JP2003003152A - Method for producing oxidation decomposable gas of organic substance - Google Patents
Method for producing oxidation decomposable gas of organic substanceInfo
- Publication number
- JP2003003152A JP2003003152A JP2001192680A JP2001192680A JP2003003152A JP 2003003152 A JP2003003152 A JP 2003003152A JP 2001192680 A JP2001192680 A JP 2001192680A JP 2001192680 A JP2001192680 A JP 2001192680A JP 2003003152 A JP2003003152 A JP 2003003152A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- ozone
- hydrogen peroxide
- ultraviolet rays
- organic substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title abstract description 10
- 230000003647 oxidation Effects 0.000 title abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 49
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101000650817 Homo sapiens Semaphorin-4D Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 102100027744 Semaphorin-4D Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、水や土壌などを
殺菌または淨化する場合などに用いられる有機物の酸化
分解性ガスの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oxidatively decomposable gas of an organic substance used for sterilizing or sterilizing water or soil.
【０００２】[0002]
【従来の技術】一般に、殺菌性などの効果が期待できる
有機物酸化分解性のある気体の代表例としては、オゾン
が知られている。オゾンは、分子式Ｏ3で表わされる酸
素の同素体であって、空気にも希薄なガス濃度で混じっ
ており、例えば０．０１〜０．１ｐｐｍ含有されている
と生臭い刺激臭を感じさせるものである。2. Description of the Related Art Generally, ozone is known as a typical example of a gas having an oxidative decomposable property for organic substances, which is expected to have effects such as sterilization. Ozone is an allotrope of oxygen represented by the molecular formula O 3 , and is mixed with air at a dilute gas concentration. For example, when it is contained in an amount of 0.01 to 0.1 ppm, it gives off a pungent odor. .
【０００３】オゾンは、酸化還元電位（酸化条件下）で
２．０７eVという酸化力があり、また標準生成自由エネ
ルギーが高く、全ての温度で酸素へ分解する物性を示
す。このようなオゾンが酸化剤として作用する反応とし
ては、生成物として酸素を生ずる反応がある他、有機オ
ゾン化物を形成するように３個の酸素原子が全て反応し
て最終生成物に化合する反応もある。Ozone has an oxidizing power of 2.07 eV under a redox potential (under oxidizing conditions), has a high standard free energy of formation, and exhibits physical properties of being decomposed into oxygen at all temperatures. As a reaction in which ozone acts as an oxidant, there is a reaction in which oxygen is generated as a product, and a reaction in which all three oxygen atoms are reacted to form an organic ozonide and combined into a final product. There is also.
【０００４】また、オゾンは、水中で分解すると約半分
がヒドロキシラジカル（以下、ＨＯラジカルと略記す
る。）に転化し、このラジカルは酸化還元電位（酸化条
件下）で２．８５eVという強い酸化力があり、水素引き
抜き反応、二重結合への付加反応または電子移動反応を
起こして有機物と酸化反応をする。When ozone is decomposed in water, about half of it is converted into hydroxy radicals (hereinafter abbreviated as HO radicals), and the radicals have a strong oxidizing power of 2.85 eV at a redox potential (under oxidizing conditions). There is a hydrogen abstraction reaction, an addition reaction to a double bond, or an electron transfer reaction to cause an oxidation reaction with an organic substance.
【０００５】例えば、オゾンおよびＨＯラジカルが微生
物の細胞表層に接すると、その蛋白質または脂質を酸化
して、細胞は破壊されまたは酵素活性を失い、細菌など
の微生物であれば死に至ると考えられる。For example, it is considered that when ozone and HO radicals come into contact with the cell surface of a microorganism, the protein or lipid is oxidized and the cell is destroyed or loses its enzymatic activity.
【０００６】このようなオゾンおよびＨＯラジカルの殺
菌力、すなわち有機物（微生物などを含めていう。）に
対する分解力を利用する浄化・殺菌処理の態様として、
廃水処理方法が良く知られ、特に促進酸化処理方法と呼
ばれているものがある。[0006] As a mode of purification / sterilization treatment utilizing the sterilizing power of ozone and HO radicals, that is, the decomposing power for organic substances (including microorganisms).
Wastewater treatment methods are well known, and in particular, there is one called an accelerated oxidation treatment method.
