JP3931258B2 - Ozone decomposition apparatus and decomposition method - Google Patents

Ozone decomposition apparatus and decomposition method Download PDF

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JP3931258B2
JP3931258B2 JP2003283586A JP2003283586A JP3931258B2 JP 3931258 B2 JP3931258 B2 JP 3931258B2 JP 2003283586 A JP2003283586 A JP 2003283586A JP 2003283586 A JP2003283586 A JP 2003283586A JP 3931258 B2 JP3931258 B2 JP 3931258B2
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ozone
ozonolysis
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decomposition
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伸一 永野
孝雄 小林
満 植竹
康雄 谷藤
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Hitachi Engineering and Services Co Ltd
Hitachi Ltd
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Description

本発明は、原子力施設の有機物を含んだ液をオゾンにより有機物分解処理するオゾン分解装置及び分解方法に関する。 The present invention relates to an ozone decomposing apparatus and a decomposing method for decomposing organic matter in a nuclear facility using ozone.

従来、原子力発電所や原子力関連の研究所等原子力施設では、作業着等を洗濯した際の洗濯廃液,作業者がシャワーを浴びた際のシャワードレン等には、有機物が混在しており、放射性物質の除去以外に有機物の除去が必要であった。有機物を除去するためのオゾン分解処理装置としては、例えば、特開2001−986号公報に記載されているように、有機物の錯をオゾンで切り、分解して処理するものが知られている。   Conventionally, in nuclear power facilities such as nuclear power plants and nuclear research institutes, washing waste liquid when washing work clothes, etc., shower drain when workers take a shower, etc. are mixed with organic matter and radioactive In addition to removing the material, it was necessary to remove organic matter. As an ozonolysis apparatus for removing organic substances, for example, as described in Japanese Patent Application Laid-Open No. 2001-986, an apparatus that cuts and removes complex of organic substances with ozone is known.

特開2001−986号公報JP 2001-986 A

しかしながら、特開2001−986号公報に記載されている有機物処理では、その処理状況の確認はTOCまたはCODの測定により確認するが、その測定には、液のサンプリング、分析が必要であり、時間と手間が掛かるため、処理が終了したかどうかの確認が遅れ、そのため終了確認が取れるまでの間を処理時間として見込まむ必要があり、また、その間処理を続ける必要があり、処理に時間を要するという問題があった。   However, in the organic matter treatment described in Japanese Patent Laid-Open No. 2001-986, the treatment status is confirmed by measuring the TOC or COD. However, the measurement requires sampling and analysis of the liquid, and the time Since it takes time and effort, it is necessary to allow the processing time until the end confirmation can be taken, and it is necessary to continue the processing during that time. There was a problem.

本発明の目的は、オゾンによる有機物分解処理において、処理終了の確認を容易に短時間で行うことができるオゾン分解処理装置及び分解方法を提供することにある。 An object of the present invention is to provide an ozone decomposition treatment apparatus and a decomposition method capable of easily confirming the completion of treatment in a short time in an organic matter decomposition treatment using ozone.

(1)上記目的を達成するために、本発明は、オゾンによる処理対象液中の有機物を分解処理するオゾン分解装置において、前記有機物のオゾンによる分解時に、前記処理対象液のTOCが時間とともに減少し、そのとき、pHは、一旦酸性になった後、有機酸が減少すると、再び中正となる特性を有し、pHを検出するpH計を備え、このpH計により、前記処理対象液のpHが酸性から再び中性になることを確認することによりオゾン分解処理の状況を監視するようにしたものである。
かかる構成により、オゾンによる有機物分解処理時に、pH計によるpHの確認により、処理終了の確認を容易に短時間で行い得るものとなる。
(1) In order to achieve the above object, the present invention provides an ozonolysis apparatus for decomposing an organic substance in a treatment target liquid by ozone , wherein the TOC of the treatment target liquid decreases with time when the organic substance is decomposed by ozone. At this time, the pH is once acidic, and once the organic acid is reduced, it has a characteristic that it becomes neutral again, and includes a pH meter that detects the pH. Is to monitor the status of ozonolysis treatment by confirming that the acid goes from neutral to neutral again .
With this configuration, when the organic substance is decomposed with ozone, the completion of the treatment can be easily confirmed in a short time by confirming the pH with a pH meter.

