JP2007152185A - Process and apparatus for treating surfactant-containing water - Google Patents

Process and apparatus for treating surfactant-containing water Download PDF

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JP2007152185A
JP2007152185A JP2005348475A JP2005348475A JP2007152185A JP 2007152185 A JP2007152185 A JP 2007152185A JP 2005348475 A JP2005348475 A JP 2005348475A JP 2005348475 A JP2005348475 A JP 2005348475A JP 2007152185 A JP2007152185 A JP 2007152185A
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ozone
surfactant
containing water
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alkali
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JP4983011B2 (en
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Naoto Ichiyanagi
直人 一柳
Taeko Ushiyama
妙子 牛山
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Kurita Water Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4616—Power supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process and an apparatus for treating surfactant-containing water by which foaming by blowing-in of ozone-containing gas is suppressed and stable treatment can be carried out. <P>SOLUTION: The surfactant-containing water is introduced into a flow passage 5 and is made to flow in a direction from an entrance 51 to an exit 52 and ozone is added thereto at two or more positions along a stream of the surfactant-containing water. Addition amount of ozone is largest at a last stage ozone reaction facility 20 arranged at a position nearest the exit 52. When ozone is added at two places, for example at a preceding side ozone reaction facility 10 and the last stage ozone reaction facility 20, about 5 to 40 vol.% of total ozone addition amount is added at the preceding side ozone reaction facility 10 and residual ozone is added at the last stage ozone reaction facility 20. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、電子部品洗浄廃水等の界面活性剤含有水の処理方法および処理装置に関し、特に、オゾンガスによる界面活性剤含有水の処理方法および処理装置に関する。   The present invention relates to a method and apparatus for treating surfactant-containing water such as electronic component cleaning wastewater, and more particularly to a method and apparatus for treating surfactant-containing water with ozone gas.

従来、半導体製造工場や液晶等の表示装置製造工場では、製品の製造過程でウェハ等を洗浄する洗浄用水として不純物濃度が極めて少ない超純水が使用されている。しかし、超純水のみによる洗浄では、表面張力のためにウェハ等の微細な部分の洗浄が困難となる場合がある。そこで近年、超純水に界面活性剤やアルコール等の有機物を添加して表面張力を低下させてウェハ等を洗浄する方法が用いられるようになっている。   Conventionally, in semiconductor manufacturing factories and display device manufacturing factories such as liquid crystals, ultrapure water having an extremely low impurity concentration is used as cleaning water for cleaning wafers and the like in the manufacturing process of products. However, cleaning with only ultrapure water may make it difficult to clean fine portions such as wafers due to surface tension. Therefore, in recent years, a method of cleaning a wafer or the like by adding an organic substance such as a surfactant or alcohol to ultrapure water to lower the surface tension has been used.

このため、半導体製造過程等で排出される廃水には超純水に添加された界面活性剤が含まれる場合がある。こうした電子部品洗浄廃水等の界面活性剤含有水の処理方法としては、活性炭吸着法、泡沫分離法、化学的分解法、および生物処理法等が知られている。化学的分解法としては、界面活性剤含有水に紫外線を照射する紫外線照射法、オゾン等の酸化剤を添加する酸化剤添加法等がある。   For this reason, the waste water discharged | emitted in a semiconductor manufacturing process etc. may contain the surfactant added to the ultrapure water. Known methods for treating surfactant-containing water such as electronic component washing wastewater include activated carbon adsorption, foam separation, chemical decomposition, and biological treatment. Examples of the chemical decomposition method include an ultraviolet irradiation method of irradiating surfactant-containing water with ultraviolet rays, an oxidant addition method of adding an oxidizing agent such as ozone, and the like.

例えば、特許文献１には、界面活性剤含有水にオゾンを添加した後、水素を添加する界面活性剤含有水の処理方法が開示されている。特許文献１に開示された方法では、界面活性剤含有水にオゾンを添加して界面活性剤を酸化分解させる。次に、水素を添加することにより、処理水に残存するオゾン等の酸化剤を還元する。
特開２０００−２７１５７７号公報 For example, Patent Document 1 discloses a method for treating surfactant-containing water in which hydrogen is added after ozone is added to the surfactant-containing water. In the method disclosed in Patent Document 1, ozone is added to surfactant-containing water to oxidatively decompose the surfactant. Next, an oxidizing agent such as ozone remaining in the treated water is reduced by adding hydrogen.
JP 2000-271577 A

ところでオゾンの生成方法としては、空気または酸素を原料として放電を行うことによりオゾンを発生させる放電方式と、純水を電気分解してオゾンを発生させる電解方式とがある。電解方式では、オゾン濃度が２０質量％程度のオゾン水溶液が得られる等の理由で、特許文献１では電解方式により発生させたオゾンを用いることが好ましいとされている。しかし、電解方式で発生させることができるオゾンは１ｇ／ｈ程度にも満たず、電解方式では大量のオゾンを発生させることができない。   By the way, as a method for generating ozone, there are a discharge method in which ozone is generated by performing discharge using air or oxygen as a raw material, and an electrolysis method in which ozone is generated by electrolyzing pure water. In the electrolysis method, it is preferable to use ozone generated by the electrolysis method in Patent Document 1 because an ozone aqueous solution having an ozone concentration of about 20% by mass is obtained. However, the ozone that can be generated by the electrolysis method is less than about 1 g / h, and a large amount of ozone cannot be generated by the electrolysis method.

一方、放電方式によれば３００ｋｇ／ｈ程度ものオゾンを発生させることができる。このため、従来、大量の界面活性剤含有水をオゾンにより処理する場合、放電方式で発生させたオゾン含有ガスが用いられている。しかし、放電方式で発生させたオゾンを含むオゾン含有ガスのオゾン濃度は低い。例えば、空気を原料として発生させたオゾン含有ガスのオゾン濃度は４０ｇ／Ｎｍ３（２．７質量％）程度であり、酸素を原料として発生させたオゾン含有ガスでもオゾン濃度は１５０〜２００ｇ／Ｎｍ３（１０〜１３質量％）程度に留まる。 On the other hand, according to the discharge method, ozone of about 300 kg / h can be generated. For this reason, conventionally, when a large amount of surfactant-containing water is treated with ozone, an ozone-containing gas generated by a discharge method has been used. However, the ozone concentration of the ozone-containing gas containing ozone generated by the discharge method is low. For example, the ozone concentration of an ozone-containing gas generated using air as a raw material is about 40 g / Nm 3 (2.7% by mass), and the ozone concentration of an ozone-containing gas generated using oxygen as a raw material is 150 to 200 g / Nm. 3 (about 10-13 mass%).