【０００７】この処理方法は、廃水などにオゾンを注入
した後、紫外線を照射し、次いで過酸化水素水を添加す
るか、またはオゾン注入後に過酸化水素水を添加し、さ
らに紫外線を照射して、オゾンの酸化力ばかりでなくＨ
Ｏラジカルを発生させる方法である。This treatment method involves injecting ozone into waste water and then irradiating it with ultraviolet rays and then adding hydrogen peroxide solution, or adding ozone solution and then adding hydrogen peroxide solution and further irradiating with ultraviolet rays. , Not only the oxidizing power of ozone, but also H
This is a method of generating O radicals.
【０００８】例えば図２に示す排水処理装置は、促進酸
化処理方法を利用したものであり、バルブ２０を開閉し
て有機物を含む被処理水を導入可能な容器２１を設け、
この容器２１の中央部に上下方向に延びる仕切り壁２２
を形成し、仕切られた一室にはオゾンガスを散気する散
気管２３を配置すると共に、他の一室には耐水性の紫外
線電球２４を電源に接続して設け、散気によって上昇す
る水流にはオゾンガスを混合溶解し、このオゾン溶解水
を循環させる下降水流中に紫外線を照射して、水中にＨ
Ｏラジカルを発生させ、循環する排水中の有機物に対し
て繰り返し促進酸化処理を行なう装置である。また、バ
ルブ２５には適宜に過酸化水素水を導入して紫外線を吸
収した過酸化水素水からもＨＯラジカルを発生させるよ
うにしている。For example, the waste water treatment apparatus shown in FIG. 2 uses the accelerated oxidation treatment method, and a valve 21 is opened and closed to provide a container 21 into which water to be treated containing organic matter can be introduced.
A partition wall 22 extending in the vertical direction is provided at the center of the container 21.
A diffusing tube 23 for diffusing ozone gas is arranged in one partitioned room, and a water resistant ultraviolet light bulb 24 is connected to a power source in the other room to provide a water flow rising by diffusing. Ozone gas is mixed and dissolved in the water, and ultraviolet rays are radiated into the descending water flow that circulates the ozone-dissolved water, so that H
This is a device that generates O radicals and repeatedly accelerates and oxidizes organic substances in circulating waste water. Further, hydrogen peroxide water is appropriately introduced into the valve 25 so that HO radicals are also generated from the hydrogen peroxide water that has absorbed the ultraviolet rays.
【０００９】[0009]
【発明が解決しようとする課題】しかし、上記した従来
の促進酸化処理方法では、オゾンガスを水中に散気（曝
気）する段階で、水に対するオゾンの溶解度が低いため
に、ＨＯラジカルの生成効率が低く、これが処理速度を
規制するという問題点がある。However, in the above-mentioned conventional accelerated oxidation treatment method, since the solubility of ozone in water is low at the stage of aeration (aeration) of ozone gas, the efficiency of HO radical generation is low. It is low, which limits the processing speed.
【００１０】また、ＨＯラジカルは、例えば微量濃度の
環境ホルモンなどのように、オゾンでは充分に酸化分解
できないような汚染物質をも完全に分解できる好ましい
酸化剤であるが、ＨＯラジカルを水中以外で簡単に発生
させる方法がなく、それゆえ水槽を使用せずに簡易な設
備でＨＯラジカルを製造する方法が要望されていた。The HO radical is a preferable oxidant capable of completely decomposing pollutants that cannot be sufficiently oxidatively decomposed by ozone, such as environmental hormones in a trace amount. There is no method for easy generation, and therefore, a method for producing HO radicals with simple equipment without using a water tank has been desired.
【００１１】そこで、本願の発明の課題は、上記した問
題点を解決して、ＨＯラジカルの生成効率が高く、ＨＯ
ラジカルの殺菌力、すなわち有機物や微生物に対する分
解力を充分に利用できる有機物の酸化分解性ガスを製造
し、また製造工程を比較的簡易にして製造効率を高める
ことである。Therefore, an object of the invention of the present application is to solve the above-mentioned problems and to improve the production efficiency of HO radicals.
The purpose is to produce an oxidatively decomposable gas of an organic substance that can fully utilize the sterilizing power of radicals, that is, the decomposing power for organic substances and microorganisms, and to relatively simplify the manufacturing process to enhance the manufacturing efficiency.
