているイオン交換膜の劣化の状態を判断することができる。また、水素ガス濃度が所定の値に達したとき、ライトの点滅やブザーなどにより、水素計測装置から警報を発することができる。さらに、水素計測装置にあらかじめ水素ガス濃度の閾値を設定しておき、水素計測装置と電解装置の間にインターロックシステムを構成し、水素ガス濃度が閾値に達したとき、自動的に電解装置の運転を停止し、高濃度の水素ガスによる事故を未然に防止することができる。
【0011】
図4に示す態様のオゾン溶解水製造装置においては、オゾンガス発生装置で発生したオゾン含有ガスの全量を常にガス溶解装置に送って、オゾン溶解水を調製するので、定常状態を乱すことなく安定してオゾン溶解水を製造することができる。本態様の装置においては、電解装置の陽極室から排出されるオゾン含有ガスの全量をガス溶解装置に送り、オゾン溶解水を調製したのちの排ガスについて、水素ガス濃度を測定するので、ガス溶解装置におけるオゾン、酸素ガス及び水素ガスの溶解による減少量を考慮して、排ガス中の水素ガス濃度から、電解装置の陰極室側から陽極室側へ移動した水素ガスの量を想定し、水素ガス濃度の閾値を定めることが好ましい。水素ガスの水への溶解の程度は、オゾン含有ガスと水との供給条件や圧力などのオゾン溶解水製造条件によって変動するので、条件ごとに検討する必要がある。また、オゾンと水素ガスが反応して水素ガスが減少する可能性もあるので、考慮に入れることが好ましい。
本発明のオゾン溶解水製造装置において、オゾン含有ガスを水に溶解させてオゾン溶解水を調製するガス溶解装置に特に制限はなく、例えば、気体透過膜を用いるガス溶解装置、エジェクターと気液分離器とを組み合わせたガス溶解装置、散気方式のガス溶解装置、水配管へのガス注入口とスタティックミキサーを組み合わせたガス溶解装置などを挙げることができる。図3に示す態様においては、気体透過膜モジュール1個を用いたガス溶解装置が示されているが、複数個の気体透過膜モジュールを直列に連結し、オゾン含有ガスとオゾン溶解水を向流で接触させることにより、溶解オゾン濃度の高いオゾン溶解水を製造することができる。
【0012】
【発明の効果】
本発明のオゾンガス発生装置によれば、陽極室から排出されるオゾン含有ガス中の水素ガス濃度又は陰極室から排出される水素ガス中のオゾン又は酸素ガスの濃度を測定することにより、電極槽の隔膜の劣化の状態を的確に把握し、隔膜を可能な限り長期間使用した上で、必要が生じた時期に交換し、隔膜を有効かつ経済的に使用することができる。また、本発明のオゾンガス発生装置及びオゾン溶解水製造装置によれば、電解式オゾン発生器固有の問題として避けられないオゾン、酸素ガス及び水素ガスの混合状況を正しく見極め、水素ガス濃度の上昇がもたらす不測の事故を未然に防ぐことができる。
【図面の簡単な説明】
【図1】図1は、本発明のオゾンガス発生装置の一態様の説明図である。
【図2】図2は、本発明のオゾンガス発生装置の他の態様の説明図である。
【図3】図3は、本発明のオゾン溶解水製造装置の一態様の説明図である。
【図4】図4は、本発明のオゾン溶解水製造装置の他の態様の説明図である。
【符号の説明】
1 イオン交換膜
2 陰極室
3 陽極室
4 電解装置
5 オゾン分解装置
6 水素計測装置
7 オゾン又は酸素計測装置
8 ガス溶解装置
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ozone gas generator and an ozone dissolved water production apparatus. More specifically, the present invention makes it possible to accurately grasp the state of deterioration of the diaphragm of the electrolytic ozone generator, to replace the diaphragm at an appropriate time, and to use hydrogen gas in an ozone gas system and an ozone-dissolved water system. The present invention relates to an ozone gas generator and an ozone-dissolved water production apparatus that can prevent accidents caused by the above.
