JP2001264248A - Detection method of chlorinated organic matter and detection device - Google Patents
Detection method of chlorinated organic matter and detection deviceInfo
- Publication number
- JP2001264248A JP2001264248A JP2000081412A JP2000081412A JP2001264248A JP 2001264248 A JP2001264248 A JP 2001264248A JP 2000081412 A JP2000081412 A JP 2000081412A JP 2000081412 A JP2000081412 A JP 2000081412A JP 2001264248 A JP2001264248 A JP 2001264248A
- Authority
- JP
- Japan
- Prior art keywords
- chlorinated organic
- organic substance
- wavelength
- transmittance
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005416 organic matter Substances 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims description 85
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 135
- 238000002834 transmittance Methods 0.000 claims description 83
- 235000017168 chlorine Nutrition 0.000 claims description 66
- 125000001309 chloro group Chemical class Cl* 0.000 claims description 49
- 230000003287 optical effect Effects 0.000 claims description 35
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 230000005284 excitation Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 11
- 239000011368 organic material Substances 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 abstract description 12
- 238000007689 inspection Methods 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 68
- 235000010290 biphenyl Nutrition 0.000 description 35
- 239000004305 biphenyl Substances 0.000 description 34
- 238000004140 cleaning Methods 0.000 description 19
- 238000000926 separation method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- RIMXLXBUOQMDHV-UHFFFAOYSA-N 1,2-dichloro-4-(2-chlorophenyl)benzene Chemical compound C1=C(Cl)C(Cl)=CC=C1C1=CC=CC=C1Cl RIMXLXBUOQMDHV-UHFFFAOYSA-N 0.000 description 1
- 101100408296 Autographa californica nuclear polyhedrosis virus AC24 gene Proteins 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】塩素化有機物の検出方法に関
し、特に、結合している塩素の数が異なる複数の塩素化
有機物の分解工程や洗浄工程の進行状況や終了時点を確
認するための検出方法と検出装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for detecting a chlorinated organic substance, and more particularly to a method for confirming the progress and end points of a decomposition step and a washing step of a plurality of chlorinated organic substances having different numbers of bound chlorine. And a detection device.
【０００２】[0002]
【従来の技術】ポリ塩化ビフェニル（polychlorinated
biphenyls：以下、ＰＣＢと記す）などの有害な塩素化
有機物を含む物品を処理する場合は、これら有害な塩素
化有機物が環境に排出されないように、上限濃度が法的
に規制されている。このため、有害な塩素化有機物を含
む物品を洗浄して有害な塩素化有機物を除去する場合
や、有害な塩素化有機物を分解処理する場合には、法的
な規制値以下の濃度となったことを検出する手段が必要
である。この規制値は、例えば、ＰＣＢの上限濃度であ
る０．５ｐｐｍに見られるようなきわめて低い濃度であ
るため、検出手段として質量分析装置を用いた検出方法
が使用されていた。2. Description of the Related Art Polychlorinated biphenyl
When processing articles containing harmful chlorinated organic substances such as biphenyls (hereinafter referred to as PCB), the upper limit concentration is legally regulated so that these harmful chlorinated organic substances are not discharged to the environment. For this reason, when the articles containing harmful chlorinated organic substances are washed to remove harmful chlorinated organic substances, or when the harmful chlorinated organic substances are decomposed, the concentration is lower than the legally regulated value. There is a need for a means for detecting this. Since this regulation value is a very low concentration, for example, found at 0.5 ppm, which is the upper limit concentration of PCB, a detection method using a mass spectrometer has been used as a detection means.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、質量分
析装置を用いるこの検出方法は、高感度、高精度に分析
できる反面、測定のために処理装置を一旦開放にする必
要があることから、有害成分に接触したり、有害成分が
漏洩する可能性があった。また、分解や除去の進行状況
をリアルタイムで知ることができないため、分解や除去
が不十分で再度処理を行う必要が生じたり、必要以上に
処理をして無駄を生じたりする可能性があった。また、
有害な塩素化有機物には結合している塩素の数が異なる
ものも多く、これらの混合物からなる塩素化有機物の分
解工程や洗浄工程の進行状況や終了時点を確認するため
に濃度を検出するのは困難であった。この発明の目的
は、有害な塩素化有機物を環境に放出する恐れがなく、
結合している塩素の数が異なる混合物からなる塩素化有
機物であっても分解工程や洗浄工程の進行状況や終了時
点を確認することが可能な検出方法を提供することであ
る。However, this detection method using a mass spectrometer can perform high-sensitivity and high-precision analysis, but requires the treatment apparatus to be once opened for measurement, so that harmful components can be analyzed. And harmful components may leak. In addition, since the progress of decomposition and removal cannot be known in real time, there is a possibility that decomposition and removal are insufficient and processing needs to be performed again, or unnecessary processing may result in waste. . Also,
Many of the harmful chlorinated organic substances have different numbers of chlorine bound, and the concentration of these chlorinated organic substances is detected to confirm the progress and end points of the decomposition and cleaning steps of the chlorinated organic substances composed of these mixtures. Was difficult. The object of the present invention is to not release harmful chlorinated organic substances to the environment,
It is an object of the present invention to provide a detection method capable of confirming the progress and the end point of a decomposition step or a cleaning step even for a chlorinated organic substance composed of a mixture having different numbers of bound chlorine.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記問題
を解決するため、廃棄物に含まれる塩素化有機物の分解
処理や洗浄過程における塩素化有機物の検出方法とし
て、光の吸収や励起発光を使った方法に着目して鋭意検
討を行った。その結果、塩素化有機物の結合している塩
素の数と光の吸収量や励起発光量の間に濃度検出に適し
た関係を有する波長域を見いだし、この発明を完成する
に至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have proposed a method of detecting chlorinated organic substances in a process of decomposing and cleaning chlorinated organic substances contained in waste and absorbing or exciting light. Focusing on the method using light emission, we conducted intensive studies. As a result, the inventors have found a wavelength region having a relationship suitable for concentration detection between the number of chlorines bonded to chlorinated organic substances and the amount of light absorption and the amount of excitation light emission, and have completed the present invention.