【００１２】[0012]
【課題を解決するための手段】上記の課題を解決するた
め、本願の有機物の酸化分解性ガスの製造方法に係る発
明においては、オゾンガスに霧状化した過酸化水素水を
混合し、この気液混合系に紫外線を照射してヒドロキシ
ラジカルを生成する製造方法としたのである。In order to solve the above-mentioned problems, in the invention relating to the method for producing an oxidative-decomposable gas of an organic substance of the present application, ozone gas is mixed with atomized hydrogen peroxide water, and this gas is mixed. The production method was to irradiate the liquid mixture system with ultraviolet rays to generate hydroxy radicals.
【００１３】オゾンに対して水中で紫外線を照射する
と、以下のようなオゾン酸化反応により、ＨＯラジカル
（・ＯＨ）が生成する。When ozone is irradiated with ultraviolet rays in water, HO radicals (.OH) are generated by the following ozone oxidation reaction.
【００１４】以下のは、オゾンから直接にＨＯラジ
カルが生成する反応を示し、、は、オゾンから過酸
化水素の生成を経由してＨＯラジカルが生成する反応を
示している。
Ｏ3 →Ｏ2＋Ｏ（1Ｄ）
Ｏ（1Ｄ）＋Ｈ2Ｏ→２・ＯＨ
Ｏ3 ＋Ｈ2Ｏ→Ｏ2＋Ｈ2Ｏ2
Ｈ2Ｏ2→２・ＯＨ The following shows the reaction in which HO radicals are directly produced from ozone, and the above is the reaction in which HO radicals are produced from ozone through the production of hydrogen peroxide. O 3 → O 2 + O ( 1 D) O ( 1 D) + H 2 O → 2 · OH O 3 + H 2 O → O 2 + H 2 O 2 H 2 O 2 → 2 · OH
【００１５】また、過酸化水素共存下でのオゾン酸化に
より、反応が起こり、・ＯＨ（ヒドロキシラジカル）
が生成される。この反応をより多段階に分けてみると、
第１段階としては、（ａ）式に示されるような過酸化水
素の解離が必要であり、次いでこの反応で生成したＨＯ
2 -が（ｂ）に示されるようにオゾンと反応し、・ＯＨが
生成される。
Ｏ3＋Ｈ2Ｏ2→・ＯＨ＋ＨＯ2＋Ｏ2
Ｈ2Ｏ2＝ＨＯ2 -＋Ｈ+ （ａ）
Ｏ3＋ＨＯ2 -→・ＯＨ＋Ｏ2 -＋Ｏ2 （ｂ）Further, a reaction occurs by ozone oxidation in the presence of hydrogen peroxide, resulting in .OH (hydroxy radical).
Is generated. If you divide this reaction into multiple stages,
As the first step, dissociation of hydrogen peroxide as shown in the formula (a) is required, and then the HO produced in this reaction is
2 - reacts with the ozone, as shown in (b), · OH is generated. O 3 + H 2 O 2 → · OH + HO 2 + O 2 H 2 O 2 = HO 2 − + H + (a) O 3 + HO 2 − → · OH + O 2 − + O 2 (b)
【００１６】上記の製造方法は、オゾンガスと霧状の過
酸化水素水を混合した気液混合系であるから、両物質の
接触面積が広く、接触効率が高くなる。そのため、紫外
線もしくは超音波または両者併用したエネルギー波を吸
収したオゾンが分解し、このとき生成した酸素原子が、
効率よく過酸化水素水と反応し、多量のＨＯラジカルを
発生させる。Since the above manufacturing method is a gas-liquid mixing system in which ozone gas and atomized hydrogen peroxide solution are mixed, the contact area of both substances is wide and the contact efficiency is high. Therefore, ozone that absorbs ultraviolet rays or ultrasonic waves or energy waves used in combination with both decomposes, and the oxygen atoms generated at this time are
Efficiently reacts with hydrogen peroxide water to generate a large amount of HO radicals.
【００１７】また、上記の製造方法において、紫外線に
代えて超音波を照射する有機物の酸化分解性ガスの製造
方法とすることもできる。Further, in the above manufacturing method, a method of manufacturing an oxidatively decomposable gas of an organic substance in which ultrasonic waves are irradiated instead of ultraviolet rays may be used.