したがって、界面活性剤含有水に含まれる界面活性剤等の有機物を酸化分解させるためには大量のオゾン含有ガスを界面活性剤含有水に吹き込む必要がある。例えば、界面活性剤含有水に含まれる全有機態炭素（ＴＯＣ）を分解するために必要なオゾン量をＴＯＣの８倍（質量比）とした場合、ＴＯＣ濃度が２０ｍｇ／Ｌの廃水処理に必要なオゾン量は１６０ｍｇ／Ｌとなる。この場合、濃度１５０ｍｇ／Ｌのオゾン含有ガスを使用しても、オゾンによる酸化分解を行う反応槽の気液比は１．０を超え、反応槽に大量のオゾン含有ガスを吹き込むことにより、激しい発泡が生じる。   Therefore, in order to oxidatively decompose organic substances such as surfactants contained in the surfactant-containing water, it is necessary to blow a large amount of ozone-containing gas into the surfactant-containing water. For example, when the amount of ozone required to decompose total organic carbon (TOC) contained in surfactant-containing water is 8 times (mass ratio) of TOC, it is necessary for wastewater treatment with a TOC concentration of 20 mg / L. The amount of ozone is 160 mg / L. In this case, even if an ozone-containing gas having a concentration of 150 mg / L is used, the gas-liquid ratio of the reaction tank that performs oxidative decomposition with ozone exceeds 1.0, and a large amount of ozone-containing gas is blown into the reaction tank. Foaming occurs.

特に、ＴＯＣ成分として非イオン性の界面活性剤を含む界面活性剤含有水を反応槽に導入し、反応槽の下部に設けた散気管からオゾン含有ガスを吹き込む場合、激しい発泡が生じる。この結果、反応槽の気液界面を安定させることができず、廃オゾン含有ガスを排出する廃オゾン管から泡が流出するといったトラブルが生じる。   In particular, when surfactant-containing water containing a nonionic surfactant as a TOC component is introduced into a reaction tank and ozone-containing gas is blown from an air diffuser provided at the bottom of the reaction tank, severe foaming occurs. As a result, the gas-liquid interface of the reaction tank cannot be stabilized, and troubles such as bubbles flowing out from the waste ozone pipe that discharges the waste ozone-containing gas occur.

本発明は上記課題に対し、発泡性の強い界面活性剤含有水のオゾン処理に際し、オゾン含有ガスの吹き込みによる発泡を抑制し、安定した処理を行うことができる界面活性剤含有水の処理方法および処理装置を提供することを目的とする。   In the present invention, in the ozone treatment of highly foamable surfactant-containing water, the surfactant-containing water treatment method capable of suppressing foaming due to blowing of ozone-containing gas and performing stable treatment, and An object is to provide a processing apparatus.

具体的には、本発明は以下を提供する。   Specifically, the present invention provides the following.

（１） 界面活性剤含有水にオゾンを添加する界面活性剤含有水の処理方法であって、 前記界面活性剤含有水を、入口および出口を備える流路に流して前記流路に沿う複数の位置で前記オゾンを前記界面活性剤含有水に添加し、前記出口に最も近い位置において最も多くのオゾンを添加する界面活性剤含有水の処理方法。   (1) A method for treating surfactant-containing water in which ozone is added to surfactant-containing water, wherein the surfactant-containing water is allowed to flow through a flow path having an inlet and an outlet, and a plurality of the water is provided along the flow path. A method for treating surfactant-containing water, wherein the ozone is added to the surfactant-containing water at a position and the most ozone is added at a position closest to the outlet.

（２） 前記オゾンを添加する前に、前記界面活性剤含有水にアルカリを添加する（１）に記載の界面活性剤含有水の処理方法。   (2) The method for treating surfactant-containing water according to (1), wherein an alkali is added to the surfactant-containing water before the ozone is added.

（３） 前記オゾンを添加する前に、前記界面活性剤含有水にアルカリと過酸化水素とを添加する（１）に記載の界面活性剤含有水の処理方法。   (3) The method for treating surfactant-containing water according to (1), wherein alkali and hydrogen peroxide are added to the surfactant-containing water before adding the ozone.

（４） 入口から出口に向かって界面活性剤含有水が流れる流路を含む界面活性剤含有水の処理装置であって、 前記流路に沿って設けられ、前記流路を流れる前記界面活性剤含有水に前記オゾンを添加して界面活性剤を酸化分解する複数のオゾン反応設備をさらに含み、 前記複数のオゾン反応設備のうち、前記出口に最も近い位置に設けられた最終段オゾン反応設備は、他のオゾン反応設備より多くの前記オゾンを前記界面活性剤含有水に添加する界面活性剤含有水の処理装置。   (4) A surfactant-containing water treatment apparatus including a flow path through which surfactant-containing water flows from an inlet toward an outlet, the surfactant provided along the flow path and flowing through the flow path It further includes a plurality of ozone reaction facilities that oxidatively decompose the surfactant by adding the ozone to the contained water, and among the plurality of ozone reaction facilities, the final stage ozone reaction facility provided at a position closest to the outlet is An apparatus for treating surfactant-containing water that adds more ozone to the surfactant-containing water than other ozone reaction equipment.

（５） 前記最終段オゾン反応設備は、オゾン供給手段を有する気液接触型の反応槽であり、 前記他のオゾン反応設備として、前記流路に前記オゾンを供給する流路内オゾン供給手段と、前記流路内の界面活性剤含有水を攪拌する攪拌手段と、を有する攪拌反応設備を含む（４）に記載の界面活性剤含有水の処理装置。   (5) The final stage ozone reaction facility is a gas-liquid contact type reaction tank having an ozone supply means, and as the other ozone reaction facility, an in-flow path ozone supply means for supplying the ozone to the flow path; The surfactant-containing water treatment apparatus according to (4), further comprising a stirring reaction facility having stirring means for stirring the surfactant-containing water in the flow path.

（６） 前記複数のオゾン反応設備の少なくともいずれか一つより入口に近い位置に設けられ、前記界面活性剤含有水にアルカリを添加するアルカリ添加手段をさらに含む（４）または（５）に記載の界面活性剤含有水の処理装置。   (6) The method according to (4) or (5), further including an alkali addition unit that is provided at a position closer to the inlet than at least one of the plurality of ozone reaction facilities and adds an alkali to the surfactant-containing water. Water treatment equipment for surfactants.

（７） 前記複数のオゾン反応設備の少なくともいずれか一つより入口に近い位置に設けられ、前記界面活性剤含有水にアルカリを添加するアルカリ添加手段と、過酸化水素を添加する過酸化水素添加手段と、をさらに含む（４）または（５）に記載の界面活性剤含有水の処理装置。   (7) Alkali addition means for adding alkali to the surfactant-containing water and hydrogen peroxide addition for adding hydrogen peroxide, which is provided at a position closer to the inlet than at least one of the plurality of ozone reaction facilities And the surfactant-containing water treatment apparatus according to (4) or (5).

本発明により処理される被処理液は、少なくとも界面活性剤を含む。界面活性剤の濃度は特に限定されず、例えば界面活性剤の濃度が３〜３０ｍｇ／Ｌであって、界面活性剤以外の有機物を含んでＴＯＣ濃度が５〜５０ｍｇ／Ｌ程度の界面活性剤含有水の処理に用いることができる。本発明は特に、電子部品製造工場廃水のような低ＴＯＣ濃度廃水にも使用でき、具体的には界面活性剤の濃度が１〜５ｍｇ／Ｌ程度、ＴＯＣ濃度が２〜１０ｍｇ／Ｌ程度の界面活性剤含有水にも適用できる。   The liquid to be treated to be treated according to the present invention contains at least a surfactant. The concentration of the surfactant is not particularly limited. For example, the surfactant concentration is 3 to 30 mg / L, and the surfactant contains an organic substance other than the surfactant and has a TOC concentration of about 5 to 50 mg / L. Can be used for water treatment. In particular, the present invention can be used for low TOC concentration wastewater such as electronic component manufacturing factory wastewater. Specifically, the interface has a surfactant concentration of about 1 to 5 mg / L and a TOC concentration of about 2 to 10 mg / L. It can also be applied to activator-containing water.

