JP2008237950A - Production method for hydroxyl radical-containing water and hydroxyl radical-containing water - Google Patents

Production method for hydroxyl radical-containing water and hydroxyl radical-containing water Download PDF

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JP2008237950A
JP2008237950A JP2007077781A JP2007077781A JP2008237950A JP 2008237950 A JP2008237950 A JP 2008237950A JP 2007077781 A JP2007077781 A JP 2007077781A JP 2007077781 A JP2007077781 A JP 2007077781A JP 2008237950 A JP2008237950 A JP 2008237950A
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water
microbubbles
ozone
generated
hydroxyl radical
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Kaneo Chiba
金夫 千葉
Masayoshi Takahashi
正好 高橋
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National Institute of Advanced Industrial Science and Technology AIST
REO Laboratory Co Ltd
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National Institute of Advanced Industrial Science and Technology AIST
REO Laboratory Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which easily and efficiently produces water containing a large amount of hydroxyl radical by advanced oxidation with ozone regardless of pH condition. <P>SOLUTION: In the production method for hydroxyl radical-containing water, ozone-containing microbubbles having a particle size of 50 μm or less are generated in water. The water in which the microbubbles are generated has a pH of 5 or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、あらゆる技術分野にその有用性が潜在する特別な機能を付与した水としての水酸基ラジカルを含む水の製造方法および当該方法により製造されてなる水酸基ラジカルを含む水に関する。   The present invention relates to a method for producing water containing a hydroxyl radical as water imparted with a special function that is potentially useful in all technical fields, and water containing a hydroxyl radical produced by the method.

水酸基ラジカル（・ＯＨ）は水中において最も反応性の高い物質の一つであり、酸化能力に優れるので汚水処理などの水処理や有害物質の分解処理などに利用できることは当業者によく知られた事実である。水中における水酸基ラジカルの生成方法はいくつか知られているが、その中にオゾンの促進酸化による方法がある。この方法は、不安定な物質であるオゾンを水中で促進的に分解させることで水酸基ラジカルを生成させるものであるが、オゾンは酸性条件下では安定化されるため、アルカリ性条件下で行われるのが一般的である。   It is well known to those skilled in the art that the hydroxyl radical (.OH) is one of the most reactive substances in water and has excellent oxidation ability and can be used for water treatment such as sewage treatment and decomposition treatment of harmful substances. It is a fact. Several methods for generating hydroxyl radicals in water are known. Among them, there is a method by accelerated oxidation of ozone. In this method, ozone, which is an unstable substance, is decomposed in water in an accelerated manner to generate hydroxyl radicals. However, ozone is stabilized under acidic conditions, so it is performed under alkaline conditions. Is common.

オゾンの促進酸化によって水中に水酸基ラジカルを生成させることを酸性条件下で行いたい場合、例えば、系内に紫外線を照射する方法（特許文献１）や系内に過酸化水素水を共存させる方法（特許文献２）などが採用される。しかしながら、紫外線を照射する方法は、水質の汚濁によって効果が低減するといった問題や紫外線を照射するための特別な装置が必要であるといった問題がある。また、過酸化水素水を共存させる方法は、コストが高くつくといった問題がある。
特開２００３−９４０７５号公報 特開平９−１２２６６２号公報 When it is desired to generate a hydroxyl radical in water by accelerated oxidation of ozone under acidic conditions, for example, a method of irradiating ultraviolet rays into the system (Patent Document 1) or a method of coexisting hydrogen peroxide water in the system ( Patent document 2) etc. are adopted. However, the method of irradiating ultraviolet rays has a problem that the effect is reduced due to water quality contamination and a problem that a special device for irradiating ultraviolet rays is required. Further, the method of coexisting hydrogen peroxide solution has a problem of high cost.
JP 2003-94075 A JP-A-9-122626

そこで本発明は、ｐＨ条件に依らずオゾンの促進酸化によって簡易かつ効率的に水酸基ラジカルを大量に含む水を製造する方法を提供することを目的とする。   Accordingly, an object of the present invention is to provide a method for producing water containing a large amount of hydroxyl radicals simply and efficiently by accelerated oxidation of ozone regardless of pH conditions.