(2)上記(1)において、好ましくは、オゾン分解槽に供給された処理対象液は、戻り配管による循環ラインにより循環するとともに、この循環ライン中にオゾンが供給される構成であり、前記pH計は、前記循環ライン中に設けるようにしたものである。   (2) In the above (1), preferably, the treatment target liquid supplied to the ozonolysis tank is circulated by a circulation line by a return pipe, and ozone is supplied into the circulation line, and the pH The total is provided in the circulation line.

(3)上記(1)において、好ましくは、オゾン分解槽に供給された処理対象液に対してオゾンが供給される構成であり、前記pH計は、前記オゾン分解槽中に設けるようにしたものである。   (3) In the above (1), preferably, ozone is supplied to the treatment target liquid supplied to the ozone decomposition tank, and the pH meter is provided in the ozone decomposition tank. It is.

(4)上記(1)において、好ましくは、処理対象液を溜めることなく処理する構成であり、前記pH計は、オゾン分解装置の出口に設けるようにしたものである。
(5)また、上記目的を達成するために、本発明は、オゾンによる処理対象液中の有機物を分解処理するオゾン分解方法において、前記有機物のオゾンによる分解時に、前記処理対象液のTOCが時間とともに減少し、そのとき、pHは、一旦酸性になった後、有機酸が減少すると、再び中性となる特性を有し、前記処理対象液のpHが酸性から再び中性になることを確認することによりオゾン分解処理の状況を監視するようにしたものである。
かかる方法により、オゾンによる有機物分解処理時に、pH計によるpHの確認により、処理終了の確認を容易に短時間で行い得るものとなる。
(4) In the above (1), preferably, the treatment target liquid is treated without accumulating, and the pH meter is provided at the outlet of the ozonolysis apparatus.
(5) Moreover, in order to achieve the said objective, this invention is the ozone decomposition | disassembly method which decomposes | disassembles the organic substance in the process target liquid by ozone, TOC of the said process target liquid is time at the time of decomposition | disassembly by the ozone of the said organic substance. When the pH once becomes acidic and then the organic acid decreases, the pH becomes neutral again, and it is confirmed that the pH of the solution to be treated changes from acidic to neutral again. By doing so, the status of the ozonolysis treatment is monitored.
By this method, the end of the treatment can be easily confirmed in a short time by confirming the pH with a pH meter during the organic substance decomposition treatment with ozone.

本発明によれば、オゾンによる有機物分解処理において、処理終了の確認を容易に短時間で行うことができる。   According to the present invention, in the organic matter decomposition treatment with ozone, it is possible to easily confirm the completion of the treatment in a short time.

以下、図1及び図2を用いて、本発明の第1の実施形態によるオゾン分解装置の構成について説明する。
図1は、本発明の第1の実施形態によるオゾン分解装置の構成を示す構成図である。図2は、本発明の第1の実施形態によるオゾン分解装置における測定原理の説明図である。
Hereinafter, the configuration of the ozonolysis apparatus according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a configuration diagram showing a configuration of an ozonolysis apparatus according to a first embodiment of the present invention. FIG. 2 is an explanatory diagram of the measurement principle in the ozonolysis apparatus according to the first embodiment of the present invention.

図1に示すように、本実施形態によるオゾン分解装置は、pH計1と、オゾン供給機2と、オゾン分解槽3と、オゾンミキサ4と、ポンプ5と、排出弁6とから構成される。   As shown in FIG. 1, the ozonolysis apparatus according to the present embodiment includes a pH meter 1, an ozone supplier 2, an ozonolysis tank 3, an ozone mixer 4, a pump 5, and a discharge valve 6.

オゾン分解槽3に供給された処理対象液11は、排出弁6が閉じた状態で、ポンプ5によりpH計1、オゾンミキサ4を通りオゾン分解槽3に戻る配管内を循環する。オゾン供給機2よりオゾン21がオゾンミキサ4に供給され、処理対象液11とオゾン21が混合されることで、オゾン21が処理対象液11に溶け込み、オゾン21による分解処理が始まる。処理が始まると有機酸が発生する。   The liquid 11 to be treated supplied to the ozonolysis tank 3 is circulated in the pipe returning to the ozonolysis tank 3 through the pH meter 1 and the ozone mixer 4 by the pump 5 with the discharge valve 6 closed. Ozone 21 is supplied from the ozone supplier 2 to the ozone mixer 4, and the treatment target liquid 11 and the ozone 21 are mixed, so that the ozone 21 is dissolved in the treatment target liquid 11 and the decomposition process using the ozone 21 is started. When the treatment starts, organic acids are generated.

