JP5532017B2 - Industrial wastewater treatment method and treatment equipment - Google Patents
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Description
本発明は、各種の生産設備から排出される産業排水の処理方法及び処理装置に関する。 The present invention relates to a method and apparatus for treating industrial wastewater discharged from various production facilities.
各種産業において限りある水資源の節約および地球環境保全の観点から産業排水の再利用が積極的に行われている。また、生産している製品により様々な薬品が使用されているため、排水処理が必須である。 Industrial wastewater is actively reused from the viewpoint of conserving limited water resources and protecting the global environment in various industries. In addition, wastewater treatment is essential because various chemicals are used depending on the products being produced.
例えば、半導体製造工場では半導体のエッチング処理のため大量のフッ酸が使用されており、フッ素イオンを含んだ産業排水が大量に排出される。 For example, a large amount of hydrofluoric acid is used in semiconductor manufacturing plants for semiconductor etching, and a large amount of industrial wastewater containing fluorine ions is discharged.
フッ素イオンを含む産業排水の処理は、塩化カルシウム、水酸化カルシウム、炭酸カルシウム、硫酸カルシウムなどのカルシウム塩を加えて排水中のフッ素イオンを不溶化させた後、固液分離して排水中からフッ素を除去する方法が、従来より行われている。 Treatment of industrial wastewater containing fluoride ions is accomplished by adding calcium salts such as calcium chloride, calcium hydroxide, calcium carbonate, and calcium sulfate to insolubilize fluoride ions in the wastewater, and then separating the solid and liquid to remove fluorine from the wastewater. The removal method has been conventionally performed.
フッ素イオンの排出基準値は８ｍｇ／Ｌ以下であるので、各メーカーではこの基準値を超えないような排水処理を実施している。 Since the emission standard value of fluoride ions is 8 mg / L or less, each manufacturer implements waste water treatment so as not to exceed this standard value.
特許文献１には、フッ素含有水にカルシウム塩を添加してフッ素をフッ化カルシウムとして沈殿分離する方法において、該フッ素含有水中のフッ素イオン量及びカルシウムと難溶性塩を生成するフッ素イオン以外のイオンの量に基いて、前記カルシウム塩の添加量を設定することを特徴とするフッ素含有水の処理方法が開示されている。 In Patent Document 1, in a method of adding calcium salt to fluorine-containing water and precipitating and separating fluorine as calcium fluoride, the amount of fluorine ions in the fluorine-containing water and ions other than fluorine ions that form calcium and sparingly soluble salts A method for treating fluorine-containing water is disclosed in which the addition amount of the calcium salt is set based on the amount of the calcium salt.
産業排水中に含まれるフッ素イオンなどの処理対象成分の濃度を正確に把握できれば、処理薬剤の使用量を最適化できる。例えば、フッ素イオンを測定する測定器として、フッ素イオンを選択的に透過するフッ化ランタンを用いたイオン電極方式による測定器がある。この測定器は、低価格で、取り扱いが容易であり、排水処理の監視に広く用いられているが、排水中の陰イオンや金属イオン等の共存成分の影響を受け易く、実際の濃度と、測定濃度とで乖離が生じることが多かった。イオンクロマトグラフなどの精密分析であれば、処理対象成分の濃度を正確に測定できるが、測定に時間や手間を要するため、処理対象成分の濃度に変動が生じた場合、速やかに対応することができなかった。このため、従来より、処理薬剤を過剰に添加して排水基準値を満たすように処理しており、処理薬剤の消費コストや、汚泥処理コストが嵩む問題があった。 If the concentration of components to be treated such as fluorine ions contained in industrial wastewater can be accurately grasped, the amount of treatment chemical used can be optimized. For example, as a measuring instrument for measuring fluorine ions, there is an ion electrode type measuring instrument using lanthanum fluoride that selectively transmits fluorine ions. This measuring instrument is low in price, easy to handle, and widely used for monitoring wastewater treatment, but is easily affected by coexisting components such as anions and metal ions in wastewater, In many cases, there was a deviation from the measured concentration. With precision analysis such as ion chromatography, it is possible to accurately measure the concentration of the target component, but it takes time and effort to measure, so if the concentration of the target component fluctuates, it can respond quickly. could not. For this reason, conventionally, the treatment chemical is excessively added so as to satisfy the drainage standard value, and there is a problem that the consumption cost of the treatment chemical and the sludge treatment cost increase.
よって、本発明の目的は、処理薬剤の使用量を必要最小限に抑えつつ、処理対象成分を確実に処理して、経済的に産業排水を処理することが可能な産業排水の処理方法及び産業排水の処理装置を提供することにある。 Therefore, an object of the present invention is to provide an industrial wastewater treatment method and industry capable of economically treating industrial wastewater by reliably treating the components to be treated while minimizing the amount of treatment chemical used. The object is to provide a wastewater treatment device.