【００１８】この方法では、水溶液中にキャビテーショ
ンが起こるような超音波を照射する。このようにする
と、水中に微小な空洞（キャビティ）が生成し、このキ
ャビティは、圧縮時につぶれて崩壊するが、液体分子は
極めて大きな加速度で衝突するために局所的に超高温高
圧の状態が衝撃的に発生する。このため、オゾンの自己
分解や水中遊離基の活性が増大し、ＨＯラジカルや過酸
化水素が生成されやすくなる。In this method, ultrasonic waves are applied so that cavitation occurs in the aqueous solution. By doing this, a minute cavity is created in water, and this cavity collapses and collapses during compression, but since liquid molecules collide with extremely large acceleration, the state of ultra-high temperature and high pressure is locally impacted. Occurring in a sudden way. Therefore, the self-decomposition of ozone and the activity of free radicals in water are increased, and HO radicals and hydrogen peroxide are easily generated.
【００１９】本願の発明においては、これらの方法を総
合し、オゾンガスに霧状化した過酸化水素水を混合し、
この気液混合系に紫外線および超音波を照射してＨＯラ
ジカルを生成することからなる有機物の酸化分解性ガス
の製造方法とすることが、可及的に多量のＨＯラジカル
を発生させるために好ましい。In the invention of the present application, these methods are integrated, ozone gas is mixed with atomized hydrogen peroxide solution,
It is preferable to use a method for producing an oxidatively decomposable gas of an organic matter, which comprises irradiating this gas-liquid mixture system with ultraviolet rays and ultrasonic waves to generate HO radicals, in order to generate as much HO radicals as possible. .
【００２０】[0020]
【発明の実施の形態】以下に、この発明の有機物の酸化
分解性ガスの製造方法を添付図面に基づいて説明する。BEST MODE FOR CARRYING OUT THE INVENTION A method for producing an oxidatively decomposable gas of an organic substance according to the present invention will be described below with reference to the accompanying drawings.
【００２１】図１に示す装置は、オゾンガスに霧状化し
た過酸化水素水を混合し、この気液混合系に紫外線を照
射してガス中にヒドロキシラジカルを生成する有機物の
酸化分解性ガスの製造方法に用いる装置である。The apparatus shown in FIG. 1 mixes ozone gas with atomized hydrogen peroxide water, and irradiates the gas-liquid mixing system with ultraviolet rays to generate an organic radical oxidative-decomposable gas that produces hydroxy radicals in the gas. This is an apparatus used in the manufacturing method.
【００２２】すなわち、この装置は、酸素ボンベ１から
原料の酸素を減圧弁２を介してオゾナイザー３に供給
し、このオゾナイザー３で生成したオゾンガスが、管４
を介して噴霧器５に送られるようにしている。噴霧器５
の容器６には所定濃度の過酸化水素水７を入れ、これを
噴霧器５の管で吸い上げると共にその先端のノズルから
噴霧して過酸化水素水の微粒子含有のオゾンガス（気液
混合系ガス）をガラス管製の反応容器８内に導入する。
そして、気液混合系ガスを導入した反応容器８に接近さ
せて紫外線電球９を設けて紫外線を照射し、紫外線照射
後の気液混合系ガスを分解処理容器１０に導入し、分解
処理容器１０には被処理用物質を導入する管１１を逆止
弁１２を介して接合すると共に、処理後に残留するオゾ
ンを除去するためのオゾン分解器１３（活性炭やマンガ
ン系の触媒を充填したもの）を経由したガスを大気に放
出するようにした有機物の酸化分解性ガスの製造および
処理装置である。That is, in this apparatus, the raw material oxygen is supplied from the oxygen cylinder 1 to the ozonizer 3 through the pressure reducing valve 2, and the ozone gas generated by the ozonizer 3 is supplied to the pipe 4
It is sent to the sprayer 5 via the. Atomizer 5
A hydrogen peroxide solution 7 having a predetermined concentration is put in the container 6 and is sucked up by the pipe of the sprayer 5 and is sprayed from the nozzle at the tip of the container to spray the ozone gas (gas liquid mixture gas) containing fine particles of the hydrogen peroxide solution. It is introduced into the reaction vessel 8 made of a glass tube.