上記の点に鑑みてなされた本発明の水酸基ラジカルを含む水の製造方法は、請求項１記載の通り、粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることを特徴とする。
また、請求項２記載の製造方法は、請求項１記載の製造方法において、微小気泡を発生させる水のｐＨが５以下であることを特徴とする。
また、請求項３記載の製造方法は、請求項１記載の製造方法において、水中に微小気泡を発生させた後、少なくとも１０秒間、微小気泡を水中で自然浮遊させることを特徴とする。
また、請求項４記載の製造方法は、請求項１記載の製造方法において、水中に微小気泡を発生させた後、微小気泡に圧力変動を加えることを特徴とする。
また、本発明の水中における水酸基ラジカルの生成方法は、請求項５記載の通り、粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることを特徴とする。
また、本発明の水酸基ラジカルを含む水は、請求項６記載の通り、粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることにより製造されてなることを特徴とする。
また、本発明の酸化対象物の処理方法は、請求項７記載の通り、請求項６記載の水酸基ラジカルを含む水の中に酸化対象物を存在せしめ、水中の水酸基ラジカルにより酸化することを特徴とする。 The method for producing water containing a hydroxyl radical of the present invention made in view of the above points is characterized in that, as described in claim 1, microbubbles containing ozone having a particle size of 50 μm or less are generated in water. .
The manufacturing method according to claim 2 is characterized in that, in the manufacturing method according to claim 1, the pH of water for generating microbubbles is 5 or less.
The manufacturing method according to claim 3 is characterized in that, in the manufacturing method according to claim 1, after generating microbubbles in water, the microbubbles are naturally suspended in water for at least 10 seconds.
The manufacturing method according to claim 4 is characterized in that, in the manufacturing method according to claim 1, after microbubbles are generated in water, pressure fluctuation is applied to the microbubbles.
Moreover, the method for producing hydroxyl radicals in water according to the present invention is characterized in that microbubbles containing ozone having a particle size of 50 μm or less are generated in water as described in claim 5.
In addition, the water containing a hydroxyl radical of the present invention is produced by generating microbubbles containing ozone having a particle size of 50 μm or less in water as described in claim 6.
Moreover, the method for treating an oxidation target of the present invention is characterized in that, as described in claim 7, the oxidation target is present in water containing the hydroxyl radical according to claim 6 and is oxidized by the hydroxyl radical in water. And

本発明によれば、ある程度の水深（例えば２０ｃｍ以上）を有する水槽内や天然水域において、粒径が５０μｍ以下のオゾンを含んだ微小気泡を発生させることで、気体溶解に伴う微小気泡の縮小の際、微小気泡の気液界面に高濃度に濃縮された電荷とオゾンが反応し、オゾンが促進的に分解されるので、酸性条件下でも大量の水酸基ラジカルを水中に生成させることができる。従って、本発明によれば、ｐＨ条件に依らず水酸基ラジカルを大量に含む水を製造することができる。本発明の方法によって製造される水酸基ラジカルを含む水は、酸化能力に優れるので、汚水処理などの水処理や有害物質の分解処理などに利用することができる。   According to the present invention, microbubbles containing ozone having a particle size of 50 μm or less are generated in a water tank or a natural water area having a certain depth (for example, 20 cm or more), thereby reducing microbubbles accompanying gas dissolution. At this time, the highly concentrated charge reacts with the ozone at the gas-liquid interface of the microbubbles and ozone is decomposed in an accelerated manner, so that a large amount of hydroxyl radicals can be generated in water even under acidic conditions. Therefore, according to the present invention, water containing a large amount of hydroxyl radicals can be produced regardless of pH conditions. Since the water containing a hydroxyl radical produced by the method of the present invention is excellent in oxidizing ability, it can be used for water treatment such as sewage treatment or decomposition treatment of harmful substances.