本発明の産業排水の処理方法は、産業排水中に含まれる処理対象成分を、処理薬剤によって処理して排水する産業排水の処理方法において、前記産業排水中の前記処理対象成分の濃度を測定する工程と、前記処理対象成分の濃度の測定結果に影響を与える共存成分の濃度データを取得する工程と、前記共存成分の濃度に基づいて前記処理対象成分の測定濃度を補正して、推定される真の処理対象成分の濃度を求める工程と、前記産業排水の流量及び排水時間のデータを取得する工程と、前記推定される真の処理対象成分の濃度と前記産業排水の流量及び排水時間に基づいて、前記処理薬剤の添加量を算出する工程と、前記処理薬剤を前記算出された添加量で添加する工程とを含むことを特徴とする。 The industrial wastewater treatment method of the present invention measures the concentration of the processing target component in the industrial wastewater in the industrial wastewater processing method of treating and draining the processing target component contained in the industrial wastewater with a treatment chemical. Estimated by correcting the measured concentration of the processing target component based on the step, the step of acquiring concentration data of the coexisting component affecting the measurement result of the concentration of the processing target component, and the concentration of the coexisting component Based on the step of obtaining the concentration of the true treatment target component , the step of obtaining the flow rate and drainage time data of the industrial wastewater, the concentration of the true treatment target component and the flow rate and drainage time of the industrial wastewater. A step of calculating the amount of the treatment chemical added, and a step of adding the treatment chemical in the calculated amount of addition.
本発明の産業排水の処理方法によれば、産業排水中の処理対象成分の測定濃度を、該測定結果に影響を与える共存成分の濃度に基づいて補正して、推定される真の処理対象成分の濃度を求め、その推定される真の処理対象成分の濃度と産業排水の流量及び排水時間に基づいて処理薬剤の添加量を算出し、処理薬剤を算出された添加量で添加することにより、処理薬剤の使用量を必要最小限に抑えつつ、処理対象成分を確実に処理して、経済的な排水処理が可能となる。 According to the industrial wastewater treatment method of the present invention, the measured concentration of the treatment target component in the industrial wastewater is corrected based on the concentration of the coexisting component affecting the measurement result, and the estimated true treatment target component By calculating the amount of the treatment agent based on the estimated concentration of the true treatment target component and the flow rate of the industrial wastewater and the drainage time, and adding the treatment agent at the calculated addition amount, While minimizing the amount of treatment chemical used, it is possible to reliably treat the components to be treated and to perform economical wastewater treatment.
本発明の産業排水の処理方法の前記共存成分の濃度データを取得する工程は、前記産業排水の元となる水溶液の配合データ及び／又は前記共存成分の測定データを取得することによりなされ、前記産業排水の流量及び排水時間のデータを取得する工程は、前記産業排水を生じる生産工程のプロセスデータを取得することによってなされることが好ましい。この態様によれば、産業排水の元となる水溶液の配合データ及び／又は共存成分の測定データを取得することにより、変動しやすい成分については測定データによって求め、変動しにくい成分については配合データから求めることができるので、共存成分の濃度を簡易迅速に求めることができる。また、産業排水を生じる生産工程のプロセスデータを取得することにより、産業排水の流量及び排水時間を簡易迅速に求めることができる。 The step of acquiring the concentration data of the coexisting component of the industrial wastewater treatment method of the present invention is performed by acquiring the mixing data of the aqueous solution that is the source of the industrial wastewater and / or the measurement data of the coexisting component. It is preferable that the process of acquiring the wastewater flow rate and drainage time data is performed by acquiring process data of the production process that produces the industrial wastewater. According to this aspect, by obtaining the blending data of the aqueous solution that is the source of industrial wastewater and / or measurement data of the coexisting components, the components that are likely to fluctuate are obtained from the measurement data, and the components that are not likely to vary are blended from the blending data. Since it can obtain | require, the density | concentration of a coexisting component can be calculated | required simply and rapidly. Moreover, the flow rate and drainage time of an industrial wastewater can be calculated | required simply and quickly by acquiring the process data of the production process which produces an industrial wastewater.
本発明の産業排水の処理方法の前記推定される真の処理対象成分の濃度を求める工程は、共存成分毎に予め補正率を求めておき、各共存成分の濃度にそれぞれの補正率を掛けて該共存成分に起因する誤差量を算出し、各共存成分に起因する誤差量の合計量を算出し、この合計量を前記処理対象成分の測定濃度に対して補正することによってなされることが好ましい。この態様によれば、共存成分毎に予め補正率を求めておくことにより、共存成分に起因する補正量を迅速に求めることができる。 The step of obtaining the estimated concentration of the true treatment target component of the industrial wastewater treatment method of the present invention obtains a correction factor in advance for each coexisting component, and multiplies the concentration of each coexisting component by the respective correction factor. It is preferable that this is done by calculating the amount of error due to the coexisting component, calculating the total amount of error due to each coexisting component, and correcting this total amount with respect to the measured concentration of the processing target component. . According to this aspect, the correction amount resulting from the coexistence component can be quickly obtained by obtaining the correction rate in advance for each coexistence component.