本発明は特に、発泡性の強い非イオン性界面活性剤を含む界面活性剤含有水の処理に好適に使用でき、エチレンオキサイド（ＥＯ）鎖を有する難分解性の界面活性剤を含む界面活性剤含有水の処理にも適している。ただし、界面活性剤の種類は特に限定されず、アニオン性界面活性剤、およびカチオン性界面活性剤を含むイオン性界面活性剤を含む界面活性剤含有水の処理に本発明を用いることは排除されない。非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル（ＡＥ）、ポリオキシエチレンアルキルフェニルエーテル（ＡＰＥ）、脂肪酸アルカノールアミド、およびポリオキシエチレンソルビタン脂肪酸エステル等がある。   In particular, the present invention can be suitably used for the treatment of surfactant-containing water containing a non-ionic surfactant having a strong foaming property, and includes a hardly decomposable surfactant having an ethylene oxide (EO) chain. Suitable for treatment of contained water. However, the type of surfactant is not particularly limited, and the use of the present invention for the treatment of surfactant-containing water containing an anionic surfactant and an ionic surfactant containing a cationic surfactant is not excluded. . Nonionic surfactants include polyoxyethylene alkyl ether (AE), polyoxyethylene alkyl phenyl ether (APE), fatty acid alkanolamide, and polyoxyethylene sorbitan fatty acid ester.

オゾンは、空気または酸素を原料として製造されるオゾン含有ガスとして界面活性剤含有水に添加できるが、電解方式で製造されたオゾンを使用することは排除されない。オゾンの添加量は、界面活性剤を炭酸ガスにまで完全に分解するために必要な量（以下、「完全分解必要量」）であることが好ましい。ただし、反応効率によっては完全分解必要量を超えるオゾンを添加してもよく、本発明に係る処理を行った後、生物処理、吸着処理、または脱イオン処理等を行う場合等は、完全分解必要量未満の添加量としてもよい。   Although ozone can be added to the surfactant-containing water as an ozone-containing gas produced using air or oxygen as a raw material, the use of ozone produced by an electrolytic method is not excluded. The amount of ozone added is preferably an amount necessary for completely decomposing the surfactant into carbon dioxide (hereinafter referred to as “complete decomposition required amount”). However, depending on the reaction efficiency, ozone exceeding the amount required for complete decomposition may be added. After performing the treatment according to the present invention, complete decomposition is required when performing biological treatment, adsorption treatment, deionization treatment, etc. The addition amount may be less than the amount.

具体的には、界面活性剤を炭酸ガスにまで完全分解する場合はオゾンの添加量は、界面活性剤に対して２０〜５０倍（質量比）とすることが好ましい。また、本発明による処理後に生物処理を行う場合、オゾンの添加量は、界面活性剤に対して２〜１０倍（質量比）として界面活性剤を生物分解可能な形態、すなわち有機酸やグリコール類にまで分解することが好ましい。   Specifically, when the surfactant is completely decomposed to carbon dioxide, the amount of ozone added is preferably 20 to 50 times (mass ratio) with respect to the surfactant. When biological treatment is performed after the treatment according to the present invention, the amount of ozone added is 2 to 10 times (mass ratio) with respect to the surfactant, so that the surfactant can be biodegraded, that is, organic acids or glycols. It is preferable to decompose to.

本発明では、界面活性剤を分解するために必要なオゾンを、一定方向に流れる界面活性剤含有水の流れ方向に沿った複数の位置で分割して添加し、特に最終段、つまり出口に最も近接する位置において最も多くのオゾンを添加する。最終段で添加するオゾンの添加量は、全体の添加量の６０〜９５％とすることが好ましい。本発明では、オゾンの添加位置を複数に分割していることから、反応効率等によっては、最終段で添加するオゾン量をあらかじめ設定した添加量より多くしてもよく、逆に少なくしてもよい。   In the present invention, ozone necessary for decomposing the surfactant is divided and added at a plurality of positions along the flow direction of the surfactant-containing water flowing in a certain direction, and particularly at the final stage, that is, at the outlet. Add the most ozone in the close position. The amount of ozone added in the final stage is preferably 60 to 95% of the total amount added. In the present invention, since the ozone addition position is divided into a plurality, depending on the reaction efficiency, etc., the amount of ozone added in the final stage may be larger than the preset amount, or conversely, Good.

オゾンの添加位置は２箇所以上であればよく、オゾン添加位置を２箇所とする場合は、最終段より前段、つまり最初のオゾン添加位置で、全体の添加量の５〜４０％のオゾンを添加する。また、オゾンの添加位置を３箇所以上とする場合、最終段以外の複数のオゾン添加位置でのオゾン添加量は、互いに同一であってもよく、異なってもよい。オゾン添加位置が多いと界面活性剤の分解率を向上させることができる一方、オゾン添加のために要する機器類が多くなるため、オゾン添加位置は２〜３箇所とすることが好ましい。   The ozone addition position may be two or more. When the ozone addition position is two, ozone is added at 5 to 40% of the total addition amount before the final stage, that is, at the first ozone addition position. To do. Moreover, when the ozone addition position is three or more, the ozone addition amounts at a plurality of ozone addition positions other than the final stage may be the same or different. While there are many ozone addition positions, the decomposition rate of the surfactant can be improved. On the other hand, equipment required for ozone addition increases, and therefore the ozone addition positions are preferably two to three.

本発明に従い、界面活性剤の分解に必要なオゾンの添加位置を、界面活性剤含有水の流れに沿った複数箇所に分割すれば、１箇所でオゾンを添加する場合に比して、１箇所あたりのオゾン添加量が少なくなるため、発泡を抑制することができる。特に、本発明では、界面活性剤含有水の流路の出口に最も近接する最終段で全体の添加量の大部分を添加し、最終段より入口側、つまり前段側でのオゾン添加量を少なくすることにより、発泡を抑制しつつ、高いオゾン分解効率を得ることができる。   According to the present invention, if the ozone addition position necessary for the decomposition of the surfactant is divided into a plurality of locations along the flow of the surfactant-containing water, it is one location compared to the case where ozone is added at one location. Since the amount of ozone added per unit is reduced, foaming can be suppressed. In particular, in the present invention, most of the total addition amount is added at the final stage closest to the outlet of the surfactant-containing water flow path, and the ozone addition amount at the inlet side, that is, the front stage side is smaller than the final stage. By doing so, it is possible to obtain high ozonolysis efficiency while suppressing foaming.

これは、入口側で添加された少量のオゾンが、界面活性剤の界面活性を示す部分（疎水性部分と親水性部分との境界部）と容易かつ速やかに反応することにより、界面活性剤が変性されるためと推察される。すなわち、まず、入口側で添加された少量のオゾンにより界面活性剤が変性されることで発泡性が低減されるため、最終段で大量のオゾンを添加しても発泡を抑制できるものと考えられる。   This is because a small amount of ozone added on the inlet side reacts easily and quickly with the surface activity of the surfactant (the boundary between the hydrophobic portion and the hydrophilic portion). It is assumed that it is denatured. That is, first, since the foaming property is reduced by modifying the surfactant with a small amount of ozone added at the inlet side, it is considered that foaming can be suppressed even if a large amount of ozone is added in the final stage. .