本発明において、粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させる方法は、例えば、オゾンを含んだ気液混合物を流動下において攪拌することにより行うことができる。この場合、回転子などを利用して半径が１０ｃｍ以下の渦流を強制的に生じせしめ、壁面などの障害物や相対速度の異なる流体にオゾンを含んだ気液混合物を打ち当てることにより、渦流中に獲得したオゾンを含んだ気体成分を渦の消失とともに分散させることで、所望のオゾンを含んだ微小気泡を大量に発生させることができる。また、２気圧以上の高圧下でオゾンを含んだ気体を水中に溶解させた後、これを大気圧に開放することにより生じたオゾンを含んだ溶解気体の過飽和条件からオゾンを含んだ気泡を発生させることができる。この場合、圧力の開放部位において、水流と障害物を利用して半径が１ｍｍ以下の渦を多数発生させ、渦流の中心域における水の分子揺動を起因として多量の気相の核（気泡核）を形成させるとともに、過飽和条件に伴ってこれらの気泡核に向かって水中のオゾンを含んだ気体成分を拡散させ、気泡核を成長させることにより、所望のオゾンを含んだ微小気泡を大量に発生させることができる。なお、これらの方法によって発生した気泡群の濃度は１００個／ｍＬ以上であり、１０００個／ｍＬよりも多い値となることも稀ではない（必要であれば特開２０００−５１１０７号公報や特開２００３−２６５９３８号公報などを参照のこと）。   In the present invention, the method of generating fine bubbles containing ozone having a particle size of 50 μm or less in water can be performed, for example, by stirring a gas-liquid mixture containing ozone under flow. In this case, a vortex with a radius of 10 cm or less is forcibly generated using a rotor or the like, and a gas-liquid mixture containing ozone is applied to an obstacle such as a wall or a fluid with different relative velocities. By dispersing the gas component containing ozone obtained in the step 1 together with the disappearance of the vortex, a large amount of microbubbles containing the desired ozone can be generated. In addition, ozone-containing bubbles are generated from the supersaturated condition of the dissolved gas containing ozone generated by dissolving ozone-containing gas in water under high pressure of 2 atmospheres or more and then releasing it to atmospheric pressure. Can be made. In this case, a large number of vortices with a radius of 1 mm or less are generated at the pressure release site using water flow and obstacles, and a large amount of gas phase nuclei (bubble nuclei due to water molecular fluctuations in the central region of the vortex flow. ) And a large amount of microbubbles containing the desired ozone are generated by diffusing gaseous components containing ozone in water toward these bubble nuclei along with supersaturation conditions and growing the bubble nuclei. Can be made. The concentration of the bubbles generated by these methods is 100 / mL or more, and it is not rare that the value is higher than 1000 / mL (see Japanese Patent Application Laid-Open No. 2000-51107 or specially if necessary). (See, eg, Japanese Unexamined Patent Publication No. 2003-265938).

オゾンを含んだ微小気泡を発生させる水のｐＨは特段限定されるものではない。しかしながら、汚水処理などの水処理を行う場合、水のｐＨは酸性（例えばｐＨ５以下）であることが望ましい場合がある。水のｐＨがアルカリ性であると処理中に過剰な沈殿物が生成することで処理条件が悪化する場合があるからである。このような場合、水のｐＨが酸性であると、沈殿物の生成が抑制されることで優れた処理効率を維持できる。なお、水のｐＨを酸性にするための調整は、必要に応じて有機酸および／または無機酸を加えることで行うことが望ましい。この場合、有機酸としては酢酸やシュウ酸やクエン酸などを使用することができる。無機酸としては塩酸や硫酸や硝酸などを使用することができる。   The pH of water that generates microbubbles containing ozone is not particularly limited. However, when water treatment such as sewage treatment is performed, it may be desirable that the pH of the water is acidic (for example, pH 5 or less). This is because if the pH of the water is alkaline, the treatment conditions may be deteriorated due to the formation of excessive precipitates during the treatment. In such a case, if the pH of the water is acidic, it is possible to maintain excellent treatment efficiency by suppressing the formation of precipitates. The adjustment for making the pH of the water acidic is desirably performed by adding an organic acid and / or an inorganic acid as necessary. In this case, acetic acid, oxalic acid, citric acid, or the like can be used as the organic acid. As the inorganic acid, hydrochloric acid, sulfuric acid, nitric acid or the like can be used.

水中にオゾンを含んだ微小気泡を発生させた後、少なくとも１０秒間、微小気泡を水中で自然浮遊させることが望ましい。微小気泡を球形を保ちながら縮小させることで、気泡の分裂に伴う表面積の増加を防止することにより、微小気泡の気液界面に電荷をより高濃度に濃縮させることができるからである。また、流動や超音波によって、微小気泡に例えば絶対値として０．１ｋＰａ以上の圧力変動を加えることにより、微小気泡の縮小速度を高めることで、微小気泡の気液界面に電荷をより高濃度に濃縮させることができる。これらの方法により、電荷とオゾンをより効率的に反応させることができるので、オゾンの促進酸化によって水酸基ラジカルをより効率的に生成させることができる。   After generating microbubbles containing ozone in water, it is desirable that the microbubbles naturally float in water for at least 10 seconds. This is because by reducing the size of the microbubbles while maintaining a spherical shape, it is possible to concentrate the charge at a higher concentration at the gas-liquid interface of the microbubbles by preventing an increase in the surface area associated with the splitting of the bubbles. Also, by applying pressure fluctuations of 0.1 kPa or more, for example, as absolute values to the microbubbles by flow or ultrasonic waves, increasing the reduction speed of the microbubbles, thereby increasing the charge at the gas-liquid interface of the microbubbles. It can be concentrated. By these methods, the charge and ozone can be reacted more efficiently, so that hydroxyl radicals can be generated more efficiently by the accelerated oxidation of ozone.