本発明の産業排水の処理方法は、前記処理対象成分が、フッ素イオンであり、前記処理薬剤がカルシウム塩であることが好ましい。 In the industrial wastewater treatment method of the present invention, it is preferable that the component to be treated is fluoride ion and the treatment agent is a calcium salt.
また、本発明の産業排水の処理装置は、産業排水中に含まれる処理対象成分を、処理薬剤によって処理して排水する産業排水の処理装置において、前記産業排水中の前記処理対象成分の濃度を測定する処理対象成分濃度測定装置と、前記処理対象成分の濃度の測定結果に影響を与える共存成分の濃度データ取得手段と、前記産業排水の流量及び排水時間のデータ取得手段と、前記処理薬剤を前記産業排水に添加する処理薬剤添加手段と、前記共存成分の濃度に基づいて前記処理対象成分の測定濃度を補正して、推定される真の処理対象成分の濃度を算出し、該推定される真の処理対象成分の濃度と前記産業排水の流量及び排水時間とに基づいて前記処理薬剤の添加量を算出する演算装置と、該演算装置からの信号を受けて前記処理薬剤を前記算出された添加量で添加する制御装置とを含むことを特徴とする。 Further, the industrial wastewater treatment apparatus of the present invention is the industrial wastewater treatment apparatus for treating and draining the treatment target component contained in the industrial wastewater with a treatment chemical, and the concentration of the treatment target component in the industrial wastewater is determined. A concentration measuring device for measuring the concentration of a processing target component, concentration data acquisition means for coexisting components that affect the measurement result of the concentration of the processing target component , data acquisition means for the flow rate and drainage time of the industrial waste water, and the processing chemical. Correcting the measured concentration of the treatment target component based on the concentration of the coexisting component with the treatment chemical addition means to be added to the industrial wastewater, calculating the estimated concentration of the true treatment target component an arithmetic unit for calculating the amount of the processing agent on the basis of the flow rate and drainage time of the industrial waste water and the concentration of the true processed component, wherein the processing agent receiving a signal from the arithmetic unit Characterized in that it comprises a controller for adding the addition amount issued.
本発明の産業排水の処理装置の前記共存成分の濃度データ取得手段は、前記産業排水の元となる水溶液の配合データベース及び／又は前記共存成分の測定装置からなり、前記産業排水の流量及び排水時間のデータを取得手段は、前記産業排水を生じる生産工程のプロセスデータベースからなることが好ましい。 The concentration data acquisition means of the coexisting component of the industrial wastewater treatment apparatus of the present invention comprises an aqueous solution formulation database and / or the coexisting component measuring device that is the source of the industrial wastewater, and the industrial wastewater flow rate and drainage time. The data acquisition means preferably comprises a process database of the production process that produces the industrial wastewater.
本発明の産業排水の処理装置は、前記共存成分毎に予め補正率を求めた補正データベースを更に有し、前記演算装置は、各共存成分の濃度に、前記補正データベースから得られるそれぞれの補正率を掛けて該共存成分に起因する誤差量を算出し、各共存成分に起因する誤差量の合計量を算出し、この合計量を前記処理対象成分の測定濃度に対して補正することにより、前記推定される真の処理対象成分の濃度を算出するように構成されていることが好ましい。 The industrial wastewater treatment apparatus of the present invention further includes a correction database in which a correction factor is obtained in advance for each coexisting component, and the arithmetic unit calculates each correction factor obtained from the correction database for the concentration of each coexisting component. To calculate the amount of error due to the coexisting component, calculate the total amount of error due to each coexisting component, and correct the total amount with respect to the measured concentration of the processing target component, It is preferable that the estimated concentration of the true processing target component is calculated .
本発明の産業排水の処理装置は、前記産業排水が半導体製造工程のエッチング処理で生じる、フッ素イオンを含有する排水であり、前記処理薬剤がカルシウム塩であり、前記処理対象成分濃度測定装置は、フッ素イオンを選択的に透過するフッ化ランタンを用いたイオン電極方式による簡易型フッ化物イオン濃度計であることが好ましい。 The industrial wastewater treatment apparatus of the present invention is a wastewater containing fluorine ions, which is produced by an etching process in a semiconductor manufacturing process, the treatment agent is a calcium salt, A simple fluoride ion concentration meter by an ion electrode method using lanthanum fluoride that selectively transmits fluorine ions is preferable.