[0002]
[Prior art]
The use of ozone is not limited to conventional sterilization and bleaching, but also in the field of water treatment such as organic matter decomposition and cleaning with ozone-dissolved water prepared by dissolving ozone in water with guaranteed purity such as ultrapure water. Extensive.
As a means of ozone generation, high purity oxygen, oxygen with high concentration, oxygen in the air, etc. are used as a raw material, a discharge method in which discharge energy is given and part of it is converted into ozone, and special water is used as a raw material. There is an electrolysis method in which a mixed gas of ozone and oxygen gas is extracted from the anode side by a catalyst and appropriate electrolysis conditions. Both types have their advantages and disadvantages and are used separately.
The electrolysis method is often used in an apparatus for producing ozone-dissolved water for cleaning, because it only needs pure water and electricity, and easily obtains ozone gas having a relatively high concentration and high purity. Although it is an easy method, it is also characterized in that hydrogen gas is generated as a by-product on the cathode side simultaneously with the generation of ozone.
The electrolytic ozone generator has a structure in which a solid polymer membrane partitions between the negative and positive electrodes. As a practical solid polymer membrane, an ion exchange membrane based on ozone-resistant polytetrafluoroethylene is used. Polytetrafluoroethylene-based ion exchange membranes are virtually the only membranes that can be used in this application. However, due to the inherent gas permeability of polytetrafluoroethylene, hydrogen gas can be mixed into the anode side. In addition, ozone and oxygen gas are inevitably mixed into the cathode side. When these gas components are mixed and become a gas that satisfies the explosion condition, it is assumed that an explosion will occur if any ignition source such as static electricity is applied to the gas, and such cases are also recognized.
On the other hand, the current risk avoidance measure is a general means to periodically perform membrane exchange in anticipation of an increase in gas permeability due to aging and abnormality of the ion exchange membrane. However, due to variations in membrane quality, electrolytic cell assembly enforcement technology, etc., the progress of the increase in the amount of mixed gas on the counter electrode also varies, and there are cases in which danger cannot be avoided by simple periodic replacement. Increasing the frequency of periodic replacement is desirable in terms of safety, but it is needless to say that there is a limit in terms of labor and cost increase because of increased waste.
As another means for avoiding the risk of ion exchange membrane degradation, a method of monitoring the voltage between the negative and positive electrodes partitioned by the membrane has been proposed and partially put into practical use. Under low-current electrolysis conditions that do not substantially generate ozone, the transmembrane voltage can be used as a membrane degradation indicator, but under normal current generation conditions, which are ozone generation conditions, membrane degradation can be determined by the transmembrane voltage. There was a problem that it was difficult. In particular, when continuous operation is required on the production line, low current electrolysis cannot be performed frequently, and it cannot be said that the monitoring means is easy to use.
The most important thing for ensuring safety is to keep the hydrogen gas from being mixed into the ozone gas. At worst, it must be kept below the explosion limit (4% by volume in the air-hydrogen gas system). It is the most direct and reliable to monitor the hydrogen gas in the product ozone gas, but there is currently no practical hydrogen gas monitor and detector that can withstand the ozone atmosphere. There was a situation that had to rely on.
[0003]
[Problems to be solved by the invention]
The present invention makes it possible to accurately grasp the state of deterioration of the diaphragm of the electrolytic ozone generator, replace the diaphragm at an appropriate time, and prevent accidents caused by hydrogen gas in the ozone gas system and the ozone-dissolved water system. The object of the present invention is to provide an ozone gas generator and an ozone-dissolved water production device that can be used.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have decomposed ozone in the ozone-containing gas discharged from the anode chamber of the ozone gas generator using an ozone decomposing apparatus. By measuring the hydrogen gas concentration in the passed gas using a hydrogen measuring device, the state of deterioration of the diaphragm of the ozone gas generator and the state of mixing of hydrogen gas into the mixed gas of ozone and oxygen gas should be accurately grasped. By measuring the ozone or oxygen gas concentration in the hydrogen-containing gas discharged from the cathode chamber of the ozone gas generator using a measuring device, the state of deterioration of the diaphragm of the ozone gas generator can be grasped. Furthermore, by adding the above gas measuring device to an ozone-dissolved water production device equipped with an ozone gas generation device and a gas dissolution device, the ozone-dissolved water production device and the ozone solution are obtained. Found that the dissolved water using apparatus capable of safe operation, and have completed the present invention based on this finding.