オゾン添加位置には、界面活性剤含有水にオゾンを添加することでオゾンと界面活性剤とを反応させるオゾン反応設備を設ける。オゾン反応設備は、界面活性剤含有水にオゾンを添加するオゾン供給手段を備えていればよいが、オゾンと界面活性剤とを十分に反応させるため、界面活性剤含有水が所定の時間滞留できる反応槽をさらに備えることが好ましい。特に、界面活性剤含有水が流れる流路の出口に最も近い位置に設けられるオゾン反応設備（最終段オゾン反応設備）は、界面活性剤とオゾンとの反応時間を確保するため、散気管等のオゾン供給手段を有する気液接触型の反応槽を備えることが好ましい。   At the ozone addition position, an ozone reaction facility for reacting ozone with the surfactant by adding ozone to the surfactant-containing water is provided. The ozone reaction equipment only needs to include an ozone supply means for adding ozone to the surfactant-containing water. However, in order to sufficiently react ozone with the surfactant, the surfactant-containing water can stay for a predetermined time. It is preferable to further comprise a reaction vessel. In particular, the ozone reaction facility (final stage ozone reaction facility) provided at the position closest to the outlet of the flow path through which the surfactant-containing water flows is used to secure the reaction time between the surfactant and ozone. It is preferable to provide a gas-liquid contact type reaction tank having ozone supply means.

一方、界面活性剤の界面活性を示す部分はオゾンとの反応速度が高いため、最終段オゾン反応設備より入口側に設けられるオゾン反応設備（以下、「前段側オゾン反応設備」は、流路内を流れる界面活性剤にオゾンを添加する流路内オゾン供給手段を少なくとも備えていればよい。流路内オゾン供給手段としては、オゾン注入用の配管、エジェクタ、多孔管、および給気口付き渦流ポンプ等が挙げられる。前段側オゾン反応設備は、特に、オゾンと界面活性剤含有水との接触効率を高めるため、流路内オゾン供給手段に加え、流路内の界面活性剤含有水を攪拌する作用を有する攪拌手段を備えることが好ましい。攪拌手段としては、含気運転可能な渦流ポンプ、およびラインミキサ等が挙げられる。このように、前段側オゾン反応設備では反応槽を省略することで装置を簡素にできる。   On the other hand, since the surface activity of the surfactant has a high reaction rate with ozone, the ozone reaction facility (hereinafter referred to as the “previous stage ozone reaction facility”) provided on the inlet side of the final stage ozone reaction facility The ozone supply means in the flow path for adding ozone to the surfactant flowing in the flow path may include at least an ozone supply pipe, an ejector, a perforated pipe, and a vortex with an air supply port. Pumps, etc. The former stage ozone reaction equipment, in particular, stirs the surfactant-containing water in the flow path in addition to the ozone supply means in the flow path, in order to increase the contact efficiency between ozone and the surfactant-containing water. The stirring means preferably includes a vortex pump capable of aeration operation, a line mixer, etc. In this way, the front-stage ozone reaction equipment is not suitable. The apparatus by omitting the bath can be simplified.

本発明では、オゾンによる酸化反応を促進するために、界面活性剤含有水にオゾンを添加する前にアルカリを添加し、アルカリの共存下で界面活性剤含有水にオゾンが添加されるようにしてもよい。アルカリの添加量は、界面活性剤含有水のｐＨを９〜１１にするために必要な量とすることが好ましい。添加するアルカリの種類は特に限定されず、水酸化ナトリウムおよび水酸化カリウム等を使用できる。   In the present invention, in order to promote the oxidation reaction by ozone, an alkali is added before adding ozone to the surfactant-containing water, and ozone is added to the surfactant-containing water in the presence of the alkali. Also good. The amount of alkali added is preferably an amount necessary to adjust the pH of the surfactant-containing water to 9-11. The kind of alkali to add is not specifically limited, Sodium hydroxide, potassium hydroxide, etc. can be used.

また、アルカリに加え過酸化水素も界面活性剤含有水に添加してもよい。オゾン添加前の界面活性剤含有水にアルカリおよび過酸化水素を添加する場合、アルカリと過酸化水素の添加順序は特に限定されない。また、アルカリの添加量は過酸化水素を添加しない場合と同様とすればよく、過酸化水素の添加量は、オゾンの添加量に対して質量比で０．１〜１となる程度が好ましい。   In addition to alkali, hydrogen peroxide may also be added to the surfactant-containing water. When alkali and hydrogen peroxide are added to the surfactant-containing water before the addition of ozone, the order of addition of alkali and hydrogen peroxide is not particularly limited. Further, the amount of alkali added may be the same as in the case where hydrogen peroxide is not added, and the amount of hydrogen peroxide added is preferably about 0.1 to 1 by mass ratio with respect to the amount of ozone added.

このように、界面活性剤含有水にアルカリを単独または過酸化水素とともに添加した後、オゾンを添加することで、ヒドロキシルラジカルを生成させ、酸化反応を促進できる。アルカリ（および過酸化水素）は、複数に分割したオゾン添加位置の少なくとも１箇所で、オゾン添加に先立って添加すればよいが、各オゾン添加位置の前で添加してもよい。特に、ヒドロキシルラジカルの生成効率を向上させるためには、最も出口に近いオゾン添加位置の前でアルカリ（および過酸化水素）を添加することが好ましい。   As described above, after adding alkali alone or together with hydrogen peroxide to the surfactant-containing water, by adding ozone, hydroxyl radicals can be generated to promote the oxidation reaction. Alkaline (and hydrogen peroxide) may be added prior to ozone addition at at least one of the ozone addition positions divided into a plurality of positions, but may be added before each ozone addition position. In particular, in order to improve the production efficiency of hydroxyl radicals, it is preferable to add alkali (and hydrogen peroxide) in front of the ozone addition position closest to the outlet.

反応槽の形状は限定されず、反応槽の下部からオゾン含有ガスを界面活性剤含有水に供給し、反応槽の上部から廃オゾン含有ガスを取り出す構成を有していることが好ましい。また、被処理水は反応槽下部から供給してもよいし、反応槽の上部に散水手段を設けて被処理水を散水手段から散水して供給してもよい。このように液面に散水すれば発泡をより抑制しやすい。   The shape of the reaction tank is not limited, and it is preferable to have a configuration in which an ozone-containing gas is supplied to the surfactant-containing water from the lower part of the reaction tank and the waste ozone-containing gas is taken out from the upper part of the reaction tank. Further, the water to be treated may be supplied from the lower part of the reaction tank, or a watering means may be provided at the upper part of the reaction tank, and the water to be treated may be supplied from the watering means. Thus, if it sprays on a liquid level, it will be easier to suppress foaming.

本発明によれば、界面活性剤含有水の発泡を抑制し、界面活性剤を酸化分解するために必要な量のオゾンを添加できる。このため本発明によれば、高い分解率で界面活性剤を分解させ、かつ、発泡によるトラブルを防止して安定して界面活性剤含有水を処理することができる。   According to the present invention, it is possible to add a necessary amount of ozone to suppress foaming of surfactant-containing water and oxidatively decompose the surfactant. For this reason, according to this invention, surfactant can be decomposed | disassembled with a high decomposition rate, the trouble by foaming can be prevented, and surfactant-containing water can be processed stably.