本発明によれば、産業排水中の処理対象成分の測定濃度を、該測定結果に影響を与える共存成分の濃度に基づいて補正して、推定される真の処理対象成分の濃度を求め、その推定される真の処理対象成分の濃度と産業排水の流量及び排水時間に基づいて処理薬剤の添加量を算出し、処理薬剤を算出された添加量で添加することにより、処理薬剤の使用量を必要最小限に抑えつつ、処理対象成分を確実に処理して、経済的な排水処理が可能となる。 According to the present invention, the measured concentration of the processing target component in the industrial wastewater is corrected based on the concentration of the coexisting component that affects the measurement result, and the estimated concentration of the true processing target component is obtained. Calculate the amount of treatment chemical added based on the estimated concentration of the true treatment target , the industrial wastewater flow rate and drainage time, and add the treatment chemical at the calculated addition amount to reduce the amount of treatment chemical used. While minimizing the necessary amount, the component to be treated can be reliably treated, and economical wastewater treatment can be performed.
以下、図面を参照して、本発明の産業排水の処理装置の実施形態を説明する。ただし、これらの例は本発明の範囲を限定するものではない。 Hereinafter, with reference to the drawings, an embodiment of the industrial wastewater treatment apparatus of the present invention will be described. However, these examples do not limit the scope of the present invention.
図１，２には、半導体製造設備１の半導体製造工程のエッチング処理で生じる、フッ素イオンを含有する産業排水の処理に適用した一実施形態が示されている。したがって、この実施形態では、フッ素イオンが、本発明における処理対象成分に該当する。なお、産業排水としては、半導体製造設備から排出されるものに限らず、例えば液晶製造、太陽電池製造、金属表面加工等の生産設備から排出される産業排水の処理にも適用することができる。 1 and 2 show an embodiment applied to the treatment of industrial wastewater containing fluorine ions, which is generated by the etching process in the semiconductor manufacturing process of the semiconductor manufacturing facility 1. Therefore, in this embodiment, a fluorine ion corresponds to the process target component in this invention. Industrial wastewater is not limited to those discharged from semiconductor manufacturing equipment, and can also be applied to treatment of industrial wastewater discharged from production equipment such as liquid crystal manufacturing, solar cell manufacturing, and metal surface processing.
図１に示すように、この産業排水処理装置は、半導体製造設備１の排水処理に適用されるものである。半導体製造設備１は、エッチング処理工程及び洗浄処理工程を行い、フッ素イオンを含む産業排水が、配管Ｌ１を通して装置外に流出される。 As shown in FIG. 1, this industrial wastewater treatment apparatus is applied to wastewater treatment of a semiconductor manufacturing facility 1. The semiconductor manufacturing facility 1 performs an etching process and a cleaning process, and industrial wastewater containing fluorine ions flows out of the apparatus through the pipe L1.
半導体製造設備１には、原料及び洗浄液の配合組成などを記憶させた配合データベース１０が設けられている。また、該設備におけるプロセスデータ信号を送信するプロセスデータ信号送信器１１が設けられている。このプロセスデータ信号としては、例えば、排水を生じる各処理の処理時間（開始時間、終了時間等）、各処理によって生じる排水時間（開始時間、終了時間等）、各処理によって生じる排水量等が挙げられる。 The semiconductor manufacturing facility 1 is provided with a blending database 10 in which blending compositions of raw materials and cleaning liquids are stored. Further, a process data signal transmitter 11 for transmitting a process data signal in the facility is provided. Examples of the process data signal include the processing time (start time, end time, etc.) of each process that generates drainage, the drainage time (start time, end time, etc.) generated by each process, and the amount of drainage generated by each process. .
配管Ｌ１は、フッ素イオン濃度計１２が設置され、原水タンク３に連結している。この実施形態では、フッ素イオン濃度計１２が、本発明における処理対象成分濃度測定装置に相当する。フッ素イオン濃度計としては、連続して測定できるものであればよく、排水処理において従来一般的に用いられているものを用いることができる。例えば、フッ素イオンを選択的に透過するフッ化ランタンを用いたイオン電極方式による簡易型フッ化物イオン濃度計は、安価で取り扱い性が良いため、好ましく用いることができる。 The pipe L1 is provided with a fluorine ion concentration meter 12 and connected to the raw water tank 3. In this embodiment, the fluorine ion concentration meter 12 corresponds to the processing target component concentration measuring apparatus in the present invention. Any fluorine ion concentration meter may be used as long as it can be continuously measured, and a conventional one generally used in wastewater treatment can be used. For example, a simple fluoride ion densitometer based on an ion electrode method using lanthanum fluoride that selectively transmits fluorine ions can be preferably used because it is inexpensive and easy to handle.