Then, the ultraviolet light bulb 9 is provided in the vicinity of the reaction container 8 into which the gas-liquid mixed system gas has been introduced to irradiate the ultraviolet rays, and the gas-liquid mixed system gas after the irradiation of the ultraviolet rays is introduced into the decomposition treatment container 10 and A pipe 11 for introducing the substance to be treated is joined via a check valve 12, and an ozone decomposer 13 (filled with activated carbon or manganese-based catalyst) for removing ozone remaining after the treatment is connected to the pipe 11. It is an apparatus for producing and treating an oxidatively decomposable gas of an organic substance, in which the gas passed through is released to the atmosphere.
【００２３】この発明に用いる過酸化水素水は、特にそ
の濃度を限定して使用するものではないが、ＨＯラジカ
ルの生成反応経路からみて所定濃度の水溶液であること
が好ましい。高濃度な過酸化水素水は、ＨＯラジカルを
消滅させる反応を起こす場合がある。実施形態では、１
０重量％濃度の過酸化水素水溶液を用いて好ましい結果
を得ており、好ましい過酸化水素水の濃度範囲を例示す
れば１〜２０重量％であり、より好ましくは１〜１０重
量％である。Although the hydrogen peroxide solution used in the present invention is not particularly limited in its concentration, it is preferably an aqueous solution having a predetermined concentration in view of the HO radical generation reaction route. A high-concentration hydrogen peroxide solution may cause a reaction that extinguishes HO radicals. In the embodiment, 1
A preferable result has been obtained by using a hydrogen peroxide aqueous solution having a concentration of 0% by weight, and the preferable concentration range of the hydrogen peroxide solution is, for example, 1 to 20% by weight, and more preferably 1 to 10% by weight.
【００２４】過酸化水素水を噴霧するには、周知の噴霧
装置を用いて過酸化水素水をオゾン含有の気流中に吸い
上げ、ノズルから微細粒として噴霧分散させる方式と、
超音波振動を利用して過酸化水素水を微細粒とし、これ
をオゾン含有の雰囲気中に分散させる方式などがあり、
いずれの方式でも採用することができる。In order to spray the hydrogen peroxide solution, there is used a method of sucking the hydrogen peroxide solution into an ozone-containing air stream using a well-known spraying device and spraying it as fine particles through a nozzle,
There is a method that uses ultrasonic vibration to make hydrogen peroxide water into fine particles and disperse this in an atmosphere containing ozone.
Either method can be adopted.
【００２５】この発明に用いる紫外線は、オゾンが吸収
する波長の光のうち、通常、紫外域とされる波長２２０
〜３００ｎｍの波長域の紫外線を含むものであれば良
い。因みに、オゾンの紫外吸収スペクトルからみて、吸
収ピークは２５５ｎｍ付近である。また、真空紫外線と
呼ばれる波長２００ｎｍ以下の紫外線は、直接水分子を
分解してＨＯラジカルを生成する性質を有する。そのた
め、このような真空紫外線を含む紫外線を採用すること
も好ましいことである。低圧水銀ランプ（ＶＵＶラン
プ）を用いると、主波長に１８５ｎｍ（真空紫外線）と
２５４ｎｍ（近紫外線）をもち、この発明に好適な紫外
線が得られる。The ultraviolet rays used in the present invention have a wavelength of 220, which is usually in the ultraviolet region, of the light of the wavelength absorbed by ozone.
Any material containing ultraviolet rays in the wavelength range of up to 300 nm may be used. Incidentally, the absorption peak is around 255 nm as seen from the ultraviolet absorption spectrum of ozone. Further, ultraviolet rays having a wavelength of 200 nm or less called vacuum ultraviolet rays have a property of directly decomposing water molecules to generate HO radicals. Therefore, it is also preferable to adopt ultraviolet rays including such vacuum ultraviolet rays. When a low-pressure mercury lamp (VUV lamp) is used, it has 185 nm (vacuum ultraviolet rays) and 254 nm (near ultraviolet rays) as main wavelengths, and ultraviolet rays suitable for the present invention can be obtained.