以下、本発明について図面を用いて詳細に説明する。以下、同一部材には同一符号を付し、説明を省略又は簡略化する。図１は、本発明の一実施形態に係る界面活性剤含有水の処理装置（以下、単に「処理装置」という）１の模式図である。処理装置１は、被処理液である界面活性剤を含む界面活性剤含有水が流れる流路５と、流路５の途中に設けられた前段側オゾン反応設備１０と、最終段オゾン反応設備２０と、を含む。流路５は入口５１および出口５２を備え、界面活性剤含有水は入口５１から出口５２に向かって流れるように入口５１から処理装置１内に導入され、出口５２から排出される。   Hereinafter, the present invention will be described in detail with reference to the drawings. Hereinafter, the same members are denoted by the same reference numerals, and description thereof is omitted or simplified. FIG. 1 is a schematic view of a surfactant-containing water treatment apparatus (hereinafter simply referred to as “treatment apparatus”) 1 according to an embodiment of the present invention. The treatment apparatus 1 includes a flow path 5 through which a surfactant-containing water containing a surfactant to be treated flows, a front-stage ozone reaction facility 10 provided in the middle of the flow path 5, and a final-stage ozone reaction facility 20. And including. The flow path 5 includes an inlet 51 and an outlet 52, and the surfactant-containing water is introduced into the processing apparatus 1 from the inlet 51 so as to flow from the inlet 51 toward the outlet 52, and is discharged from the outlet 52.

本実施形態では、前段側オゾン反応設備１０より入口５１側に第１過酸化水素添加手段および第１アルカリ添加手段が設けられている。また、最終段オゾン反応設備２０より入口５１側には、第２過酸化水素添加手段および第２アルカリ添加手段が設けられている。上述したとおり、これらの過酸化水素添加手段およびアルカリ添加手段は省略することもできる。   In the present embodiment, the first hydrogen peroxide addition means and the first alkali addition means are provided on the inlet 51 side from the front-stage ozone reaction facility 10. Further, a second hydrogen peroxide addition unit and a second alkali addition unit are provided on the inlet 51 side from the final stage ozone reaction facility 20. As described above, these hydrogen peroxide addition means and alkali addition means can be omitted.

過酸化水素添加手段は、流路５内を流れる界面活性剤含有水に過酸化水素を添加できる部材で構成でき、例えば一端が過酸化水素を貯留する貯槽に接続された配管とすることができる。本実施形態では、第１過酸化水素添加手段は、第１過酸化水素注入管３１で構成され、第２過酸化水素添加手段は、第２過酸化水素注入管３２で構成されている。第１過酸化水素注入管３１および第２過酸化水素注入管３２は、どちらも一端が過酸化水素貯槽３０に接続され、他端が流路５を構成する配管に接続されている。   The hydrogen peroxide addition means can be constituted by a member capable of adding hydrogen peroxide to the surfactant-containing water flowing in the flow path 5, for example, a pipe having one end connected to a storage tank storing hydrogen peroxide. . In the present embodiment, the first hydrogen peroxide addition means is constituted by the first hydrogen peroxide injection pipe 31, and the second hydrogen peroxide addition means is constituted by the second hydrogen peroxide injection pipe 32. Each of the first hydrogen peroxide injection pipe 31 and the second hydrogen peroxide injection pipe 32 has one end connected to the hydrogen peroxide storage tank 30 and the other end connected to a pipe constituting the flow path 5.

アルカリ添加手段は、流路５内を流れる界面活性剤含有水にアルカリを添加できる部材で構成でき、例えば一端がアルカリを貯留する貯槽に接続された配管とすることができる。本実施形態では、第１アルカリ添加手段は、第１アルカリ注入管４１で構成され、第２アルカリ添加手段は、第２アルカリ注入管４２で構成されている。第１アルカリ注入管４１および第２アルカリ注入管４２は、どちらも一端がアルカリ貯槽４０に接続され、他端が流路５を構成する配管に接続されている。   The alkali addition means can be constituted by a member capable of adding alkali to the surfactant-containing water flowing in the flow path 5, and can be, for example, a pipe connected at one end to a storage tank storing the alkali. In the present embodiment, the first alkali addition means is constituted by a first alkali injection pipe 41, and the second alkali addition means is constituted by a second alkali injection pipe 42. One end of each of the first alkali injection pipe 41 and the second alkali injection pipe 42 is connected to the alkali storage tank 40, and the other end is connected to a pipe constituting the flow path 5.

前段側オゾン反応設備１０は、流路５の途中に設けられた攪拌手段としての渦流ポンプ１１および渦流ポンプ１１より入口５１側の流路５に接続された流路内オゾン供給手段を含んで構成されている。本実施形態では、流路内オゾン供給手段は、オゾン含有ガスを流路５に吹き込む部材で構成でき、例えば本実施形態では、一端が流路５に接続されたオゾン注入管１２で構成されている。オゾン注入管１２の他端は、オゾン発生器２５に接続されている。   The front-stage ozone reaction facility 10 includes a vortex pump 11 as stirring means provided in the middle of the flow path 5 and an in-flow path ozone supply means connected to the flow path 5 on the inlet 51 side from the vortex pump 11. Has been. In the present embodiment, the ozone supply means in the flow path can be constituted by a member that blows ozone-containing gas into the flow path 5. For example, in this embodiment, the ozone supply means is constituted by an ozone injection pipe 12 having one end connected to the flow path 5. Yes. The other end of the ozone injection pipe 12 is connected to the ozone generator 25.

最終段オゾン反応設備２０は、被処理水（前段側オゾン反応設備１０からの処理水）供給手段としての散水管２３とオゾン供給手段としての散気管２１を有する気液接触型の反応槽２２で構成されている。散気管２１は、一端がオゾン発生器２５と接続されており、オゾン発生器２５で生成されたオゾン含有ガスが散気管２１を介して反応槽２２下部から界面活性剤含有水に添加される。反応槽２２の大きさは特に限定されないが、界面活性剤含有水の滞留時間が、界面活性剤がオゾンにより酸化分解されるために必要な時間となるようにすることが好ましく、例えば、界面活性剤含有水の滞留時間が５〜１０分となるようにするとよい。   The final stage ozone reaction facility 20 is a gas-liquid contact type reaction tank 22 having a sprinkling pipe 23 as supply water (treated water from the preceding ozone reaction equipment 10) supply means and a diffusion pipe 21 as ozone supply means. It is configured. One end of the air diffuser 21 is connected to the ozone generator 25, and the ozone-containing gas generated by the ozone generator 25 is added to the surfactant-containing water from the lower part of the reaction tank 22 through the air diffuser 21. Although the size of the reaction tank 22 is not particularly limited, it is preferable that the residence time of the surfactant-containing water is set to be a time necessary for the surfactant to be oxidatively decomposed by ozone. The residence time of the agent-containing water is preferably 5 to 10 minutes.