原水タンク３から、配管Ｌ２が伸びて、沈殿槽４に接続している。配管Ｌ２には、カルシウム塩タンク５内のカルシウム塩が、ポンプＰ１を介して流入するようになっている。カルシウム塩の添加量は、演算装置２０により算出された添加量となるように、演算装置２０からの信号を受けて、制御装置３０によってポンプＰ１を制御することによって調整されるようになっている。カルシウム塩としては、塩化カルシウム、水酸化カルシウム、炭酸カルシウム、硫酸カルシウム等が用いられる。この実施形態では、カルシウム塩が、本発明における処理薬剤に相当する。 A pipe L <b> 2 extends from the raw water tank 3 and is connected to the settling tank 4. The calcium salt in the calcium salt tank 5 flows into the pipe L2 via the pump P1. The addition amount of the calcium salt is adjusted by receiving a signal from the calculation device 20 and controlling the pump P1 by the control device 30 so that the addition amount calculated by the calculation device 20 is obtained. . As the calcium salt, calcium chloride, calcium hydroxide, calcium carbonate, calcium sulfate and the like are used. In this embodiment, the calcium salt corresponds to the treatment agent in the present invention.
沈殿槽４には、凝集剤タンク６内の凝集剤が、ポンプＰ２を介して流入するようになっている。凝集剤としては、ポリ塩化アルミニウム等が挙げられる。沈殿槽４の底部には、配管Ｌ３が設けられており、底部に沈降した汚泥は、配管Ｌ３を通して系外に排出される。また、沈殿槽４の上部側壁には、配管Ｌ４が設けられており、上澄水が下水放流される。 The coagulant in the coagulant tank 6 flows into the settling tank 4 via the pump P2. Examples of the aggregating agent include polyaluminum chloride. A pipe L3 is provided at the bottom of the settling tank 4, and the sludge settled on the bottom is discharged out of the system through the pipe L3. A pipe L4 is provided on the upper side wall of the settling tank 4, and the supernatant water is discharged into the sewage.
次に、上記した処理装置を用いて半導体製造設備１の半導体製造工程のエッチング処理で生じる、フッ素イオンを含有する産業排水を処理する場合を例に挙げて、本発明の産業排水の処理方法の一実施形態を説明する。 Next, an example of processing industrial wastewater containing fluorine ions generated by etching processing in the semiconductor manufacturing process of the semiconductor manufacturing facility 1 using the above-described processing apparatus will be described. One embodiment will be described.
半導体製造設備１から排出される産業排水を、配管Ｌ１を通して原水タンクに一時的に貯留する。 Industrial wastewater discharged from the semiconductor manufacturing facility 1 is temporarily stored in the raw water tank through the pipe L1.
配管Ｌ１を流通する産業排水のフッ素イオン濃度は、フッ素イオン濃度計１２で測定し、演算装置２０に入力する。 The fluorine ion concentration of the industrial wastewater flowing through the pipe L <b> 1 is measured by the fluorine ion concentration meter 12 and input to the arithmetic unit 20.
また、半導体製造設備１におけるプロセスデータ信号を、プロセスデータ信号送信器１１から演算装置２０に入力する。 In addition, a process data signal in the semiconductor manufacturing facility 1 is input from the process data signal transmitter 11 to the arithmetic unit 20.
また、フッ素イオン濃度計１２におけるフッ素イオン濃度の測定結果に影響を与える共存成分の濃度データを配合データベース１０から取得して、演算装置２０に入力する。共存成分の濃度データとしては、配合データベース１０の他に、半導体製造設備１から排出される産業排水の一部を取出して分析した測定値を用いてもよい。なお、共存成分の濃度データは、生産工程で使用される原料及び洗浄液が決められていれば、殆ど変動しないと考えられるため、産業排水の分析は毎回行う必要がなく、使用原料の変更や、製品変更があった場合にのみ測定すればよい。更に、共存成分の濃度データとして、一部の共存成分のみ、産業排水を分析した測定値を用い、その他の成分については配合データベース１０の値を用いてもよい。 Further, the concentration data of coexisting components that affect the measurement result of the fluorine ion concentration in the fluorine ion concentration meter 12 is acquired from the blending database 10 and input to the arithmetic unit 20. As the concentration data of the coexisting components, in addition to the blending database 10, a measurement value obtained by analyzing a part of industrial wastewater discharged from the semiconductor manufacturing facility 1 may be used. It should be noted that the concentration data of coexisting components is considered to hardly fluctuate if the raw materials and cleaning liquid used in the production process are determined, so it is not necessary to analyze the industrial wastewater every time. It is only necessary to measure when there is a product change. Furthermore, as the concentration data of the coexisting components, only a part of the coexisting components may be measured values obtained by analyzing industrial wastewater, and values of the blending database 10 may be used for other components.
原水タンク３に貯留した産業排水は、配管Ｌ２から引き抜き、カルシウム塩を添加して沈殿槽４に送液する。 The industrial wastewater stored in the raw water tank 3 is extracted from the pipe L2, added with calcium salt, and sent to the settling tank 4.