That is, the present invention
(1) In an ozone gas generator that supplies pure water to an electrolyzer that is partitioned by a diaphragm and has one side as a cathode chamber and the other side as an anode chamber, and electrolyzes, and discharges the generated ozone-containing gas from the anode chamber And an ozone decomposing apparatus for decomposing ozone in the discharged ozone-containing gas, and a hydrogen measuring apparatus for measuring the hydrogen gas concentration in the gas by contacting with the gas passed through the ozone decomposing apparatus. Ozone gas generator,
(2) An ozone-dissolved water production apparatus comprising: the ozone gas generator according to item 1; and a gas dissolver that dissolves the ozone-containing gas discharged from the ozone gas generator into water; and
( 3 ) an ozone gas generator that supplies pure water to an electrolyzer that is partitioned by a diaphragm and has one side as a cathode chamber and the other side as an anode chamber, and discharges the generated ozone-containing gas from the anode chamber; An ozone-dissolved water production apparatus comprising a gas-dissolving device for dissolving the discharged ozone-containing gas in water, an ozone decomposing device for decomposing ozone in the surplus ozone-containing gas discharged from the gas-dissolving device; An ozone-dissolved water production apparatus comprising: a hydrogen measuring device that is brought into contact with a gas that has passed through an ozonolysis device to detect a hydrogen gas concentration in the gas;
Is to provide.
Furthermore, as a preferred embodiment of the present invention,
( 4 ) The ozone gas generator according to item 1, wherein the ozonolysis apparatus is an activated carbon packed tower, a catalyst packed tower or an ultraviolet irradiation apparatus,
( 5 ) The ozone gas generator according to item 1, wherein the hydrogen measuring device issues an alarm according to the measured hydrogen gas concentration,
( 6 ) The ozone gas generator according to item 1, wherein an interlock system is configured between the hydrogen measurement device and the electrolysis device, and the operation of the electrolysis device is stopped when the measured hydrogen gas concentration reaches a predetermined threshold value. , and,
( 7 ) The ozone gas generator according to item 6 , wherein the predetermined threshold value of the hydrogen gas concentration is a value equal to or lower than the explosion limit concentration of hydrogen gas,
Can be mentioned.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The first aspect of the ozone gas generator of the present invention is an ozone-containing gas generated by electrolyzing by supplying pure water to an electrolyzer divided by a diaphragm and having one side as a cathode chamber and the other side as an anode chamber. In an ozone gas generator for discharging ozone from the anode chamber, an ozone decomposition device for decomposing ozone in the discharged ozone-containing gas, and hydrogen for contacting the gas passed through the ozone decomposition device and measuring a hydrogen gas concentration in the gas This is an ozone gas generator provided with a measuring device.
FIG. 1 is an explanatory diagram of an embodiment of the ozone gas generator of the present invention. Pure water is supplied and electrolyzed to an electrolysis apparatus 4 partitioned by the ion exchange membrane 1 and having one side as the cathode chamber 2 and the other side as the anode chamber 3. By electrolysis of pure water, hydrogen gas is generated in the cathode chamber, and a mixed gas of ozone and oxygen gas is generated in the anode chamber. The ozone-containing gas discharged as a mixed gas of ozone and oxygen gas is sent to the hydrogen measuring device 6 after the ozone in the gas is decomposed in the ozone decomposing device 5, and the hydrogen gas concentration in the gas is measured.
There is no restriction | limiting in particular in the ozonolysis apparatus used for this invention apparatus, For example, an activated carbon packed tower, an ozone decomposition catalyst packed tower, an ultraviolet irradiation apparatus etc. can be mentioned. Since the mixed gas of ozone and oxygen gas containing a small amount of hydrogen gas passes through an ozone decomposition device, the ozone in the mixed gas is decomposed into an oxygen gas containing a small amount of hydrogen gas. Can stably measure the hydrogen gas concentration without being erroneously measured and without being deteriorated or obstructed by ozone.