【０００５】この発明の塩素化有機物の検出方法は、結
合している塩素の数が異なる複数の塩素化有機物を含む
物品からこれらの塩素化有機物を除去する工程における
塩素化有機物の残留濃度が所定値以下となったことを検
出する方法であって、塩素化有機物を含む物品に所定の
溶媒を接触させて塩素化有機物を選択的に溶出させ、塩
素化有機物を含む溶媒に紫外線を照射して所定波長の透
過率を測定し、この透過率が所定の透過率以上となった
ときに塩素化有機物の残留濃度を所定値以下の濃度と判
定するようにし、所定波長を結合している塩素の数が少
ない塩素化有機物ほど高い透過率を示す波長域から選択
し、所定の透過率を結合している塩素の数が最も少ない
塩素化有機物の所定値の濃度における透過率としたこと
によって特徴づけられる。この場合、溶媒の一実施例
は、超臨界二酸化炭素を用いる。また、塩素化有機物の
一実施例は、ポリ塩化ビフェニルであり、２００ｎｍ以
上２４５ｎｍ以下、あるいは２８０ｎｍ以上３００ｎｍ
以下の波長域を用いる。According to the method for detecting chlorinated organic substances of the present invention, the residual concentration of chlorinated organic substances in a step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of chlorine bonded thereto is predetermined. It is a method of detecting that the value is less than or equal to the value, by selectively eluting the chlorinated organic substance by contacting a predetermined solvent to the article containing the chlorinated organic substance, and irradiating the solvent containing the chlorinated organic substance with ultraviolet rays. The transmittance of a predetermined wavelength is measured, and when this transmittance becomes equal to or higher than a predetermined transmittance, the residual concentration of the chlorinated organic substance is determined to be a concentration equal to or lower than a predetermined value, and the chlorine of the predetermined wavelength is bound. Chlorinated organic substances with a small number are selected from the wavelength range that shows high transmittance, and the specified transmittance is characterized by the transmittance at the concentration of the specified value of the chlorinated organic substance with the smallest number of bound chlorine. It is. In this case, one embodiment of the solvent uses supercritical carbon dioxide. One example of the chlorinated organic material is polychlorinated biphenyl, which is 200 nm or more and 245 nm or less, or 280 nm or more and 300 nm.
The following wavelength range is used.
【０００６】この検出方法の別の実施例は、結合してい
る塩素の数が異なる複数の塩素化有機物を含む物品から
これらの塩素化有機物を除去する工程における塩素化有
機物の残留濃度が所定値以下となったことを検出する方
法であって、塩素化有機物を含む物品に所定の溶媒を接
触させて塩素化有機物を選択的に溶出、分解させ、塩素
化有機物と分解生成物とを含む溶媒に紫外線を照射し
て、第１の波長の透過率と第２の波長の透過率とをそれ
ぞれ測定し、第１の波長で分解生成物を検出し、第２の
波長の透過率が所定の透過率以上となったときに塩素化
有機物の残留濃度を所定値以下の濃度と判定するように
し、第１の波長を結合している塩素の数が少ない塩素化
有機物ほど高い透過率を示し、かつ分解生成物の吸収を
受ける第１の波長域から選択し、第２の波長を結合して
いる塩素の数が少ない塩素化有機物ほど高い透過率を示
し、かつ分解生成物の吸収を受けない第２の波長域から
選択し、所定の透過率を結合している塩素の数が最も少
ない塩素化有機物の所定値の濃度における透過率とした
ことによって特徴づけられる。この場合、溶媒の一実施
例は、超臨界水を用いる。また、塩素化有機物の一実施
例は、ポリ塩化ビフェニルであり、第１の波長域を２０
０ｎｍ以上２３５ｎｍ以下とし、第２の波長域を２９５
ｎｍ以上３００ｎｍ以下とした。In another embodiment of the detection method, the residual concentration of the chlorinated organic substance in the step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having a different number of bound chlorine is a predetermined value. A method for detecting the following, wherein a predetermined solvent is brought into contact with an article containing a chlorinated organic substance to selectively elute and decompose the chlorinated organic substance, and a solvent containing a chlorinated organic substance and a decomposition product is provided. Is irradiated with ultraviolet light, the transmittance of the first wavelength and the transmittance of the second wavelength are measured, the decomposition product is detected at the first wavelength, and the transmittance of the second wavelength is a predetermined value. The residual concentration of the chlorinated organic material is determined to be a concentration equal to or less than a predetermined value when the transmittance becomes equal to or higher than the transmittance, and the chlorinated organic material having a smaller number of chlorines binding the first wavelength shows a higher transmittance, And the first wavelength range that receives absorption of decomposition products Chlorinated organic substances having a smaller number of chlorines binding to the second wavelength exhibit higher transmittance and are selected from a second wavelength range in which the decomposition products are not absorbed, and a predetermined transmittance is selected. Is defined as the transmittance at a predetermined concentration of the chlorinated organic substance having the least number of chlorine bonded thereto. In this case, one embodiment of the solvent uses supercritical water. One example of a chlorinated organic material is polychlorinated biphenyl, which has a first wavelength range of 20.
0 nm or more and 235 nm or less, and the second wavelength range is 295
nm or more and 300 nm or less.