カルシウム塩の添加量は、演算装置２０により算出された添加量となるように、演算装置２０からの信号を受けて、制御装置３０によってポンプＰ１を制御することによって調整する。以下、演算装置２０で行われるカルシウム塩の添加量の算出処理について、図２を用いて説明する。 The addition amount of the calcium salt is adjusted by receiving a signal from the calculation device 20 and controlling the pump P1 by the control device 30 so that the addition amount calculated by the calculation device 20 is obtained. Hereinafter, the calculation process of the addition amount of the calcium salt performed by the arithmetic unit 20 will be described with reference to FIG.
この演算装置２０は、フッ素イオン濃度算出部２１と、処理薬剤添加量算出部２２とを備える。 The computing device 20 includes a fluorine ion concentration calculation unit 21 and a treatment agent addition amount calculation unit 22.
フッ素イオン濃度算出部２１では、共存成分毎に予め補正率を求めた補正データベースを参照して、各共存成分の濃度に、それぞれの補正率を掛けて誤差量を算出し、各共存成分に起因する誤差量の合計量と、フッ素イオン濃度計１２の測定値とを合計することにより、補正されたフッ素イオン濃度、すなわち、推定される真のフッ素イオン濃度を算出する。すなわち、下式（１），（２）の演算を行って、推定される真のフッ素イオン濃度を算出する。 The fluorine ion concentration calculation unit 21 refers to a correction database obtained in advance for each coexisting component, calculates the error amount by multiplying the concentration of each coexisting component by the respective correction factor, and is attributed to each coexisting component. The corrected fluorine ion concentration, that is, the estimated true fluorine ion concentration is calculated by summing the total amount of error to be performed and the measured value of the fluorine ion concentration meter 12. That is, the estimated true fluorine ion concentration is calculated by calculating the following expressions (1) and (2).
（各共存成分に起因する誤差量の合計量）
＝（成分Ａ１の濃度×成分Ａ１の補正率）＋（成分Ａ２の濃度×成分Ａ２の補正率）・・・＋（成分Ａｎの濃度×成分Ａｎの補正率） ・・・（１）
（真のフッ素イオン濃度）＝（フッ素イオン濃度計１１の測定値）＋（各共存成分に起因する誤差量の合計量） ・・・（２）
(Total amount of error due to each coexisting component)
= (Component correction factor A 1 concentration × component A 1) + (correction factor concentration × component A 2 components A 2) · · · + (correction factor concentration × components A n components A n) · ·・ (1)
(True fluorine ion concentration) = (measured value of the fluorine ion concentration meter 11) + (total amount of error caused by each coexisting component) (2)
ここで、補正データベースの補正率は、共存する成分の濃度Ｘｉにより、フッ素濃度計１２による測定値が、真のフッ素イオン濃度に対して影響を受ける値（真の濃度−測定値）をＸＦとしたとき、Ｘｆ／Ｘｉで求めることができる。 Here, the correction rate of the correction database is the value (true concentration-measured value) that the measured value by the fluorine densitometer 12 is affected by the true fluorine ion concentration by the concentration Xi of the coexisting component is XF Then, it can be obtained by Xf / Xi.
例えば、簡易型フッ化物イオンセンサ（東亜ＤＫＫ製）における、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、鉄イオン、リン酸イオン、硫酸イオン、硝酸イオンの補正率は、表１に示すような値を示す。 For example, correction factors for calcium ions, magnesium ions, aluminum ions, iron ions, phosphate ions, sulfate ions, and nitrate ions in a simple fluoride ion sensor (manufactured by Toa DKK) show values as shown in Table 1. .
例えば、カルシウムイオンを１ｍｏｌ含む場合においては、フッ素イオン濃度計１１の測定値に対して、１ｍｏｌ（カルシウムイオン濃度）×１（補正率）＝１ｍｏｌを、誤差量として加える。また、マグネシウムイオンを１ｍｏｌ含む場合においては、フッ素イオン濃度計１１の測定値に対して、１ｍｏｌ（マグネシウムイオン濃度）×０．１（補正率）＝０．１ｍｏｌを誤差量として加える。また、リン酸イオンを１ｍｏｌ含む場合においては、フッ素イオン濃度計１１の測定値に対して、１ｍｏｌ（リン酸イオン濃度）×（−０．００１）（補正率）＝−０．００１ｍｏｌを誤差量として加える。すなわち、各共存成分の濃度に、それぞれの補正率を掛けて、共存成分に起因する誤差量を算出し、その合計量を測定濃度に対して補正することによって、真の濃度を算出することができる。ただし、リン酸イオン、硫酸イオン、硝酸イオンなどの陰イオンは、極めて誤差量が小さいので、これらの濃度が低い産業排水の場合は、実質的には無視してもよい。 For example, when 1 mol of calcium ions is included, 1 mol (calcium ion concentration) × 1 (correction rate) = 1 mol is added as an error amount to the measurement value of the fluorine ion concentration meter 11. When 1 mol of magnesium ions is included, 1 mol (magnesium ion concentration) × 0.1 (correction rate) = 0.1 mol is added as an error amount to the measurement value of the fluorine ion concentration meter 11. When 1 mol of phosphate ion is included, 1 mol (phosphate ion concentration) × (−0.001) (correction rate) = − 0.001 mol with respect to the measurement value of the fluorine ion concentration meter 11 is an error amount. Add as. In other words, the true concentration can be calculated by multiplying the concentration of each coexisting component by the respective correction factor to calculate the amount of error due to the coexisting component and correcting the total amount with respect to the measured concentration. it can. However, anions such as phosphate ions, sulfate ions, and nitrate ions have a very small error amount. Therefore, in the case of industrial wastewater having a low concentration, they may be substantially ignored.