すなわち、オゾン分解の処理では、処理対象液に投入されたオゾンが液に溶け込み加水分解を経て、高い酸化力を持つヒドロキシラジカル(OH*)が生成する。このヒドロキシラジカルが有機物を分解する。その分解は、有機物→有機酸→炭酸等(無機物)の過程で行われる。このオゾンによる有機物分解の過程で一時的に有機酸が発生する。そのため、処理中は生成する有機酸の影響で酸性を維持する。一時的に生成された有機酸は、処理が進むにつれ炭酸等無機物に処理されるため、処理液のpHが酸性側から中性になる。   That is, in the ozonolysis treatment, the ozone charged into the liquid to be treated dissolves in the solution and undergoes hydrolysis to generate hydroxy radicals (OH *) having high oxidizing power. This hydroxy radical decomposes organic matter. The decomposition is performed in the process of organic matter → organic acid → carbonic acid or the like (inorganic matter). An organic acid is temporarily generated in the process of organic matter decomposition by ozone. Therefore, the acidity is maintained under the influence of the organic acid produced during the treatment. Since the temporarily generated organic acid is treated with an inorganic substance such as carbonic acid as the treatment proceeds, the pH of the treatment liquid becomes neutral from the acidic side.

そこで、本実施形態においては、pH計1を用いて処理液のpHを測定し、pH計1の値が中性に戻ったのを確認し、オゾン21による分解処理終了として排出弁6を開し、処理終了した処理済液31を排出する。   Therefore, in the present embodiment, the pH of the treatment liquid is measured using the pH meter 1 to confirm that the value of the pH meter 1 has returned to neutrality, and the discharge valve 6 is opened when the decomposition treatment by the ozone 21 is completed. Then, the processed liquid 31 that has been processed is discharged.

ここで、図2を用いて、pH値の変化について説明する。図2(A)は、オゾン分解中の処理対象液のTOC濃度の変化を示している。また、図2(B)は、オゾン分解中の処理対象液のpHの変化を示している。図2(A),(B)の横軸は廃液処理時間(h)を示している。   Here, the change in pH value will be described with reference to FIG. FIG. 2A shows a change in the TOC concentration of the liquid to be treated during the ozonolysis. FIG. 2 (B) shows the change in pH of the liquid to be treated during ozonolysis. 2A and 2B, the horizontal axis represents the waste liquid treatment time (h).

図2(A)に示すように、処理対象液のTOC濃度は、廃液処理時間の経過と共に減少し、廃棄処理終了時には0ppmとなる。一方、図2(B)に示すように、処理対象液のpHは、処理開始時はほぼ中性を示しているが、処理が進むと、処理中に生成する有機酸の影響で酸性になり、酸性を維持する。一時的に生成された有機酸は、処理が進むにつれ炭酸等無機物に処理されるため、処理液のpHが酸性側から中性になる。図2(B)に示す状態では、廃液処理時間40hで、pHが7.0となり、中性となっている。この時点では、図2(A)に示すように、TOC濃度も0ppmとなっており、廃液処理が終了していることが理解される。したがって、本実施形態では、一般的なpH計を用いることができ、サンプリングや分析を不要として、容易に短時間に処理終了が確認できる。   As shown in FIG. 2A, the TOC concentration of the liquid to be treated decreases with the lapse of the waste liquid treatment time and becomes 0 ppm at the end of the waste treatment. On the other hand, as shown in FIG. 2 (B), the pH of the solution to be treated is almost neutral at the start of the treatment, but when the treatment proceeds, it becomes acidic due to the influence of the organic acid generated during the treatment. Maintain acidity. Since the temporarily generated organic acid is treated with an inorganic substance such as carbonic acid as the treatment proceeds, the pH of the treatment liquid becomes neutral from the acidic side. In the state shown in FIG. 2 (B), the pH becomes 7.0 at a waste liquid treatment time of 40 h, which is neutral. At this point in time, as shown in FIG. 2A, the TOC concentration is also 0 ppm, and it is understood that the waste liquid treatment has been completed. Therefore, in this embodiment, a general pH meter can be used, and sampling and analysis are unnecessary, and the end of the process can be easily confirmed in a short time.

以上説明したように、本実施形態によれば、処理対象液を循環しながら、一般的なpH計を用いることができ、処理終了の確認を容易に短時間で行うことができる。   As described above, according to the present embodiment, a general pH meter can be used while circulating the liquid to be treated, and the completion of the treatment can be easily confirmed in a short time.