【０００７】この検出方法のさらに別の実施例は、結合
している塩素の数が異なる複数の塩素化有機物を含む物
品からこれらの塩素化有機物を除去する工程における塩
素化有機物の残留濃度が所定値以下となったことを検出
する方法であって、塩素化有機物を含む物品に所定の溶
媒を接触させて塩素化有機物を選択的に溶出、分解さ
せ、塩素化有機物と分解生成物とを含む溶媒に紫外線を
照射して励起発光させて所定波長の発光量を測定し、こ
の発光量が所定の発光量以下となったときに塩素化有機
物の残留濃度を所定値以下の濃度と判定するようにし、
所定波長を分解生成物の励起発光がなく、かつ塩素基の
数が少ない塩素化有機物ほど励起発光量が多い波長域か
ら選択し、所定の発光量を結合している塩素の数が最も
少ない塩素化有機物の所定値の濃度における発光量とし
たことによって特徴づけられる。この場合、溶媒の一実
施例は、超臨界水を用いる。また、塩素化有機物の一実
施例は、ポリ塩化ビフェニルであり、３８０ｎｍ以上４
００ｎｍ以下の波長域を用いる。[0007] In still another embodiment of the detection method, the residual concentration of chlorinated organic substances in the step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of chlorine bonded thereto is predetermined. A method for detecting that the value has become equal to or less than a value, wherein a predetermined solvent is brought into contact with an article containing a chlorinated organic substance to selectively elute and decompose the chlorinated organic substance, and contains a chlorinated organic substance and a decomposition product. The solvent is irradiated with ultraviolet light to cause excitation light emission, and the light emission amount of a predetermined wavelength is measured. When the light emission amount becomes equal to or less than a predetermined light emission amount, the residual concentration of the chlorinated organic substance is determined to be a concentration equal to or less than a predetermined value. West,
A predetermined wavelength is selected from a wavelength range in which the amount of excited luminescence is larger for a chlorinated organic substance having no excitation light emission of a decomposition product and a smaller number of chlorine groups, and having the least number of chlorines binding a predetermined light emission amount. It is characterized by the amount of light emission at a predetermined concentration of the organic compound. In this case, one embodiment of the solvent uses supercritical water. One example of a chlorinated organic material is polychlorinated biphenyl, which is not less than 380 nm.
A wavelength range of 00 nm or less is used.
【０００８】また、この発明の塩素化有機物の検出装置
は、結合している塩素の数が異なる複数の塩素化有機物
を含む物品からこれらの塩素化有機物を除去する工程に
おける塩素化有機物の残留濃度が所定値以下となったこ
とを検出する検出装置であって、紫外線光源と、紫外線
が透過可能に構成され物品から溶出された塩素化有機物
を含む溶媒が通過する分光セルと、結合している塩素の
数が少ない塩素化有機物ほど高い透過率を示す波長域か
ら選択した波長の紫外線を透過させる分光器と、分光器
を透過した光量を測定する光パワーメーターと、光パワ
ーメーターの測定値が入力されて透過率を算出し、透過
率が結合している塩素の数が最も少ない塩素化有機物の
所定値に対応する透過率以上となったときに所定値以下
の濃度と判定し、通知するように構成された制御部とを
備えたことによって特徴づけられる。Further, the chlorinated organic substance detection apparatus of the present invention provides a residual concentration of chlorinated organic substance in a step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of bound chlorine. Is a detection device that detects that is less than or equal to a predetermined value, and is coupled to an ultraviolet light source, a spectroscopic cell configured to be able to transmit ultraviolet light and through which a solvent containing chlorinated organic substances eluted from the article passes. A chlorinated organic substance with a smaller number of chlorines transmits ultraviolet light of a wavelength selected from the wavelength range showing higher transmittance, a light power meter that measures the amount of light transmitted through the spectrometer, and a light power meter that measures the light amount. Calculate the transmittance that is input, when the transmittance is equal to or greater than the transmittance corresponding to the predetermined value of the chlorinated organic matter with the smallest number of chlorine bound, it is determined that the concentration is less than the predetermined value, It characterized by comprising a configured controlled unit such that knowledge.