なお、共存成分の濃度は、配合データベース１０だけでなく、例えば、カルシウムなどのように製造工程中に変動し易い成分については、実際に産業排水中の当該成分濃度を測定した値を用いてもよい。 In addition, the concentration of the coexisting component is not limited to the blending database 10, but for a component that is likely to fluctuate during the manufacturing process, such as calcium, a value obtained by actually measuring the concentration of the component in industrial wastewater may be used. Good.
処理薬剤添加量算出部２２には、フッ素イオン濃度算出部２１での算出結果と、プロセスデータ信号送信器１１からのプロセスデータ信号が入力され、これらのデータに基づいてカルシウム塩の添加量を算出する。すなわち、算出されたフッ素イオン濃度と、産業排水の流量及び排水時間に基づいて、添加すべきカルシウム塩の量を算出する。 The processing agent addition amount calculation unit 22 receives the calculation result of the fluorine ion concentration calculation unit 21 and the process data signal from the process data signal transmitter 11, and calculates the addition amount of calcium salt based on these data. To do. That is, the amount of calcium salt to be added is calculated based on the calculated fluorine ion concentration, the flow rate and drainage time of industrial wastewater.
このようにして演算装置２０で算出した添加量を、制御装置３０に入力する。制御装置３０では、演算装置２０により算出された添加量となるようにポンプＰ１を制御し、カルシウム塩の添加量を調整する。 The addition amount calculated by the arithmetic device 20 in this way is input to the control device 30. In the control apparatus 30, the pump P1 is controlled so that it may become the addition amount computed by the arithmetic unit 20, and the addition amount of calcium salt is adjusted.
こうして、所定量のカルシウム塩が添加された産業排水を、沈殿槽４に送液し、ここで、ポリ塩化アルミニウム等の凝集剤を添加して、カルシウムイオンとフッ素インとが反応して生成したフッ化カルシウムを凝集沈殿させる。 In this way, the industrial wastewater to which a predetermined amount of calcium salt is added is sent to the settling tank 4, where a flocculant such as polyaluminum chloride is added, and calcium ions and fluorine-in react to form. Coagulate and precipitate calcium fluoride.
沈殿槽４の底部に設けられた配管Ｌ３から汚泥を排出するとともに、上部側壁に設けられた配管Ｌ４から上澄水を排出して下水放流する。 The sludge is discharged from the pipe L3 provided at the bottom of the settling tank 4, and the supernatant water is discharged from the pipe L4 provided on the upper side wall to discharge the sewage.
このように、本発明によれば、産業排水中の処理対象成分（この実施形態では、フッ素イオン）の測定濃度を、該測定結果に影響を与える共存成分（この実施形態では、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、鉄イオン、リン酸イオン、硫酸イオン、硝酸イオンなど）の濃度に基づいて補正して、真の処理対象成分の濃度を求め、該濃度データに基づいて、処理対象成分の処理に必要な処理薬剤（この実施形態ではカルシウム塩）の添加量を算出するので、処理薬剤の使用量を必要最小限に抑えつつ、処理対象成分を確実に処理できる。 Thus, according to the present invention, the measurement concentration of the treatment target component (fluorine ions in this embodiment) in the industrial wastewater is changed to the coexisting components (calcium ions, magnesium in this embodiment) that affect the measurement results. Ion, aluminum ion, iron ion, phosphate ion, sulfate ion, nitrate ion, etc.), the concentration of the true processing target component is obtained, and the processing of the processing target component is performed based on the concentration data. Since the amount of treatment chemical (calcium salt in this embodiment) required for the calculation is calculated, the processing target component can be reliably treated while minimizing the amount of treatment chemical used.