【００２６】製造された有機物の酸化分解性ガスは、非
常に酸化力の強いＨＯラジカルを多量に含むので、有機
物を炭酸イオンなどにまで、完全分解することが可能な
ものである。また、微量汚染物質を分解することにも有
効であり、その他に脱色、脱臭、殺菌効果もある有用性
の高いものになる。Since the produced oxidatively decomposable gas of organic matter contains a large amount of HO radicals having a very strong oxidizing power, it is possible to completely decompose organic matter into carbonate ions and the like. In addition, it is effective in decomposing trace contaminants, and in addition, it is highly useful because it has decolorizing, deodorizing, and bactericidal effects.
【００２７】[0027]
【実施例】図１に示した製造装置を用いて、以下の条件
で有機物の酸化分解性ガスを製造した。Example An oxidatively decomposable gas of an organic substance was produced under the following conditions using the production apparatus shown in FIG.
【００２８】すなわち、オゾナイザー（スイス国オゾニ
ア社製）３で生成したオゾン（濃度１４１ｇ／ｍ3）を
噴霧器５に供給し、容器６には１０重量％濃度の過酸化
水素水を１００ミリリットル収容し、この過酸化水素を
１５リットル／分のオゾンガスで噴霧しながらガラス管
（長さ３０ｃｍ）からなる反応容器８に一端から導入す
ると共に、この気液混合系に対して紫外線電球９（波長
２５４ｎｍ、１５ワット、東芝社製ブラックライト）で
紫外線を照射し、ＨＯラジカルを生成することによって
有機物の酸化分解性ガスを製造した。That is, ozone (concentration: 141 g / m 3 ) generated by an ozonizer (manufactured by Ozonia, Switzerland) 3 was supplied to a sprayer 5, and 100 ml of hydrogen peroxide solution having a concentration of 10% by weight was contained in a container 6. While spraying this hydrogen peroxide with 15 l / min of ozone gas, it was introduced from one end into a reaction vessel 8 consisting of a glass tube (length 30 cm), and an ultraviolet light bulb 9 (wavelength 254 nm, An oxidatively decomposable gas of an organic substance was produced by irradiating ultraviolet rays with a 15 watt, Toshiba Corporation black light) to generate HO radicals.
【００２９】得られた酸化分解性ガスの優れた物性を以
下の実験で確認した。すなわち、５リットル容のポリエ
チレン製袋にダイオキシンに汚染された土壌サンプル
（ダイオキシン濃度９７ｐｇ−ＴｅＱ/ｇ）３０ｇを入
れ、同袋内に前記のようにして得られた酸化分解性ガス
３．５リットルを入れて常温で１時間振とう攪拌し、再
度ダイオキシン濃度を計測したところ５０ｐｇ−ＴｅＱ
/ｇであり、４９％の分解率であった。The excellent physical properties of the obtained oxidatively decomposable gas were confirmed by the following experiments. That is, 30 g of a dioxin-contaminated soil sample (dioxin concentration 97 pg-TeQ / g) was placed in a polyethylene bag of 5 liters, and 3.5 liters of the oxidatively decomposable gas obtained as described above in the same bag. 50g-TeQ when the dioxin concentration was measured again after stirring and shaking at room temperature for 1 hour.
/ g, which was a decomposition rate of 49%.
【００３０】一方、比較のために、酸化分解性ガスに代
えてオゾン１４１ｇを含む空気（オゾンガス）を用いた
こと以外は全く同様にして、同じ汚染土壌のサンプルを
処理した。処理の前後でサンプルのダイオキシン濃度を
計測したところ、処理前：ダイオキシン濃度９７ｐｇ−
ＴｅＱ/ｇ、処理後：６９ｐｇ−ＴｅＱ/ｇであり、分解
率は２８％にとどまった。On the other hand, for comparison, the same contaminated soil sample was treated in exactly the same manner except that air containing 141 g of ozone (ozone gas) was used in place of the oxidatively decomposable gas. When the dioxin concentration of the sample was measured before and after the treatment, before treatment: dioxin concentration 97 pg-
TeQ / g, after treatment: 69 pg-TeQ / g, and the decomposition rate was 28%.