次に、図3を用いて、本発明の第2の実施形態によるオゾン分解装置の構成について説明する。
図3は、本発明の第2の実施形態によるオゾン分解装置の構成を示す構成図である。なお、図1と同一符号は、同一部分を示している。
Next, the configuration of the ozonolysis apparatus according to the second embodiment of the present invention will be described with reference to FIG.
FIG. 3 is a block diagram showing a configuration of an ozonolysis apparatus according to the second embodiment of the present invention. The same reference numerals as those in FIG. 1 indicate the same parts.

図1に示した実施形態では、オゾンを循環させるようにしていたのに対して、本実施形態では、図1に示したオゾン分解装置の循環する配管、オゾンミキサ4が無く、その代わりに、オゾン分解槽3にオゾン供給機2からのオゾン21を直接投入している。pH計1は、オゾン分解槽3に設けられており、pH値を測定するようにしている。オゾン供給機2から供給されたオゾン21がオゾン分解槽3の処理対象液11に溶け込みオゾンによる分解処理が始まり、有機酸が発生しpH計1の数値が酸性側に振られる。処理中は生成する有機酸の影響で酸性を維持し、処理が終了すると有機酸が炭酸等に分解されるのでpH計1の値が中性にもどる。pH計の値が中性に戻ったのを確認し、オゾン21による分解処理終了として排出弁6を開し、処理終了した処理済液31を排出する。   In the embodiment shown in FIG. 1, ozone is circulated. In this embodiment, however, there is no circulating pipe and ozone mixer 4 of the ozonolysis apparatus shown in FIG. The ozone 21 from the ozone feeder 2 is directly put into the decomposition tank 3. The pH meter 1 is provided in the ozonolysis tank 3, and measures the pH value. The ozone 21 supplied from the ozone supplier 2 is dissolved in the treatment target liquid 11 of the ozone decomposition tank 3 and the decomposition process using ozone is started, an organic acid is generated, and the numerical value of the pH meter 1 is shaken to the acid side. During the treatment, the acidity is maintained under the influence of the generated organic acid. When the treatment is completed, the organic acid is decomposed into carbonic acid and the like, so that the value of the pH meter 1 returns to neutral. After confirming that the value of the pH meter has returned to neutral, the discharge valve 6 is opened at the end of the decomposition process by the ozone 21, and the processed liquid 31 that has been processed is discharged.

以上説明したように、本実施形態によれば、処理対象液をオゾン分解槽だけでオゾン分解するようにしながら、一般的なpH計を用いることができ、処理終了の確認を容易に短時間で行うことができる。   As described above, according to the present embodiment, a general pH meter can be used while ozonolysis of the liquid to be treated only in an ozonolysis tank, and confirmation of the end of the treatment can be easily performed in a short time. It can be carried out.

次に、図4を用いて、本発明の第3の実施形態によるオゾン分解装置の構成について説明する。
図4は、本発明の第3の実施形態によるオゾン分解装置の構成を示す構成図である。なお、図1と同一符号は、同一部分を示している。
Next, the configuration of the ozonolysis apparatus according to the third embodiment of the present invention will be described with reference to FIG.
FIG. 4 is a configuration diagram showing a configuration of an ozonolysis apparatus according to the third embodiment of the present invention. The same reference numerals as those in FIG. 1 indicate the same parts.

図1に示した実施形態では、オゾン分解槽を用いてオゾンを分解するようにしていたのに対して、本実施形態では、図1に示したオゾン分解槽3を無くし、その代わりに、オゾンミキサ4により装置内を廃液が移動する間にオゾン21を供給し、分解処理を行うものである。この場合、pH計1は、処理装置出口に設け、出口から処理済液31が排出される際のpHを測定し、処理の状態を確認する。   In the embodiment shown in FIG. 1, ozone is decomposed using an ozone decomposition tank, but in this embodiment, the ozone decomposition tank 3 shown in FIG. 1 is eliminated, and an ozone mixer is used instead. In step 4, ozone 21 is supplied while the waste liquid moves through the apparatus, and the decomposition process is performed. In this case, the pH meter 1 is provided at the outlet of the processing apparatus, measures the pH when the processed liquid 31 is discharged from the outlet, and confirms the processing state.

以上説明したように、本実施形態によれば、処理対象液を溜めること無くオゾン分解しながら、一般的なpH計を用いることができ、処理終了の確認を容易に短時間で行うことができる。
As described above, according to the present embodiment, a general pH meter can be used while ozonolysis without accumulating the liquid to be treated, and confirmation of the end of the treatment can be easily performed in a short time. .