以下の表２に示す共存成分を含有する産業排水Ａ，Ｂについて、簡易型フッ化物イオンセンサ（東亜ＤＫＫ製）で測定した値（補正前の値）、本発明の方法により該フッ素イオン濃度を共存成分に起因する誤差量を補正して算出した値（補正後の値）、イオンクロマトグラフ法により測定した値（分析値）を表３にまとめて記す。 For industrial wastewater A and B containing the coexisting components shown in Table 2 below, the value (value before correction) measured with a simple fluoride ion sensor (manufactured by Toa DKK), the fluorine ion concentration by the method of the present invention Table 3 summarizes values calculated by correcting the amount of error due to coexisting components (values after correction) and values (analytical values) measured by ion chromatography.
上記結果から明らかなように、簡易型フッ化物イオンセンサ（東亜ＤＫＫ製）で測定したフッ素イオン濃度を、共存成分に起因する誤差量を補正することで、分析値に極めて近い値が得られた。 As is clear from the above results, the fluorine ion concentration measured by a simple fluoride ion sensor (manufactured by Toa DKK) was corrected for the amount of error caused by the coexisting components, and a value very close to the analytical value was obtained. .
１：半導体製造設備
３：原水タンク
４：沈殿槽
５：カルシウム塩タンク
６：凝集剤タンク
１１：プロセスデータ信号送信器
１２：フッ素イオン濃度計
２０：演算装置
２１：フッ素イオン濃度算出部
２２：処理薬剤添加量算出部
３０：制御装置
Ｌ１〜Ｌ４：配管
Ｐ１、Ｐ２：ポンプ
1: Semiconductor manufacturing equipment 3: Raw water tank 4: Precipitation tank 5: Calcium salt tank 6: Coagulant tank 11: Process data signal transmitter 12: Fluorine ion concentration meter 20: Computing device 21: Fluorine ion concentration calculation unit 22: Processing Drug addition amount calculation unit 30: control devices L1 to L4: piping P1, P2: pump
Claims (8)
前記産業排水中の前記処理対象成分の濃度を測定する工程と、
前記処理対象成分の濃度の測定結果に影響を与える共存成分の濃度データを取得する工程と、
前記共存成分の濃度に基づいて前記処理対象成分の測定濃度を補正して、推定される真の処理対象成分の濃度を求める工程と、
前記産業排水の流量及び排水時間のデータを取得する工程と、
前記推定される真の処理対象成分の濃度と前記産業排水の流量及び排水時間に基づいて、前記処理薬剤の添加量を算出する工程と、
前記処理薬剤を前記算出された添加量で添加する工程とを含むことを特徴とする産業排水の処理方法。 In the industrial wastewater treatment method of treating and draining the processing target components contained in industrial wastewater with treatment chemicals,
Measuring the concentration of the component to be treated in the industrial waste water;
Obtaining concentration data of coexisting components that affect the measurement results of the concentration of the component to be processed;
Correcting the measured concentration of the processing target component based on the concentration of the coexisting component to obtain the estimated true processing target component concentration ;
Obtaining the flow rate and drainage time data of the industrial wastewater;
Calculating the amount of the treatment agent to be added based on the estimated concentration of the true treatment target component and the flow rate and drainage time of the industrial wastewater;
And a step of adding the treatment chemical in the calculated addition amount.
前記産業排水中の前記処理対象成分の濃度を測定する処理対象成分濃度測定装置と、
前記処理対象成分の濃度の測定結果に影響を与える共存成分の濃度データ取得手段と、
前記産業排水の流量及び排水時間のデータ取得手段と、
前記処理薬剤を前記産業排水に添加する処理薬剤添加手段と、
前記共存成分の濃度に基づいて前記処理対象成分の測定濃度を補正して、推定される真の処理対象成分の濃度を算出し、該推定される真の処理対象成分の濃度と前記産業排水の流量及び排水時間とに基づいて前記処理薬剤の添加量を算出する演算装置と、
該演算装置からの信号を受けて前記処理薬剤を前記算出された添加量で添加する制御装置とを含むことを特徴とする産業排水の処理装置。 In the industrial wastewater treatment equipment for treating and draining the processing target components contained in industrial wastewater with treatment chemicals,
A processing target component concentration measuring device for measuring the concentration of the processing target component in the industrial waste water;
Concentration component concentration data acquisition means that affects the measurement result of the concentration of the processing target component;
Data acquisition means of the industrial wastewater flow rate and drainage time;
A treatment chemical addition means for adding the treatment chemical to the industrial waste water;
The measured concentration of the processing target component is corrected based on the concentration of the coexisting component , the estimated concentration of the true processing target component is calculated , and the estimated concentration of the true processing target component and the industrial wastewater An arithmetic device that calculates the amount of the treatment chemical added based on the flow rate and drainage time;
An industrial wastewater treatment apparatus comprising: a control device that receives the signal from the arithmetic device and adds the treatment chemical in the calculated addition amount.
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