【０００９】この検出装置の別の実施例は、結合してい
る塩素の数が異なる複数の塩素化有機物を含む物品から
これらの塩素化有機物を除去する工程における塩素化有
機物の残留濃度が所定値以下となったことを検出する検
出装置であって、紫外線光源と、紫外線が透過可能に構
成され物品から溶出された塩素化有機物と塩素化有機物
の分解生成物とを含む溶媒が通過する分光セルと、結合
している塩素の数が少ない塩素化有機物ほど高い透過率
を示し、かつ分解生成物の吸収を受ける第１の波長域か
ら選択した第１の波長と、結合している塩素の数が少な
い塩素化有機物ほど高い透過率を示し、かつ分解生成物
の吸収を受けない第２の波長域から選択した第２の波長
とをそれぞれ別に透過させる分光器と、分光器を透過し
た２つの波長の光量をそれぞれ別に測定する光パワーメ
ーターと、光パワーメーターの２つの測定値が入力され
てそれぞれの透過率を算出し、第１の波長で分解生成物
を検出し、第２の波長の透過率が結合している塩素の数
が最も少ない塩素化有機物の所定値の濃度における透過
率以上となったときに所定値以下の濃度と判定し、通知
するように構成された制御部とを備えたことによって特
徴づけられる。In another embodiment of the detection apparatus, the residual concentration of the chlorinated organic substance in the step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of bound chlorine is a predetermined value. A detection device for detecting that: a spectroscopic cell through which an ultraviolet light source and a solvent containing chlorinated organic matter eluted from an article and a decomposition product of the chlorinated organic matter, which is configured to transmit ultraviolet light, passes And a first wavelength selected from a first wavelength range in which a chlorinated organic substance having a smaller number of bound chlorines exhibits a higher transmittance and absorbs decomposition products, and a number of the bound chlorines. The chlorinated organic substance having a smaller amount exhibits a higher transmittance, and a spectroscope that separately transmits a second wavelength selected from a second wavelength range that does not receive the decomposition product, and two spectrometers that transmit the spectrometer. Wavelength light Optical power meter and optical power meter, each of which separately measures the transmittance, calculates the respective transmittances, detects decomposition products at the first wavelength, and determines the transmittance at the second wavelength. A control unit configured to determine a concentration equal to or lower than a predetermined value when the transmittance of the chlorinated organic substance having the smallest number of bound chlorine at a predetermined concentration is equal to or higher than the predetermined value, and to notify the control unit. Characterized by
【００１０】この検出装置のさらに別の実施例は、結合
している塩素の数が異なる複数の塩素化有機物を含む物
品からこれらの塩素化有機物を除去する工程における塩
素化有機物の残留濃度が所定値以下となったことを検出
する検出装置であって、紫外線光源と、紫外線が透過可
能に構成され物品から溶出された塩素化有機物と塩素化
有機物の分解生成物とを含む溶媒が通過する分光セル
と、分解生成物の励起発光がなく、かつ塩素基の数が少
ない塩素化有機物ほど励起発光量が多い波長域から選択
した波長を透過させる分光器と、分光器を透過した光量
を測定する光パワーメーターと、光パワーメーターの測
定値が入力されて発光量を算出し、発光量が結合してい
る塩素の数が最も少ない塩素化有機物の所定値の濃度に
おける発光量以下となったときに所定値以下の濃度と判
定し、通知するように構成された制御部とを備えたこと
によって特徴づけられる。[0010] In still another embodiment of the detection apparatus, the residual concentration of the chlorinated organic substance in the step of removing the chlorinated organic substance from an article containing a plurality of chlorinated organic substances having different numbers of chlorines bound thereto is predetermined. A detection device for detecting that the value has become less than or equal to a value, wherein the ultraviolet light source and a spectrometer through which a solvent containing chlorinated organic substances eluted from an article and decomposition products of the chlorinated organic substances pass through, are passed. A cell, a spectrometer that transmits no selected emission from the wavelength region where the amount of excitation light emission is higher as the chlorinated organic substance which has no excitation light emission of decomposition products and has a smaller number of chlorine groups, and measures the amount of light transmitted through the spectrometer. The optical power meter and the measured value of the optical power meter are input and the luminescence amount is calculated, and the luminescence amount is less than or equal to the luminescence amount at the concentration of the predetermined value of the chlorinated organic substance in which the number of chlorines bonded is the least. Determines that the predetermined value following concentrations when Tsu, characterized by comprising a control unit configured to notify.
【００１１】[0011]
【発明の実施の形態】以下に図を用いてこの発明の実施
の形態を説明する。はじめに、この発明の第１の実施の
形態について説明する。この第１の実施の形態は、この
発明の検出方法を塩素化有機物に汚染された物品を洗浄
する際の終了判定に適用したものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings. First, a first embodiment of the present invention will be described. In the first embodiment, the detection method of the present invention is applied to an end determination when cleaning an article contaminated with chlorinated organic matter.
【００１２】図１は、第１の実施の形態で用いる洗浄装
置の概略図である。この洗浄装置は、洗浄用の溶媒とし
て超臨界二酸化炭素を用いる。図１において、この洗浄
装置は、洗浄槽１１、検出室１２、分離室１３、超臨界
流体循環用圧縮装置１４及び塩素化有機物の検出装置２
０を備えており、洗浄槽１１と検出室１２が開閉弁１５
を介して配管接続され、検出室１２と分離室１３が開閉
弁１６を介して配管接続され、分離室１３と超臨界流体
循環用圧縮装置１４が開閉弁１７を介して配管接続さ
れ、超臨界流体循環用圧縮装置１４と洗浄槽１１が開閉
弁１８を介して配管接続されている。FIG. 1 is a schematic diagram of a cleaning apparatus used in the first embodiment. This cleaning apparatus uses supercritical carbon dioxide as a cleaning solvent. In FIG. 1, the cleaning device includes a cleaning tank 11, a detection chamber 12, a separation chamber 13, a compression device 14 for circulating a supercritical fluid, and a detection device 2 for chlorinated organic substances.
The cleaning tank 11 and the detection chamber 12 are provided with an on-off valve 15.
The detection chamber 12 and the separation chamber 13 are connected by a pipe via an on-off valve 16, and the separation chamber 13 and the compression device for supercritical fluid circulation 14 are connected by a pipe via an on-off valve 17. The fluid circulation compression device 14 and the washing tank 11 are connected to each other via a pipe 18 via an on-off valve 18.
【００１３】また、塩素化有機物の検出装置２０は、検
出室１２周りに取り付けられている。この検出装置２０
は、検出室１２を挟んで直線上に配置された光源２１と
分光器２２、光源２１と検出室１２の間に配置された光
源２１から出る紫外光３５を検出室１２に収束させる２
つのレンズ２５，２６、検出室１２と分光器２２の間に
配置された検出室１２から出る紫外光３６を分光器２２
に収束させる２つのレンズ２７，２８、分光器２２の出
力光の強度を計測する光パワーメーター２３及び光パワ
ーメーター２３の信号出力が入力され、濃度を算出する
制御部２４で構成されている。The chlorinated organic matter detection device 20 is mounted around the detection chamber 12. This detection device 20
Is to converge the ultraviolet light 35 emitted from the light source 21 and the spectroscope 22 arranged on a straight line with the detection chamber 12 therebetween, and the ultraviolet light 35 emitted from the light source 21 arranged between the light source 21 and the detection chamber 12 into the detection chamber 12.