本発明の第1の実施形態によるオゾン分解装置の構成を示す構成図である。It is a block diagram which shows the structure of the ozonolysis apparatus by the 1st Embodiment of this invention. 本発明の第1の実施形態によるオゾン分解装置における測定原理の説明図である。It is explanatory drawing of the measurement principle in the ozonolysis apparatus by the 1st Embodiment of this invention. 本発明の第2の実施形態によるオゾン分解装置の構成を示す構成図である。It is a block diagram which shows the structure of the ozonolysis apparatus by the 2nd Embodiment of this invention. 本発明の第3の実施形態によるオゾン分解装置の構成を示す構成図である。It is a block diagram which shows the structure of the ozonolysis apparatus by the 3rd Embodiment of this invention.

符号の説明Explanation of symbols

1…pH計
2…オゾン供給機
3…オゾン分解槽
4…オゾンミキサ
5…ポンプ
6…排出弁
11…処理対象液
21…オゾン
31…処理済液
DESCRIPTION OF SYMBOLS 1 ... pH meter 2 ... Ozone supply machine 3 ... Ozone decomposition tank 4 ... Ozone mixer 5 ... Pump 6 ... Discharge valve 11 ... Process target liquid 21 ... Ozone 31 ... Processed liquid

Claims (5)

オゾンによる処理対象液中の有機物を分解処理するオゾン分解装置において、
前記有機物のオゾンによる分解時に、前記処理対象液のTOCが時間とともに減少し、そのとき、pHは、一旦酸性になった後、有機酸が減少すると、再び中性となる特性を有し、
pHを検出するpH計を備え、
このpH計により、前記処理対象液のpHが酸性から再び中性になることを確認することによりオゾン分解処理の状況を監視することを特徴とするオゾン分解装置。
In the ozone decomposition device that decomposes organic matter in the liquid to be treated with ozone,
At the time of decomposition of the organic matter by ozone, the TOC of the liquid to be treated decreases with time, and at that time, the pH once becomes acidic and then has a characteristic of becoming neutral again when the organic acid is reduced,
equipped with a pH meter to detect pH,
An ozonolysis apparatus for monitoring the status of the ozonolysis treatment by confirming that the pH of the solution to be treated changes from acidic to neutral again with this pH meter.
請求項1記載のオゾン分解装置において、
オゾン分解槽に供給された処理対象液は、戻り配管による循環ラインにより循環するとともに、この循環ライン中にオゾンが供給される構成であり、
前記pH計は、前記循環ライン中に設けたことを特徴とするオゾン分解装置。
The ozonolysis apparatus according to claim 1,
The treatment target liquid supplied to the ozonolysis tank is circulated by a circulation line by a return pipe, and ozone is supplied into the circulation line.
The ozonolysis apparatus characterized in that the pH meter is provided in the circulation line.
請求項1記載のオゾン分解装置において、
オゾン分解槽に供給された処理対象液に対してオゾンが供給される構成であり、
前記pH計は、前記オゾン分解槽中に設けたことを特徴とするオゾン分解装置。
The ozonolysis apparatus according to claim 1,
It is a configuration in which ozone is supplied to the treatment target liquid supplied to the ozonolysis tank,
The ozonolysis apparatus characterized in that the pH meter is provided in the ozonolysis tank.
請求項1記載のオゾン分解装置において、
処理対象液を溜めることなく処理する構成であり、
前記pH計は、オゾン分解装置の出口に設けたことを特徴とするオゾン分解装置。
The ozonolysis apparatus according to claim 1,
It is configured to process without storing the liquid to be processed,
The ozonolysis apparatus, wherein the pH meter is provided at an outlet of the ozonolysis apparatus.
オゾンによる処理対象液中の有機物を分解処理するオゾン分解方法において、
前記有機物のオゾンによる分解時に、前記処理対象液のTOCが時間とともに減少し、そのとき、pHは、一旦酸性になった後、有機酸が減少すると、再び中性となる特性を有し、
前記処理対象液のpHが酸性から再び中性になることを確認することによりオゾン分解処理の状況を監視することを特徴とするオゾン分解方法
In the ozone decomposition method for decomposing organic matter in the liquid to be treated with ozone,
At the time of decomposition of the organic matter by ozone, the TOC of the liquid to be treated decreases with time, and at that time, the pH once becomes acidic and then has a characteristic of becoming neutral again when the organic acid is reduced,
An ozonolysis method characterized by monitoring the status of the ozonolysis treatment by confirming that the pH of the liquid to be treated changes from acidic to neutral again .
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