[0006]
The measured hydrogen gas concentration is output to a recorder, etc., and the amount of hydrogen gas transferred from the cathode chamber side to the anode chamber side is ascertained, and the state of deterioration of the ion exchange membrane used as the diaphragm of the electrolyzer is checked. Judgment can be made. Further, when the hydrogen gas concentration reaches a predetermined value, an alarm can be issued from the hydrogen measuring device by blinking a light or a buzzer. Furthermore, a threshold value below the explosion limit concentration of hydrogen gas is set in the hydrogen measurement device in advance, and an interlock system is configured between the hydrogen measurement device and the electrolysis device. When the hydrogen gas concentration reaches the threshold value, it is automatically In addition, the operation of the electrolyzer can be stopped and accidents caused by high-concentration hydrogen gas can be prevented.
In the ozone gas generator of the embodiment shown in FIG. 1, a part of the ozone-containing gas discharged from the anode side is bypassed and ventilated to the ozone decomposition device and the hydrogen measuring device. When there is a time zone in which no is used, the entire amount of the ozone-containing gas discharged from the anode chamber can be ventilated to the ozonolysis device and the hydrogen measurement device.
[0007]
FIG. 2 is an explanatory view of another aspect of the ozone gas generator of the present invention. Pure water is supplied and electrolyzed to an electrolysis apparatus 4 partitioned by the ion exchange membrane 1 and having one side as the cathode chamber 2 and the other side as the anode chamber 3. By electrolysis of pure water, hydrogen gas is generated in the cathode chamber, and a mixed gas of ozone and oxygen gas is generated in the anode chamber. The hydrogen-containing gas discharged from the cathode is sent to the ozone or oxygen measuring device 7, and the ozone concentration or oxygen gas concentration in the gas is measured.
The measured ozone concentration or oxygen gas concentration is output to a recorder, and the amount of ozone or oxygen gas transferred from the anode chamber side to the cathode chamber side is grasped, and the ion exchange membrane used as the diaphragm of the electrolysis device The state of deterioration can be determined. In addition, a threshold value of ozone or oxygen gas concentration is set in advance in the ozone or oxygen measuring device, and when the ozone or oxygen gas concentration reaches a predetermined value, an alarm is generated by blinking a light or a buzzer. Can do.
In the present invention, the method for treating the hydrogen-containing gas discharged from the cathode chamber is not particularly limited. For example, it is brought into contact with an oxidation catalyst in which platinum is supported on an alumina support in the presence of air, and is oxidized at a low temperature to form water. Can be converted.
[0008]
A first aspect of the ozone-dissolved water production apparatus of the present invention is an ozone-dissolved water comprising the ozone gas generator of the present invention and a gas dissolver that dissolves the ozone-containing gas discharged from the ozone gas generator into water. It is a manufacturing device. FIG. 3 is an explanatory view of one embodiment of the ozone-dissolved water production apparatus of the present invention. In the ozone-dissolved water production apparatus of this aspect, the mixed gas of ozone and oxygen gas discharged from the anode chamber 3 of the electrolysis apparatus 4 is decomposed into ozone in the gas by the ozone decomposition apparatus 5, and then the hydrogen measurement apparatus 6 The hydrogen-containing gas discharged from the cathode chamber 2 of the present invention in which the hydrogen gas concentration in the gas is measured by being sent to the gas or the electrolysis device 4 is sent to the ozone or oxygen measuring device 7 to be gas The ozone gas generator of the present invention in which the ozone concentration or oxygen gas concentration in the inside is measured, and the gas dissolving device 8 for dissolving the ozone-containing gas in water are provided.
When ozone-containing gas is generated by electrolysis of pure water, the number of moles of hydrogen gas generated is 2 moles or more of the total number of moles of ozone and oxygen gas generated. Using the ozone-dissolved water production apparatus of this aspect, measuring the hydrogen gas concentration in the ozone-containing gas discharged from the anode chamber, and if necessary, by configuring an interlock system of a hydrogen measuring device and an electrolysis device, In the ozone-dissolved water production apparatus, it is possible to prevent an unexpected accident from occurring due to an increase in hydrogen gas concentration.