【００３１】以上の結果から、通常のオゾンガスでは、
充分に分解できない有機物の有害汚染物質であるダイオ
キシン類に対して、実施例の酸化分解性ガスは、効率よ
くこれを酸化分解していると認められた。From the above results, with normal ozone gas,
It was recognized that the oxidatively decomposable gas of the examples efficiently oxidatively decomposes dioxins, which are harmful pollutants of organic substances that cannot be sufficiently decomposed.
【００３２】[0032]
【発明の効果】この発明は、以上説明したように、オゾ
ンガスに霧状化した過酸化水素水を混合し、この気液混
合系に紫外線を照射する有機物の酸化分解性ガスの製造
方法としたので、ＨＯラジカルの生成効率が高く、酸化
力が強力なＨＯラジカルを多量に含み、有機物や微生物
に対する分解力を充分に利用できる有機物の酸化分解性
ガスを製造でき、またこれを比較的簡易な工程で効率よ
く製造できるという利点がある。As described above, the present invention provides a method for producing an oxidatively decomposable gas of an organic substance, which comprises mixing ozone gas with atomized hydrogen peroxide solution and irradiating the gas-liquid mixture system with ultraviolet rays. Therefore, it is possible to produce an oxidatively decomposable gas of an organic substance which has a high generation efficiency of HO radicals, contains a large amount of HO radicals having a strong oxidizing power, and can sufficiently utilize the decomposing power for organic substances and microorganisms. There is an advantage that the process can be efficiently manufactured.
【図１】実施形態の有機物の酸化分解性ガスの製造装置
の説明図FIG. 1 is an explanatory diagram of an apparatus for producing an oxidatively decomposable gas for organic substances according to an embodiment.
【図２】従来例の促進酸化処理法に用いる装置の断面図FIG. 2 is a sectional view of an apparatus used for a conventional accelerated oxidation treatment method.
１ 酸素ボンベ ２ 減圧弁 ３ オゾナイザー ４、１１ 管 ５ 噴霧器 ６ 容器 ７ 過酸化水素水 ８ 反応容器 ９、２４ 紫外線電球 １０ 分解処理容器 １２ 逆止弁 １３ オゾン分解器 ２０、２５ バルブ ２１ 容器 ２２ 仕切り壁 ２３ 散気管 1 oxygen cylinder 2 Pressure reducing valve 3 Ozonizer 4, 11 tubes 5 atomizer 6 containers 7 Hydrogen peroxide water 8 reaction vessels 9,24 UV bulb 10 Decomposition container 12 Check valve 13 Ozone decomposer 20, 25 valve 21 containers 22 partition walls 23 Air diffuser
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/50 Ｃ０２Ｆ 1/50 ５５０Ｈ ５６０ ５６０Ｃ (72)発明者 内田 弘 大阪市中央区安土町１丁目３番５号 株式 会社関西総合環境センター内 (72)発明者 野上 誠 大阪市北区中之島３丁目３番22号 関西電 力株式会社内 (72)発明者 上村 直洋 大阪市北区中之島３丁目３番22号 関西電 力株式会社内 Ｆターム(参考） 4H011 AA02 BB18 DA20 DD01 DD04Front page continuation (51) Int.Cl. 7 identification code FI theme code (reference) C02F 1/50 C02F 1/50 550H 560 560C (72) Inventor Hiroshi Uchida 1-3-5 Azuchi-cho, Chuo-ku, Osaka (72) Inventor Makoto Nogami 3-22 Nakanoshima, Kita-ku, Osaka City (72) Inventor Naohiro Uemura 3-22-2 Nakanoshima, Kita-ku, Osaka Kansai Kansai Electric power company F term (reference) 4H011 AA02 BB18 DA20 DD01 DD04
Claims (3)
混合し、この気液混合系に紫外線を照射してヒドロキシ
ラジカルを生成することからなる有機物の酸化分解性ガ
スの製造方法。1. A method for producing an oxidatively decomposable gas of an organic matter, which comprises mixing atomized hydrogen peroxide water with ozone gas and irradiating the gas-liquid mixing system with ultraviolet rays to generate hydroxy radicals.
１記載の有機物の酸化分解性ガスの製造方法。2. The method for producing an oxidatively decomposable gas for an organic matter according to claim 1, wherein ultrasonic waves are irradiated instead of ultraviolet rays.