The ultraviolet light 36 emitted from the detection chamber 12 disposed between the two lenses 25 and 26 and the detection chamber 12 and the spectroscope 22 is
, A light power meter 23 for measuring the intensity of the output light from the spectroscope 22, and a signal output from the light power meter 23, and a control unit 24 for calculating the density.
【００１４】洗浄槽１１は、ステンレス等によって製作
された耐圧容器であり、物品の搬出入と密閉とが可能な
構成を有している。また、溶媒の超臨界状態を保つため
の、加熱や加圧が可能に構成されている。検出室１２
は、洗浄槽１１と同様の耐圧容器であり、紫外光を通す
直径１ｃｍ程度の石英製の光学窓を備えている。この場
合、検出室１２は、相互作用長１ｃｍの分光セルを構成
している。分離室１３は、溶媒を超臨界状態から液体又
は気体の状態に変えて塩素化有機物を分離するための冷
却や減圧が可能な構成を有している。また、分離室１３
には、分離された塩素化有機物を取り出すための取り出
し弁１９が設けられている。超臨界流体循環用圧縮装置
１４は、分離室１３から取り出した溶媒を超臨界状態に
するための加熱機構や加圧機構を備えている。The washing tank 11 is a pressure-resistant container made of stainless steel or the like, and has a structure capable of carrying in and out of articles and sealing. Further, heating and pressurization for maintaining a supercritical state of the solvent are possible. Detection chamber 12
Is a pressure-resistant container similar to the cleaning tank 11 and has an optical window made of quartz having a diameter of about 1 cm and transmitting ultraviolet light. In this case, the detection chamber 12 forms a spectral cell having an interaction length of 1 cm. The separation chamber 13 has a configuration in which the solvent can be changed from a supercritical state to a liquid or gas state to perform cooling or decompression for separating chlorinated organic substances. Also, the separation chamber 13
Is provided with a take-out valve 19 for taking out the separated chlorinated organic matter. The supercritical fluid circulation compression device 14 includes a heating mechanism and a pressurization mechanism for bringing the solvent taken out of the separation chamber 13 into a supercritical state.
【００１５】次に、この実施の形態の検出方法を塩素化
有機物の一種であるポリ塩化ビフェニル（以後ＰＣＢと
記す）に汚染された物品の洗浄に適用した場合を例に説
明する。まず、ＰＣＢについて説明すると、塩素化有機
物の一種であるＰＣＢは総称であり、２０９種類が知ら
れている。例えば、カネクロール３００（商品名、以後
ＫＣ３００と記す）やカネクロール６００（商品名、以
後ＫＣ６００と記す）は、ビフェニル環に結合する塩素
の数が異なるＰＣＢの混合物であり、これらＰＣＢの分
布がそれぞれ異なる。ＫＣ３００は塩素の数が３のＰＣ
Ｂが最も多く含まれており、ＫＣ６００は塩素の数が６
のＰＣＢが最も多く含まれている。Next, an example in which the detection method of this embodiment is applied to cleaning of articles contaminated with polychlorinated biphenyl (hereinafter referred to as PCB), which is a kind of chlorinated organic substance, will be described. First, PCB will be described. PCB, which is a kind of chlorinated organic substance, is a general term, and 209 kinds are known. For example, Kanechlor 300 (trade name, hereinafter referred to as KC300) and Kanechlor 600 (trade name, hereinafter referred to as KC600) are a mixture of PCBs having different numbers of chlorines bonded to biphenyl rings, and the distribution of these PCBs is different. Each is different. KC300 is a PC with 3 chlorine atoms
B has the highest content, and KC600 has 6 chlorine atoms.
Most of the PCBs are included.
【００１６】このように複数の種類が存在する場合は、
洗浄後の濃度が規制値以下であることを保証するため、
種類によって検出感度が異なる可能性を考慮する必要が
ある。この実施の形態のように、ＰＣＢを紫外線吸収法
で検出する場合は、塩素の数によって紫外線吸収量が変
化すると考えられるため、塩素を含まないビフェニル、
ＫＣ３００及びＫＣ６００について紫外線吸収測定の実
験を行った。図２〜図４は、塩素の数が異なるＰＣＢに
よる紫外線吸収量を示すグラフであり、図２は波長２０
０ｎｍ〜３２０ｎｍの紫外線の透過率を示す図、図３は
図２の２００ｎｍ〜２４５ｎｍの領域を拡大した図、図
４は図２の２７５ｎｍ〜３００ｎｍの領域でかつ透過率
９５％〜１００％の領域を拡大した図である。これらの
図において、ａがＫＣ３００、ｂがＫＣ６００、ｃがビ
フェニルを示し、横軸が紫外線の波長、縦軸が透過率を
示す。この実験では、相互作用長１ｃｍの分光セルを用
い、ＫＣ３００、ＫＣ６００及びビフェニルの濃度をす
べて０．５ｐｐｍとした。When there are a plurality of types as described above,
To ensure that the concentration after washing is below the regulated value,
It is necessary to consider the possibility that the detection sensitivity differs depending on the type. When the PCB is detected by the ultraviolet absorption method as in this embodiment, it is considered that the ultraviolet absorption amount changes depending on the number of chlorines.
An experiment of ultraviolet absorption measurement was performed on KC300 and KC600. 2 to 4 are graphs showing the amount of ultraviolet absorption by PCBs having different chlorine numbers, and FIG.