[0009]
A second embodiment of the ozone-dissolved water production apparatus of the present invention is the ozone generated by supplying pure water to an electrolyzer that is partitioned by a diaphragm and having one side as a cathode chamber and the other side as an anode chamber. In an ozone-dissolved water production apparatus comprising an ozone gas generator for discharging a contained gas from an anode chamber and a gas dissolving device for dissolving the discharged ozone-containing gas in water, excess ozone discharged from the gas dissolving device An ozone-dissolved water production apparatus comprising an ozonolysis apparatus for decomposing ozone in a contained gas, and a hydrogen measurement apparatus for detecting a hydrogen gas concentration in the gas by contacting with the gas that has passed through the ozonolysis apparatus.
FIG. 4 is an explanatory view of another aspect of the ozone-dissolved water production apparatus of the present invention. Pure water is supplied and electrolyzed to an electrolysis apparatus 4 partitioned by the ion exchange membrane 1 and having one side as the cathode chamber 2 and the other side as the anode chamber 3. By electrolysis of pure water, hydrogen gas is generated in the cathode chamber, and a mixed gas of ozone and oxygen gas is generated in the anode chamber. The ozone-containing gas discharged as a mixed gas of ozone and oxygen gas is sent to the gas dissolving device 8, and the ozone-containing gas is dissolved in water supplied to the gas dissolving device to prepare ozone-dissolved water. In the ozone-dissolved water producing apparatus of this aspect, the exhaust gas discharged from the gas dissolver 8 is guided to the ozone decomposition apparatus 5, and after ozone remaining in the exhaust gas is decomposed, it is sent to the hydrogen measuring apparatus 6 to be gas. The hydrogen gas concentration inside is measured.
[0010]
There is no restriction | limiting in particular in the ozonolysis apparatus used for the ozone dissolved water manufacturing apparatus of this invention, For example, an activated carbon packed tower, an ozone decomposition catalyst packed tower, an ultraviolet irradiation apparatus etc. can be mentioned. Exhaust gas composed of a mixture of ozone and oxygen gas containing a trace amount of hydrogen gas is decomposed into oxygen gas containing a trace amount of hydrogen gas by decomposing ozone in the exhaust gas via an ozone decomposition device. The measuring device can stably measure the hydrogen gas concentration without being deteriorated or disturbed by ozone. The measured hydrogen gas concentration is output to a recorder, and the amount of hydrogen gas transferred from the cathode chamber side to the anode chamber side is ascertained to determine the state of deterioration of the ion exchange membrane used as the diaphragm of the electrolyzer. can do. Further, when the hydrogen gas concentration reaches a predetermined value, an alarm can be issued from the hydrogen measuring device by blinking a light or a buzzer. Furthermore, a hydrogen gas concentration threshold value is set in advance in the hydrogen measurement device, and an interlock system is configured between the hydrogen measurement device and the electrolysis device. When the hydrogen gas concentration reaches the threshold value, the electrolysis device is automatically Operation can be stopped and accidents caused by high-concentration hydrogen gas can be prevented.
[0011]
In the ozone-dissolved water production apparatus of the embodiment shown in FIG. 4, the total amount of ozone-containing gas generated by the ozone gas generator is always sent to the gas dissolver to prepare ozone-dissolved water, so that it is stable without disturbing the steady state. Thus, ozone-dissolved water can be produced. In the apparatus of this embodiment, the total amount of ozone-containing gas discharged from the anode chamber of the electrolysis apparatus is sent to the gas dissolving apparatus, and the hydrogen gas concentration is measured for the exhaust gas after preparing ozone-dissolved water. The amount of hydrogen gas transferred from the cathode chamber side to the anode chamber side of the electrolyzer from the hydrogen gas concentration in the exhaust gas, considering the decrease due to the dissolution of ozone, oxygen gas and hydrogen gas in It is preferable to define a threshold value of. Since the degree of dissolution of hydrogen gas in water varies depending on the ozone-containing gas and water supply conditions and the ozone-dissolved water production conditions such as pressure, it is necessary to examine each condition. Moreover, since ozone and hydrogen gas may react and hydrogen gas may reduce, it is preferable to take into consideration.