混合し、この気液混合系に紫外線および超音波を照射し
てヒドロキシラジカルを生成することからなる有機物の
酸化分解性ガスの製造方法。3. A method for producing an oxidatively decomposable gas of an organic matter, which comprises mixing atomized hydrogen peroxide water with ozone gas and irradiating the gas-liquid mixing system with ultraviolet rays and ultrasonic waves to generate hydroxy radicals. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001192680A JP2003003152A (en) | 2001-06-26 | 2001-06-26 | Method for producing oxidation decomposable gas of organic substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001192680A JP2003003152A (en) | 2001-06-26 | 2001-06-26 | Method for producing oxidation decomposable gas of organic substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003003152A true JP2003003152A (en) | 2003-01-08 |
Family
ID=19031099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001192680A Pending JP2003003152A (en) | 2001-06-26 | 2001-06-26 | Method for producing oxidation decomposable gas of organic substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003003152A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014008440A (en) * | 2012-06-28 | 2014-01-20 | Koki:Kk | Method and apparatus for producing ozone-containing aqueous solution, and ozone-containing aqueous solution |
| CN113354141A (en) * | 2021-06-01 | 2021-09-07 | 广西北投环保水务集团有限公司 | Negative-pressure ozone-sludge-based activated carbon catalytic oxidation sewage treatment device and treatment process thereof |
| CN119349833A (en) * | 2024-12-26 | 2025-01-24 | 宁波元派医疗科技有限公司 | A device and method for preparing double electrolyzed water based on O3 and H2O2 in parallel |
-
2001
- 2001-06-26 JP JP2001192680A patent/JP2003003152A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014008440A (en) * | 2012-06-28 | 2014-01-20 | Koki:Kk | Method and apparatus for producing ozone-containing aqueous solution, and ozone-containing aqueous solution |
| CN113354141A (en) * | 2021-06-01 | 2021-09-07 | 广西北投环保水务集团有限公司 | Negative-pressure ozone-sludge-based activated carbon catalytic oxidation sewage treatment device and treatment process thereof |
| CN119349833A (en) * | 2024-12-26 | 2025-01-24 | 宁波元派医疗科技有限公司 | A device and method for preparing double electrolyzed water based on O3 and H2O2 in parallel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111829099B (en) | Device and method for sterilizing aerosol and degrading organic gas | |
| US8968576B2 (en) | Nebulizing treatment method | |
| JP2003190976A5 (en) | ||
| JP2003190976A (en) | Apparatus and method for treating wastewater | |
| CN212339512U (en) | Device for air aerosol disinfection and organic gas degradation | |
| JPH1057749A (en) | Air deodorizing method and air deodorizing device using ozone water | |
| JP3858326B2 (en) | Accelerated oxidation treatment equipment using ozone and photocatalyst | |
| CN106000080A (en) | Treatment method of organic waste gas | |
| CN103071165A (en) | A liquid sterilization and disinfection device | |
| JP3731257B2 (en) | Ozone water deodorization method and deodorization apparatus | |
| JP2003001237A (en) | Decomposition method of organic environmental pollutants | |
| JP3646509B2 (en) | Water treatment equipment using photocatalyst | |
| JP2003003152A (en) | Method for producing oxidation decomposable gas of organic substance | |
| JPS6377592A (en) | Method and apparatus for treatment by ozone | |
| KR100348413B1 (en) | Uv and ozone producing aop chamber and water-cleaning apparatus using same | |
| CN117902672B (en) | Intensified photocatalysis water treatment device | |
| JP2000279977A (en) | Fluid treatment method and fluid treatment device | |
| WO1994024043A1 (en) | Method and apparatus for ozone decomposition by stimulated emission of electromagnetic wave | |
| CN117945535A (en) | Novel advanced oxidation device | |
| JP2003210938A (en) | Exhaust gas purification equipment | |
| JPH11267670A (en) | Processing equipment using photocatalyst | |
| JP2004066208A (en) | Deodorizing/sterilizing device by combination of vacuum. ultrasonic wave, jet flow, and photooxidation | |
| KR102138176B1 (en) | Wastewater pre-processing system with OH reaction agitation tank | |
| KR20020088538A (en) | Water-cleaning apparatus and method using uv and ozone | |
| CN101137583A (en) | liquid handling method |