FIG. 3 is a view showing the transmittance of ultraviolet light of 0 nm to 320 nm, FIG. 3 is an enlarged view of the region of 200 nm to 245 nm in FIG. 2, and FIG. 4 is a region of 275 nm to 300 nm and 95% to 100% in FIG. FIG. In these figures, a indicates KC300, b indicates KC600, and c indicates biphenyl, the horizontal axis indicates the wavelength of ultraviolet light, and the vertical axis indicates transmittance. In this experiment, a spectroscopic cell having an interaction length of 1 cm was used, and the concentrations of KC300, KC600 and biphenyl were all 0.5 ppm.
【００１７】この実験結果から、２００ｎｍ〜２３５ｎ
ｍの領域と２８０ｎｍ〜３００ｎｍの領域で塩素の数が
少ないほど透過率が高くなることが分かった。すなわ
ち、これらの領域においては、測定された透過率が濃度
０．５ｐｐｍのビフェニルの透過率以上であれば、ＰＣ
Ｂの濃度が規制値である０．５ｐｐｍ以下であることが
保証される。なお、紫外線吸収法で検出できる濃度を確
認するため、ＫＣ３００とＫＣ６００の濃度を０．０５
ｐｐｍにして紫外線吸収測定の実験を行った結果を図５
に示す。図５は、ＰＣＢの紫外線透過率を示すグラフで
あり、同図において、ａがＫＣ３００、ｂがＫＣ６００
を示し、横軸が波長、縦軸が透過率を示す。この結果よ
り紫外線吸収法によれば、ＰＣＢが廃油として廃棄でき
る法的基準値である、０．５ｐｐｍのさらに１桁下まで
十分に検出可能であることが分かる。From the results of this experiment, it was found that 200 nm to 235 n
It was found that the transmittance was higher as the number of chlorine was smaller in the region of m and the region of 280 nm to 300 nm. That is, in these regions, if the measured transmittance is equal to or higher than the transmittance of biphenyl having a concentration of 0.5 ppm, PC
It is guaranteed that the concentration of B is equal to or less than the regulated value of 0.5 ppm. In order to confirm the concentration that can be detected by the ultraviolet absorption method, the concentrations of KC300 and KC600 were adjusted to 0.05.
FIG. 5 shows the result of an experiment of ultraviolet absorption measurement at ppm.
Shown in FIG. 5 is a graph showing the ultraviolet transmittance of the PCB, in which a is KC300 and b is KC600.
And the horizontal axis represents wavelength and the vertical axis represents transmittance. From this result, it can be seen that according to the ultraviolet absorption method, it is possible to sufficiently detect even one digit lower than 0.5 ppm, which is a legal standard value at which PCB can be discarded as waste oil.
【００１８】次に、ＰＣＢに汚染された物品の洗浄装置
を用いた洗浄方法を説明する。洗浄槽１１に物品を入れ
て密閉した後、開閉弁１８を開いて超臨界流体循環用圧
縮装置１４から洗浄槽１１に超臨界二酸化炭素３２を導
入し、ＰＣＢに汚染された物品に浸透してＰＣＢを溶か
し出すまで待つ。次に、開閉弁１５を開いて溶かし出さ
れたＰＣＢを含んだ超臨界二酸化炭素３０を検出室１２
に送り、塩素化有機物検出装置２０で紫外線吸収測定を
行う。測定終了後、開閉弁１６を開いてＰＣＢを含んだ
超臨界二酸化炭素３０を分離室１３に送り、減圧し、冷
却して気体に変化させ、ＰＣＢを分離させる。次に、開
閉弁１７を開いて分離室１３から超臨界流体循環用圧縮
装置１４に気体状態の二酸化炭素３１を送り、加圧し、
加熱して超臨界二酸化炭素３２に変化させる。以後、洗
浄終了までこのサイクルが繰り返される。洗浄が終了し
たら、物品を取り出す。分離室１３に残ったＰＣＢ３３
は、取り出し弁１９を開いて環境に放出されないように
取り出して保管又は分解処理する。Next, a method of cleaning articles contaminated with PCB using a cleaning apparatus will be described. After the articles are put in the washing tank 11 and sealed, the on-off valve 18 is opened to introduce supercritical carbon dioxide 32 from the supercritical fluid circulation compression device 14 into the washing tank 11 and penetrate the articles contaminated with PCB. Wait for the PCB to melt. Next, the on-off valve 15 is opened and the supercritical carbon dioxide 30 containing the melted PCB is supplied to the detection chamber 12.
And the ultraviolet light absorption measurement is performed by the chlorinated organic matter detection device 20. After the completion of the measurement, the on-off valve 16 is opened, and the supercritical carbon dioxide 30 containing PCB is sent to the separation chamber 13, where the pressure is reduced, cooled and changed into gas, and the PCB is separated. Next, the on-off valve 17 is opened, and the gaseous carbon dioxide 31 is sent from the separation chamber 13 to the supercritical fluid circulation compression device 14 and pressurized,
It is changed to supercritical carbon dioxide 32 by heating. Thereafter, this cycle is repeated until the cleaning is completed. When washing is completed, remove the articles. PCB 33 remaining in separation chamber 13
Open the take-out valve 19 to take out and store or disassemble it so that it is not released to the environment.
【００１９】次に、このような洗浄処理における塩素化
有機物の検出装置２０を用いたＰＣＢの検出方法につい
て説明する。塩素化有機物の検出装置２０は、紫外線光
源２１、レンズ２５〜２８、分光器２２、光パワーメー
ター２３及び制御部２４を備えており、紫外線光源２１
から出た紫外光３５を検出室１２の分光セルに集光する
ようにレンズ２５，２６が配置され、検出室１２の分光
セルから出た紫外光３６を分光器２２に集光するように
レンズ２７，２８が配置されている。また、光パワーメ
ーター２３の信号出力が制御部２４に入力されるように
構成されている。Next, a method of detecting PCB using the chlorinated organic substance detection device 20 in such a cleaning process will be described. The chlorinated organic matter detection device 20 includes an ultraviolet light source 21, lenses 25 to 28, a spectroscope 22, an optical power meter 23, and a control unit 24.