以下、本発明を実施例によって詳細に説明するが、本発明は以下の記載に限定して解釈されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is limited to the following description and is not interpreted.

実施例１：
例えば、特開２００３−２６５９３８号公報に記載の方法に従って、４気圧の高圧下で、塩酸でｐＨを２に調整され、かつ、スピントラップ剤であるＤＭＰＯ（５，５−ジメチル−１−ピロリン−Ｎ−オキシド）を約５ｍｇ／Ｌの濃度で含有する水中にオゾンを溶解させた後、これを大気圧に開放することにより生じた溶解オゾンの過飽和条件から粒径分布が１μｍ〜５０μｍのオゾンを含む微小気泡を水中に発生させた。１０秒以上、微小気泡を水中で自然浮遊させた後、水中に含まれる反応活性種を電子スピン共鳴法（ＥＳＲ）により測定した結果（スペクトル）を図１に示す。図１から明らかなように、このスペクトルからは、水酸基ラジカルに特徴的な１：２：２：１の大きさを示す４個のピークが認められ、本発明によれば、ｐＨ２という強酸性条件下でもオゾンの促進酸化によって水酸基ラジカルを水中に生成させることができることがわかった。なお、オゾンを含む微小気泡を水中に連続的に発生させてから１０秒以上、微小気泡を水中で自然浮遊させた後、水中に含まれる反応活性種をＥＳＲにより測定した場合、水酸基ラジカルに特徴的なピークは認められなかった。これはＤＭＰＯ自体が水酸基ラジカルの酸化能力により不活化されるほど水酸基ラジカルが大量に生成したことによるものと考えられた。 Example 1:
For example, according to the method described in JP-A-2003-265938, DMPO (5,5-dimethyl-1-pyrroline-), which is adjusted to pH 2 with hydrochloric acid under a high pressure of 4 atm, and is a spin trapping agent. After dissolving ozone in water containing N-oxide) at a concentration of about 5 mg / L, ozone having a particle size distribution of 1 μm to 50 μm is obtained from the supersaturated condition of dissolved ozone generated by releasing the ozone to atmospheric pressure. Contained microbubbles were generated in the water. FIG. 1 shows a result (spectrum) obtained by allowing microbubbles to naturally float in water for 10 seconds or more and then measuring reactive species contained in water by electron spin resonance (ESR). As is clear from FIG. 1, four peaks having a size of 1: 2: 2: 1 characteristic of the hydroxyl radical are recognized from this spectrum. According to the present invention, a strongly acidic condition of pH 2 is observed. It was found that hydroxyl radicals can be generated in water by accelerated oxidation of ozone. In addition, when microbubbles containing ozone are continuously generated in water for 10 seconds or more, after the microbubbles are naturally suspended in water, the reactive species contained in water are measured by ESR. No typical peak was observed. This was thought to be due to the large amount of hydroxyl radicals generated so that DMPO itself was inactivated by the oxidizing ability of hydroxyl radicals.