In the ozone-dissolved water production apparatus of the present invention, there is no particular limitation on the gas dissolver for preparing ozone-dissolved water by dissolving ozone-containing gas in water, for example, gas dissolver using gas permeable membrane, ejector and gas-liquid separation Examples include a gas dissolving device combined with a vessel, an aeration type gas dissolving device, and a gas dissolving device combined with a gas inlet to a water pipe and a static mixer. In the embodiment shown in FIG. 3, a gas dissolving apparatus using one gas permeable membrane module is shown, but a plurality of gas permeable membrane modules are connected in series to counterflow ozone-containing gas and ozone-dissolved water. By making it contact in, ozone-dissolved water with a high dissolved ozone concentration can be produced.
[0012]
【The invention's effect】
According to the ozone gas generator of the present invention, by measuring the concentration of hydrogen gas in the ozone-containing gas discharged from the anode chamber or the concentration of ozone or oxygen gas in the hydrogen gas discharged from the cathode chamber, The state of deterioration of the diaphragm can be accurately grasped, the diaphragm can be used for as long a period as possible, and can be exchanged when necessary, so that the diaphragm can be used effectively and economically. In addition, according to the ozone gas generator and the ozone-dissolved water production apparatus of the present invention, the mixing situation of ozone, oxygen gas and hydrogen gas, which is unavoidable as a problem inherent to the electrolytic ozone generator, is correctly identified, and the hydrogen gas concentration is increased. Unforeseen accidents can be prevented.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of one embodiment of an ozone gas generator of the present invention.
FIG. 2 is an explanatory view of another aspect of the ozone gas generator of the present invention.
FIG. 3 is an explanatory view of one embodiment of the ozone-dissolved water production apparatus of the present invention.
FIG. 4 is an explanatory diagram of another embodiment of the ozone-dissolved water production apparatus of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Ion exchange membrane 2 Cathode chamber 3 Anode chamber 4 Electrolyzer 5 Ozone decomposition device 6 Hydrogen measuring device 7 Ozone or oxygen measuring device 8 Gas dissolving device

Claims (3)

隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置において、前記排出されたオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を測定する水素計測装置とを設けてなることを特徴とするオゾンガス発生装置。  In an ozone gas generator that supplies pure water to an electrolyzer that is partitioned by a diaphragm and uses one side as a cathode chamber and the other side as an anode chamber for electrolysis, and discharges the generated ozone-containing gas from the anode chamber. An ozone gas comprising: an ozonolysis device for decomposing ozone in the generated ozone-containing gas; and a hydrogen measuring device for contacting the gas passed through the ozonolysis device and measuring the hydrogen gas concentration in the gas Generator. 請求項1記載のオゾンガス発生装置と、該オゾンガス発生装置から排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなることを特徴とするオゾン溶解水製造装置。  An ozone-dissolved water production apparatus comprising: the ozone gas generator according to claim 1; and a gas dissolver that dissolves ozone-containing gas discharged from the ozone gas generator in water. 隔膜で区画して一方の側を陰極室、他方の側を陽極室とした電解装置に純水を供給して電解し、発生したオゾン含有ガスを陽極室から排出するオゾンガス発生装置と、該排出されたオゾン含有ガスを水に溶解させるガス溶解装置とを備えてなるオゾン溶解水製造装置において、ガス溶解装置から排出された余剰のオゾン含有ガス中のオゾンを分解するオゾン分解装置と、オゾン分解装置を経たガスと接触させて該ガス中の水素ガス濃度を検出する水素計測装置とを設けてなることを特徴とするオゾン溶解水製造装置。  An ozone gas generator for supplying and electrolyzing pure water to an electrolysis apparatus partitioned by a diaphragm and having one side as a cathode chamber and the other side as an anode chamber, and discharging the generated ozone-containing gas from the anode chamber; An ozone-dissolved water production apparatus comprising a gas-dissolving apparatus that dissolves the ozone-containing gas into water, an ozone decomposing apparatus that decomposes ozone in excess ozone-containing gas discharged from the gas dissolving apparatus, and ozone decomposition An apparatus for producing ozone-dissolved water, comprising: a hydrogen measuring device that detects a hydrogen gas concentration in the gas by contacting the gas that has passed through the device.
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