The lenses 25 and 26 are arranged so as to converge the ultraviolet light 35 emitted from the spectroscopic cell of the detection chamber 12, and the lenses 25 and 26 are arranged such that the ultraviolet light 36 emitted from the spectroscopic cell of the detection chamber 12 is condensed to the spectroscope 22. 27 and 28 are arranged. Further, the signal output of the optical power meter 23 is configured to be input to the control unit 24.
【００２０】ここで、紫外線光源２１には、紫外光の安
定な供給源である重水素ランプを用い、レンズ２５〜２
８には、紫外光を吸収しない石英製を用いる。分光器２
２は、塩素の数が少ないＰＣＢほど吸収が少なくなる波
長域から選択した所定波長だけを透過するように構成さ
れている。光パワーメーター２３は、分光器２２を透過
した紫外線の強度を測定し、制御部２４に通知する。制
御部２４は、検出室１２にＰＣＢを含んだ超臨界二酸化
炭素３０が送られるたびに光パワーメーター２３の測定
値から洗浄終了判定を行う。Here, as the ultraviolet light source 21, a deuterium lamp, which is a stable source of ultraviolet light, is used.
8 is made of quartz which does not absorb ultraviolet light. Spectroscope 2
No. 2 is configured to transmit only a predetermined wavelength selected from a wavelength range in which the absorption of the PCB becomes smaller as the number of chlorines becomes smaller. The optical power meter 23 measures the intensity of the ultraviolet light transmitted through the spectroscope 22 and notifies the controller 24 of the intensity. Each time the supercritical carbon dioxide 30 containing PCB is sent to the detection chamber 12, the control unit 24 determines the cleaning end from the measured value of the optical power meter 23.
【００２１】洗浄終了判定は、つぎのようにして行う。
まず、あらかじめ測定し記憶していた超臨界二酸化炭素
のみを検出室１２の分光セルに満たしたときの光パワー
メーター２３の測定値を参照して、ＰＣＢを含んだ超臨
界二酸化炭素３０が検出室１２の分光セルを満たしたと
きの光パワーメーター２３の測定値からこのＰＣＢを含
んだ超臨界二酸化炭素３０の透過率を計算する。次に、
算出した透過率とあらかじめ測定し記憶していた濃度
０．５ｐｐｍのビフェニルの透過率を比較する。算出し
た透過率がビフェニルの透過率以上であれば洗浄終了と
判定して通知し、そうでなければ次の測定値を待つ。The completion of the washing is determined as follows.
First, referring to the measurement value of the optical power meter 23 when only the pre-measured and stored supercritical carbon dioxide is filled in the spectroscopic cell of the detection chamber 12, the supercritical carbon dioxide 30 containing PCB is detected in the detection chamber. The transmittance of the supercritical carbon dioxide 30 containing the PCB is calculated from the measured value of the optical power meter 23 when the twelve spectral cells are filled. next,
The calculated transmittance is compared with the transmittance of biphenyl having a concentration of 0.5 ppm, which is measured and stored in advance. If the calculated transmittance is equal to or higher than the transmittance of biphenyl, it is determined that the washing is completed and notified, otherwise, the next measurement value is waited.
【００２２】以上説明したように、同じ濃度において塩
素の数が少ないＰＣＢほど透過率が高くなり、かつビフ
ェニルの透過率がこれらＰＣＢの透過率よりも高い波長
を測定し、この波長の透過率がビフェニルの透過率以上
のとき洗浄終了と判定するようにしたので、洗浄された
物品のＰＣＢ濃度が規制値である０．５ｐｐｍ以下であ
ることが保証される。As described above, at a same concentration, a PCB having a smaller number of chlorines has a higher transmittance, and a wavelength at which the transmittance of biphenyl is higher than the transmittance of these PCBs is measured. Since it is determined that the washing is completed when the transmittance is equal to or higher than the biphenyl transmittance, it is guaranteed that the PCB concentration of the washed article is equal to or less than the regulated value of 0.5 ppm.
【００２３】次に、この発明の第２の実施の形態につい
て説明する。塩素化有機物であるＰＣＢやダイオキシン
類は、超臨界水に接触させたり、アルカリ触媒分解法を
用いることにより、脱塩素化され無害化することができ
る。この第２の実施の形態は、この発明の検出方法を塩
素化有機物の分解処理の終了判定に適用したものであ
る。図６は、この発明の検出方法に係る第２の実施の形
態で用いられる分解装置の概略図である。同図におい
て、この分解装置は、反応槽４１、検出室４２、取り出
し室４３及び塩素化有機物の検出装置５０を備えてお
り、反応槽４１と検出室４２が配管接続され、検出室４
２が三方弁４４を介して取り出し室４３と反応槽４１と
に配管接続されている。また、塩素化有機物の検出装置
５０は、検出室４２周りに取り付けられている。Next, a second embodiment of the present invention will be described. PCBs and dioxins, which are chlorinated organic substances, can be dechlorinated and made harmless by contacting with supercritical water or using an alkali catalytic decomposition method. In the second embodiment, the detection method of the present invention is applied to the end determination of the decomposition processing of a chlorinated organic substance. FIG. 6 is a schematic diagram of a decomposition apparatus used in the second embodiment according to the detection method of the present invention. In this figure, the decomposition apparatus includes a reaction tank 41, a detection chamber 42, an extraction chamber 43, and a chlorinated organic substance detection apparatus 50. The reaction tank 41 and the detection chamber 42 are connected by piping, and the detection chamber 4
2 is connected to the take-out chamber 43 and the reaction tank 41 via a three-way valve 44. The chlorinated organic matter detection device 50 is attached around the detection chamber 42.