本実施形態では、オゾン発生器２５で生成されたオゾン含有ガスは、オゾン路２５Ａを介してオゾン注入管１２と、散気管２１とに供給される。本発明では特に、界面活性剤含有水に添加されるオゾン含有ガスの大部分（６０〜９５％程度）は最終段オゾン反応設備２０から界面活性剤含有水に添加する。このため、オゾン発生器２５で生成されたオゾン含有ガスの大部分は散気管２１に供給され、オゾン注入管１２には生成されたオゾン含有ガスの５〜４０％程度が供給されるように構成されている。   In the present embodiment, the ozone-containing gas generated by the ozone generator 25 is supplied to the ozone injection pipe 12 and the diffuser pipe 21 via the ozone path 25A. Particularly in the present invention, most of the ozone-containing gas (about 60 to 95%) added to the surfactant-containing water is added to the surfactant-containing water from the final stage ozone reaction facility 20. For this reason, most of the ozone containing gas produced | generated with the ozone generator 25 is supplied to the diffuser pipe 21, and the ozone injection pipe 12 is comprised so that about 5-40% of the produced | generated ozone containing gas may be supplied. Has been.

次に、上記の処理装置１を用いて、界面活性剤含有水を処理する方法について説明する。まず、半導体製造廃水等の界面活性剤含有水を被処理液として、入口５１から流路５内に導入する。流路５の途中には必要に応じてポンプ等を設け、界面活性剤含有水が入口５１側から出口５２側に向かって流速０．５〜２ｍ／ｓｅｃ程度の速さで流路５内を流れるようにするとよい。   Next, a method for treating surfactant-containing water using the treatment apparatus 1 will be described. First, surfactant-containing water such as semiconductor manufacturing wastewater is introduced into the flow path 5 from the inlet 51 as a liquid to be treated. A pump or the like is provided in the middle of the channel 5 so that the surfactant-containing water can flow through the channel 5 at a flow rate of about 0.5 to 2 m / sec from the inlet 51 side toward the outlet 52 side. It is good to make it flow.

本実施形態に係る処理装置１では、流路５に沿って、入口５１側から出口５２側に向かって第１過酸化水素注入管３１、第１アルカリ注入管４１、オゾン注入管１２、渦流ポンプ１１、第２過酸化水素注入管３２、第２アルカリ注入管４２、および反応槽２２がこの順に設けられている。そして、入口５１側から出口５２側に向かう方向に流れる界面活性剤含有水には、その流れ方向に沿ってまず、第１過酸化水素注入管３１から過酸化水素、および第１アルカリ注入管４１から水酸化ナトリウム等のアルカリが添加され、ｐＨが９〜１１程度に調整される。   In the processing apparatus 1 according to the present embodiment, the first hydrogen peroxide injection pipe 31, the first alkali injection pipe 41, the ozone injection pipe 12, and the vortex pump along the flow path 5 from the inlet 51 side toward the outlet 52 side. 11, a second hydrogen peroxide injection pipe 32, a second alkali injection pipe 42, and a reaction tank 22 are provided in this order. Then, in the surfactant-containing water flowing in the direction from the inlet 51 side toward the outlet 52 side, first, hydrogen peroxide from the first hydrogen peroxide injection pipe 31 and the first alkali injection pipe 41 along the flow direction. Then, alkali such as sodium hydroxide is added to adjust the pH to about 9-11.

次いで、ｐＨを上げた界面活性剤にオゾン注入管１２から少量のオゾン含有ガスが添加される。オゾン注入管１２の直後には渦流ポンプ１１が設けられており、少量のオゾンが添加された界面活性剤含有水は、渦流ポンプ１１により攪拌される。前段側オゾン反応設備１０では少量のオゾンが添加できればよいため、渦流ポンプ１１は省略してもよい。また、オゾン注入管１２と渦流ポンプ１１とを設ける代わりに、エジェクタとラインミキサを流路５の途中に設けてもよい。このように、前段側オゾン反応設備１０で少量のオゾンを添加した界面活性剤含有水を、渦流ポンプ１１等で攪拌して大きなせん断力を与えることで、少量のオゾンを界面活性剤と効率よく反応させることができる。   Next, a small amount of ozone-containing gas is added from the ozone injection tube 12 to the surfactant whose pH has been raised. A vortex pump 11 is provided immediately after the ozone injection pipe 12, and the surfactant-containing water to which a small amount of ozone is added is stirred by the vortex pump 11. Since it is sufficient that a small amount of ozone can be added to the upstream ozone reaction facility 10, the vortex pump 11 may be omitted. Further, instead of providing the ozone injection pipe 12 and the vortex pump 11, an ejector and a line mixer may be provided in the middle of the flow path 5. In this way, the surfactant-containing water to which a small amount of ozone is added in the front-stage ozone reaction facility 10 is stirred with the vortex pump 11 to give a large shearing force, so that a small amount of ozone can be efficiently combined with the surfactant. Can be reacted.

前段側オゾン反応設備１０では、少量のオゾン添加により界面活性剤が変性され、発泡性が低減される。これは、少量添加されたオゾンは、主として界面活性剤の疎水性部分と親水性部分との境界部と反応して、界面活性剤の界面活性を示す部分が変性することによるものと推察される。このため、最終段オゾン反応設備２０で大量のオゾンを添加しても被処理液の発泡を抑制できる。そこで、本発明では前段側オゾン反応設備１０で、処理装置１で界面活性剤含有水に添加される全オゾン量の５〜４０％程度を添加し、最終段オゾン反応設備２０で残りの量のオゾンを添加する。   In the front-stage ozone reaction facility 10, the surfactant is denatured by adding a small amount of ozone, and foaming properties are reduced. This is presumably because ozone added in a small amount mainly reacts with the boundary portion between the hydrophobic portion and the hydrophilic portion of the surfactant, and the portion showing the surface activity of the surfactant is denatured. . For this reason, even if a large amount of ozone is added in the final stage ozone reaction facility 20, foaming of the liquid to be treated can be suppressed. Therefore, in the present invention, about 5 to 40% of the total ozone amount added to the surfactant-containing water in the processing apparatus 1 is added in the front stage ozone reaction facility 10, and the remaining amount in the final stage ozone reaction facility 20. Add ozone.

なお、オゾンと界面活性剤との反応により、界面活性剤が変性して有機酸等が生じるため、処理装置１では最終段オゾン反応設備２０の前に第２過酸化水素注入管３２と第２アルカリ注入管４２を設けている。これにより、前段側オゾン反応設備２０を通過した界面活性剤含有水に過酸化水素とアルカリを添加し、オゾンによる酸化反応が促進される状態で、最終段オゾン反応設備２０での処理を行なう。   Since the surfactant is denatured by the reaction between ozone and the surfactant and an organic acid or the like is generated, the second hydrogen peroxide injection pipe 32 and the second hydrogen peroxide injection pipe 32 are disposed in the processing apparatus 1 before the final stage ozone reaction facility 20. An alkali injection pipe 42 is provided. Thus, hydrogen peroxide and alkali are added to the surfactant-containing water that has passed through the front-stage ozone reaction facility 20, and the treatment in the final-stage ozone reaction facility 20 is performed in a state where the oxidation reaction by ozone is promoted.