実施例２：
自体公知の微小気泡発生装置（必要であれば特開２００３−２６５９３８号公報を参照のこと）を使用して粒径分布が１μｍ〜５０μｍのオゾンを含む微小気泡を水中に連続的に発生させ、これを繊維工場で発生したポリビニルアルコール（ＰＶＡ）を含む排水を満たした３０Ｌの反応容器に連続的に供給し、排水中に含まれる全有機炭素量（ＴＯＣ）の変化を経時的に分析した。なお、反応容器に供給された水中に発生させたオゾンを含む微小気泡は、その５０％以上が最低でも１０秒間はポンプに再吸入されることなく反応容器内で自然浮遊するようにした。結果を図２に示す。図２から明らかなように、排水中に含まれるＴＯＣは時間の経過とともに減少し、ＰＶＡが効率的に分解されたことがわかった。ＰＶＡはオゾンで分解されないにもかかわらずこのような結果が得られたのは、水中に生成した水酸基ラジカルの優れた酸化能力によるものと考えられた。 Example 2:
Using a microbubble generator known per se (see Japanese Patent Application Laid-Open No. 2003-265938 if necessary), microbubbles containing ozone having a particle size distribution of 1 μm to 50 μm are continuously generated in water, This was continuously supplied to a 30 L reaction vessel filled with wastewater containing polyvinyl alcohol (PVA) generated in a textile factory, and the change in the total organic carbon content (TOC) contained in the wastewater was analyzed over time. Note that 50% or more of the microbubbles containing ozone generated in the water supplied to the reaction vessel were allowed to naturally float in the reaction vessel without being re-inhaled by the pump for at least 10 seconds. The results are shown in FIG. As is clear from FIG. 2, it was found that the TOC contained in the waste water decreased with the passage of time, and PVA was efficiently decomposed. Even though PVA was not decomposed by ozone, such a result was considered to be due to the excellent oxidizing ability of hydroxyl radicals generated in water.

実施例３：
水中に発生させたオゾンを含む微小気泡に超音波によって絶対値として０．１ｋＰａ以上の圧力変動を加えた後、これをＰＶＡを含む排水を満たした反応容器に供給すること以外は実施例２と同様の実験を行うことで、実施例２と同様の結果を得た。 Example 3:
Example 2 except that a microbubble containing ozone generated in water is subjected to a pressure fluctuation of 0.1 kPa or more as an absolute value by ultrasonic waves, and then supplied to a reaction vessel filled with waste water containing PVA. By performing the same experiment, the same result as in Example 2 was obtained.

本発明は、ｐＨ条件に依らずオゾンの促進酸化によって簡易かつ効率的に水酸基ラジカルを大量に含む水を製造する方法を提供することができる点において産業上の利用可能性を有する。   The present invention has industrial applicability in that it can provide a method for producing water containing a large amount of hydroxyl radicals simply and efficiently by accelerated oxidation of ozone regardless of pH conditions.

実施例１において生成させた反応活性種としての水酸基ラジカルのＥＳＲスペクトルである。2 is an ESR spectrum of a hydroxyl radical as a reactive species generated in Example 1. FIG. 実施例２におけるＴＯＣの経時的変化を示すグラフである。6 is a graph showing changes in TOC over time in Example 2.

Claims (7)

粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることを特徴とする水酸基ラジカルを含む水の製造方法。   A method for producing water containing hydroxyl radicals, wherein microbubbles containing ozone having a particle size of 50 μm or less are generated in water. 微小気泡を発生させる水のｐＨが５以下であることを特徴とする請求項１記載の製造方法。   The production method according to claim 1, wherein the pH of water for generating microbubbles is 5 or less. 水中に微小気泡を発生させた後、少なくとも１０秒間、微小気泡を水中で自然浮遊させることを特徴とする請求項１記載の製造方法。   2. The production method according to claim 1, wherein the microbubbles are naturally suspended in water for at least 10 seconds after the microbubbles are generated in the water. 水中に微小気泡を発生させた後、微小気泡に圧力変動を加えることを特徴とする請求項１記載の製造方法。   2. The production method according to claim 1, wherein after the generation of microbubbles in water, pressure fluctuation is applied to the microbubbles. 粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることを特徴とする水中における水酸基ラジカルの生成方法。   A method for producing hydroxyl radicals in water, wherein microbubbles containing ozone having a particle size of 50 μm or less are generated in water. 粒径が５０μｍ以下のオゾンを含んだ微小気泡を水中に発生させることにより製造されてなることを特徴とする水酸基ラジカルを含む水。   Water containing hydroxyl radicals, characterized by being produced by generating microbubbles containing ozone having a particle size of 50 μm or less in water. 請求項６記載の水酸基ラジカルを含む水の中に酸化対象物を存在せしめ、水中の水酸基ラジカルにより酸化することを特徴とする酸化対象物の処理方法。   A method for treating an object to be oxidized, which comprises oxidizing an object to be oxidized in water containing a hydroxyl radical according to claim 6 and oxidizing it with a hydroxyl radical in water.
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