最終段オゾン反応設備２０では、反応槽２２に被処理液（界面活性剤含有水）を導入し、反応槽２２下部に接続した散気管２１からオゾン含有ガスを吹き込んで、被処理液を所定の時間、反応槽２２内に滞留させる。最終段オゾン反応設備２０では、処理装置１で界面活性剤含有水に添加される全オゾン量の大部分（６０〜９５％程度）を被処理液に添加して界面活性剤を分解する。最終段オゾン反応設備２０での処理後、界面活性剤が分解された処理水は出口５２から取り出し、必要に応じて生物処理等の後処理を行ない、超純水製造用の原水等として利用できる。   In the final stage ozone reaction facility 20, a liquid to be treated (surfactant-containing water) is introduced into the reaction tank 22, and an ozone-containing gas is blown from a diffuser tube 21 connected to the lower part of the reaction tank 22, thereby supplying the liquid to be treated to a predetermined level. It stays in the reaction tank 22 for a time. In the final stage ozone reaction facility 20, most of the total ozone amount (about 60 to 95%) added to the surfactant-containing water in the treatment apparatus 1 is added to the liquid to be treated to decompose the surfactant. After the treatment in the final stage ozone reaction facility 20, the treated water in which the surfactant is decomposed is taken out from the outlet 52, and after-treatment such as biological treatment is performed as necessary, and can be used as raw water for producing ultrapure water. .

[実施例]
以下、実施例に基づき、本発明をさらに詳しく説明する。実施例としては、図１に示す処理装置１を用い、界面活性剤としてＡＰＥを含む界面活性剤含有水を被処理液とした。界面活性剤含有水は、純水にＴＯＣ濃度２１ｍｇ／ＬとなるようにＡＰＥを溶解させて作成した合成廃水である。 [Example]
Hereinafter, the present invention will be described in more detail based on examples. As an example, the treatment apparatus 1 shown in FIG. 1 was used, and a surfactant-containing water containing APE as a surfactant was used as a liquid to be treated. The surfactant-containing water is a synthetic wastewater prepared by dissolving APE in pure water so as to have a TOC concentration of 21 mg / L.

渦流ポンプ１１としては、出口圧０．３Ｍｐａの渦流ポンプ（株式会社ニクニ製）を用い、界面活性剤含有水が、流路５内を入口５１から出口５２に向かって流速３５０Ｌ／ｈで流れるように処理装置１に導入した。   As the vortex pump 11, a vortex pump (manufactured by Nikuni Co., Ltd.) having an outlet pressure of 0.3 Mpa is used, and the surfactant-containing water flows in the flow path 5 from the inlet 51 to the outlet 52 at a flow rate of 350 L / h. Was introduced into the processing apparatus 1.

本実施例では各オゾン反応設備でのオゾン添加に先立ち、過酸化水素とアルカリを添加した。過酸化水素としては、濃度３５質量％のものを用い、アルカリとしては４質量％の水酸化ナトリウムを用いた。過酸化水素の添加量は、第１過酸化水素注入管３１からの添加量を１５ｍｇ／Ｌとし、第２過酸化水素注入管３２からの添加量を２５０ｍｇ／Ｌとした。なお、第２過酸化水素注入管３２は、流路５に接続せずに、反応槽２２の下部に接続するようにした点で図１の処理装置１と異なる構成とした。   In this example, hydrogen peroxide and alkali were added prior to the addition of ozone in each ozone reaction facility. Hydrogen peroxide having a concentration of 35% by mass was used, and 4% by mass of sodium hydroxide was used as the alkali. The amount of hydrogen peroxide added was 15 mg / L from the first hydrogen peroxide injection tube 31 and 250 mg / L from the second hydrogen peroxide injection tube 32. The second hydrogen peroxide injection pipe 32 is configured differently from the processing apparatus 1 of FIG. 1 in that it is connected to the lower part of the reaction tank 22 without being connected to the flow path 5.

一方、水酸化ナトリウムは、第１アルカリ注入管４１および第２アルカリ注入管４２それぞれから流路５に注入した。水酸化ナトリウムの添加量は、界面活性剤含有水のｐＨを１０にする量とした。   On the other hand, sodium hydroxide was injected into the flow path 5 from each of the first alkali injection pipe 41 and the second alkali injection pipe 42. The amount of sodium hydroxide added was such that the pH of the surfactant-containing water was 10.

オゾン発生器２５としては、酸素を原料として放電方式でオゾン濃度１５０ｇ／Ｎｍ３のオゾン含有ガスを生成する装置を用いた。オゾン発生器２５で発生されたオゾン含有ガスは、２０Ｌ／ｈの供給速度でオゾン注入管１２から流路５内に注入し、反応槽２２に取り付けられた散気管２１への供給量は３５０Ｌ／ｈの供給速度となるようにした。 As the ozone generator 25, an apparatus for generating an ozone-containing gas having an ozone concentration of 150 g / Nm 3 by a discharge method using oxygen as a raw material was used. The ozone-containing gas generated by the ozone generator 25 is injected into the flow path 5 from the ozone injection pipe 12 at a supply rate of 20 L / h, and the supply amount to the air diffusion pipe 21 attached to the reaction tank 22 is 350 L / h. The feed rate of h was set.

反応槽２２としては、直径３００ｍｍ、高さ２，７００ｍｍの円筒状の気液接触型オゾン反応塔を用いた。反応槽２２の下部には散気管２１を接続してオゾン含有ガスを界面活性剤含有水に吹き込むとともに、反応槽２２上部より散水管２３を介して被処理水（前段側処理水）を散水した。   As the reaction tank 22, a cylindrical gas-liquid contact type ozone reaction tower having a diameter of 300 mm and a height of 2,700 mm was used. A diffuser pipe 21 is connected to the lower part of the reaction tank 22 and ozone-containing gas is blown into the surfactant-containing water, and water to be treated (previous-stage treated water) is sprinkled from the upper part of the reaction tank 22 through the sprinkler pipe 23. .

上記条件で試験を行ない、渦流ポンプ１１出口で、前段側オゾン反応設備１０で処理された界面活性剤含有水（前段側処理水）を採取し、前段側処理水の界面活性剤濃度を測定した。また、反応槽２２出口で、最終段オゾン反応設備２０で処理された界面活性剤含有水（以下、最終段処理水）を採取し、最終段処理水の界面活性剤濃度の測定も行った。界面活性剤の濃度は、分光蛍光光度計（株式会社日立ハイテクノロジーズ製、Ｆ−４５００）を用い、励起波長２３０ｎｍ、蛍光波長３０５ｎｍで測定した。測定結果は、前段側処理水の界面活性剤濃度が３．３ｍｇ／Ｌ、最終段処理水の界面活性剤濃度が０．３７ｍｇ／Ｌで、界面活性剤の除去率は９８．２％であった。また、反応槽２２の気液界面は安定し、２時間以上の連続運転ができた。   The test was performed under the above conditions, and the surfactant-containing water treated in the front-stage ozone reaction facility 10 (the front-stage treated water) was collected at the outlet of the vortex pump 11 and the surfactant concentration of the front-stage treated water was measured. . Moreover, the surfactant containing water (henceforth the last stage treated water) processed by the last stage ozone reaction equipment 20 was extract | collected at the reaction tank 22 exit, and the surfactant density | concentration of the last stage treated water was also measured. The concentration of the surfactant was measured using a spectrofluorometer (manufactured by Hitachi High-Technologies Corporation, F-4500) at an excitation wavelength of 230 nm and a fluorescence wavelength of 305 nm. The measurement results showed that the surfactant concentration in the front-stage treated water was 3.3 mg / L, the surfactant concentration in the final-stage treated water was 0.37 mg / L, and the surfactant removal rate was 98.2%. It was. Moreover, the gas-liquid interface of the reaction tank 22 was stable, and continuous operation for 2 hours or more was possible.

[比較例]
比較例として、オゾン注入管１２に設けたバルブ（図示せず）を閉じることで前段側オゾン反応設備１０でのオゾン添加を行わず、反応槽２２で全オゾン量を添加するようにした。具体的には、反応槽２２に接続した散気管２１からのオゾン含有ガスの供給量を３７０Ｌ／ｈとした。その他の条件は実施例と同じにして試験を行なったところ、反応槽２２の気液界面が乱れた。この結果、最終段処理水の界面活性剤濃度は２．４ｍｇ／Ｌであり、界面活性剤の除去率は８８．５％に低下した。また、反応槽２２内に気泡が充満して気液界面が低下したため、約３０分で処理を停止せざるを得なくなった。 [Comparative example]
As a comparative example, by closing a valve (not shown) provided in the ozone injection pipe 12, the total ozone amount was added in the reaction tank 22 without adding ozone in the front-stage ozone reaction facility 10. Specifically, the supply amount of the ozone-containing gas from the air diffuser 21 connected to the reaction tank 22 was set to 370 L / h. When the test was conducted under the same conditions as in the example, the gas-liquid interface of the reaction tank 22 was disturbed. As a result, the surfactant concentration in the final stage treated water was 2.4 mg / L, and the surfactant removal rate decreased to 88.5%. Further, since the reaction tank 22 was filled with bubbles and the gas-liquid interface was lowered, the treatment had to be stopped in about 30 minutes.

このように本発明によれば、発泡による処理装置１の運転トラブルを防止し、界面活性剤を高い分解率で安定して分解することができる。   Thus, according to the present invention, it is possible to prevent the operation trouble of the processing apparatus 1 due to foaming and to stably decompose the surfactant at a high decomposition rate.

本発明は、界面活性剤を含む排水の処理に用いることができる。   The present invention can be used for treatment of waste water containing a surfactant.

本発明の一実施形態に係る界面活性剤含有水の処理装置の模式図である。It is a schematic diagram of the processing apparatus of surfactant containing water which concerns on one Embodiment of this invention.

符号の説明Explanation of symbols

１ 処理装置
５ 流路
１０ 前段側オゾン反応設備
１１ 渦流ポンプ
１２ オゾン注入管
２０ 最終段オゾン反応設備
２１ 散気管
２２ 反応槽
２３ 散水管
２５ オゾン発生器
２５Ａ オゾン路
３１ 第１過酸化水素注入管
３２ 第２過酸化水素注入管
４１ 第１アルカリ注入管
４２ 第２アルカリ注入管
５１ 入口
５２ 出口 DESCRIPTION OF SYMBOLS 1 Processing apparatus 5 Flow path 10 Previous stage ozone reaction equipment 11 Eddy current pump 12 Ozone injection pipe 20 Final stage ozone reaction equipment 21 Aeration pipe 22 Reaction tank 23 Sprinkling pipe 25 Ozone generator 25A Ozone path 31 1st hydrogen peroxide injection pipe 32 Second hydrogen peroxide injection pipe 41 First alkali injection pipe 42 Second alkali injection pipe 51 Inlet 52 Outlet

Claims (7)

界面活性剤含有水にオゾンを添加する界面活性剤含有水の処理方法であって、
前記界面活性剤含有水を、入口および出口を備える流路に流して前記流路に沿う複数の位置で前記オゾンを前記界面活性剤含有水に添加し、前記出口に最も近い位置において最も多くのオゾンを添加する界面活性剤含有水の処理方法。 A method for treating surfactant-containing water by adding ozone to the surfactant-containing water,
The surfactant-containing water is caused to flow through a flow path having an inlet and an outlet, and the ozone is added to the surfactant-containing water at a plurality of positions along the flow path. A method for treating surfactant-containing water to which ozone is added. 前記オゾンを添加する前に、前記界面活性剤含有水にアルカリを添加する請求項１に記載の界面活性剤含有水の処理方法。   The method for treating surfactant-containing water according to claim 1, wherein an alkali is added to the surfactant-containing water before the ozone is added. 前記オゾンを添加する前に、前記界面活性剤含有水にアルカリと過酸化水素とを添加する請求項１に記載の界面活性剤含有水の処理方法。   The method for treating surfactant-containing water according to claim 1, wherein an alkali and hydrogen peroxide are added to the surfactant-containing water before the ozone is added. 入口から出口に向かって界面活性剤含有水が流れる流路を含む界面活性剤含有水の処理装置であって、
前記流路に沿って設けられ、前記流路を流れる前記界面活性剤含有水に前記オゾンを添加して界面活性剤を酸化分解する複数のオゾン反応設備をさらに含み、
前記複数のオゾン反応設備のうち、前記出口に最も近い位置に設けられた最終段オゾン反応設備は、他のオゾン反応設備より多くの前記オゾンを前記界面活性剤含有水に添加する界面活性剤含有水の処理装置。 A surfactant-containing water treatment apparatus including a flow path through which surfactant-containing water flows from an inlet toward an outlet,
A plurality of ozone reaction facilities that are provided along the flow path and oxidatively decompose the surfactant by adding the ozone to the surfactant-containing water flowing through the flow path;
Of the plurality of ozone reaction facilities, the final stage ozone reaction facility provided at a position closest to the outlet includes a surfactant that adds more ozone to the surfactant-containing water than other ozone reaction facilities. Water treatment equipment. 前記最終段オゾン反応設備は、オゾン供給手段を有する気液接触型の反応槽であり、
前記他のオゾン反応設備として、前記流路に前記オゾンを供給する流路内オゾン供給手段と、前記流路内の界面活性剤含有水を攪拌する攪拌手段と、を有する攪拌反応設備を含む請求項４に記載の界面活性剤含有水の処理装置。 The final stage ozone reaction facility is a gas-liquid contact type reaction tank having ozone supply means,
The other ozone reaction facility includes an agitation reaction facility having an in-channel ozone supply unit that supplies the ozone to the channel and an agitation unit that agitates the surfactant-containing water in the channel. Item 5. A surfactant-containing water treatment apparatus according to Item 4. 前記複数のオゾン反応設備の少なくともいずれか一つより入口に近い位置に設けられ、前記界面活性剤含有水にアルカリを添加するアルカリ添加手段をさらに含む請求項４または５に記載の界面活性剤含有水の処理装置。   The surfactant-containing composition according to claim 4 or 5, further comprising an alkali adding means that is provided at a position closer to the inlet than at least one of the plurality of ozone reaction facilities and adds an alkali to the surfactant-containing water. Water treatment equipment. 前記複数のオゾン反応設備の少なくともいずれか一つより入口に近い位置に設けられ、前記界面活性剤含有水にアルカリを添加するアルカリ添加手段と、過酸化水素を添加する過酸化水素添加手段と、をさらに含む請求項４または５に記載の界面活性剤含有水の処理装置。   Provided at a position closer to the inlet than at least one of the plurality of ozone reaction facilities, an alkali adding means for adding alkali to the surfactant-containing water, and a hydrogen peroxide adding means for adding hydrogen peroxide, The surfactant-containing water treatment apparatus according to claim 4 or 5, further comprising:
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