【００２４】この検出装置５０は、検出室４２を挟んで
直線上に配置された光源５１と分光器５２、光源５１と
検出室４２の間に配置された光源５１から出る紫外光６
５を検出室４２に収束させる２つのレンズ５５，５６、
検出室４２と分光器５２の間に配置された検出室４２か
ら出る紫外光６６を分光器５２に収束させる２つのレン
ズ５７，５８、分光器５２の出力光の強度を計測する光
パワーメーター５３及び光パワーメーター５３の信号出
力が入力され、濃度を算出する制御部５４で構成されて
いる。The detection device 50 includes a light source 51 and a spectroscope 52 arranged linearly with the detection chamber 42 interposed therebetween, and ultraviolet light 6 emitted from the light source 51 disposed between the light source 51 and the detection chamber 42.
5, two lenses 55 and 56 for converging 5 into the detection chamber 42,
Two lenses 57 and 58 for converging the ultraviolet light 66 emitted from the detection chamber 42 disposed between the detection chamber 42 and the spectroscope 52 to the spectroscope 52, and an optical power meter 53 for measuring the intensity of the output light of the spectroscope 52. And a signal output of the optical power meter 53, and a control unit 54 for calculating the density.
【００２５】次に、この分解装置を用いた塩素化有機物
の分解処理についてＰＣＢを例に説明する。ＰＣＢは、
反応槽４１で超臨界水によって脱塩素化が行われて分解
される。ＰＣＢと分解生成物を含んだ超臨界水６０が検
出室４２と反応槽４１を循環することにより、ＰＣＢの
分解過程が塩素化有機物の検出装置５０によって紫外線
吸収法で計測される。検出装置５０が分解終了を通知す
ると、三方弁４４が切り替えられて取り出し室４３に分
解処理済み廃棄物が送られて処理が終了する。Next, the decomposition treatment of chlorinated organic substances using this decomposition apparatus will be described with reference to a PCB. PCB is
Dechlorination is performed by supercritical water in the reaction tank 41 to be decomposed. By circulating the supercritical water 60 containing the PCB and the decomposition products through the detection chamber 42 and the reaction tank 41, the decomposition process of the PCB is measured by the chlorinated organic substance detection device 50 by the ultraviolet absorption method. When the detection device 50 notifies the end of disassembly, the three-way valve 44 is switched, the disassembled waste is sent to the extraction chamber 43, and the process ends.
【００２６】次に、塩素化有機物の検出装置５０による
分解終了時の判定方法について説明する。この検出装置
５０は、紫外線光源５１、レンズ５５〜５８、分光器５
２、光パワーメーター５３及び制御部５４を備えてお
り、紫外線光源５１から出た紫外光６５を検出室４２の
分光セルに集光するようにレンズ５５，５６が配置さ
れ、検出室４２の分光セルから出た紫外光６６を分光器
５２に集光するようにレンズ５７，５８が配置されてい
る。また、光パワーメーター５３の信号出力が制御部５
４に入力されるように構成されている。Next, a method of judging the end of decomposition by the chlorinated organic matter detection device 50 will be described. The detection device 50 includes an ultraviolet light source 51, lenses 55 to 58, a spectroscope 5
2. The optical power meter 53 and the control unit 54 are provided, and lenses 55 and 56 are arranged so that the ultraviolet light 65 emitted from the ultraviolet light source 51 is focused on the spectral cell of the detection chamber 42. Lenses 57 and 58 are arranged so that ultraviolet light 66 emitted from the cell is focused on the spectroscope 52. The signal output of the optical power meter 53 is controlled by the control unit 5.
4 is input.
【００２７】ここで、紫外線光源５１には、紫外光の安
定な供給源である重水素ランプを用い、レンズ５５〜５
８には、紫外光を吸収しない石英製を用いる。分光器５
２は、塩素の数が少ないＰＣＢほど透過率が高くなり、
かつビフェニルの吸収が０でなく透過率がこれらＰＣＢ
の透過率よりも高い波長域から選択した第１の波長と、
塩素の数が少ないＰＣＢほど透過率が高くなり、かつビ
フェニルの吸収が０となる波長域から選択した第２の波
長とをそれぞれ別に透過するように構成されている。こ
の場合、第１の波長は、図２と図３から分かるように、
２００ｎｍ〜２３５ｎｍの波長域から任意に選択してよ
く、第２の波長は、図２と図４から分かるように、２９
５ｎｍ〜３００ｎｍの波長域から任意に選択してよい。
光パワーメーター５３は、分光器５２を透過した第１の
波長と第２の波長の紫外線強度をそれぞれ別に測定し、
制御部５４に通知する。制御部５４は、光パワーメータ
ー５３の２つの測定値から分解終了判定を行う。Here, as the ultraviolet light source 51, a deuterium lamp which is a stable supply source of ultraviolet light is used, and lenses 55 to 5 are used.
8 is made of quartz which does not absorb ultraviolet light. Spectrometer 5
2 means that the transmittance is higher for PCBs with less chlorine,
And the biphenyl absorption is not zero and the transmittance is
A first wavelength selected from a wavelength range higher than the transmittance of
The PCB is configured such that the transmittance of the PCB is lower as the number of chlorine is smaller, and the second wavelength selected from the wavelength range where the absorption of biphenyl is zero is separately transmitted. In this case, the first wavelength is, as can be seen from FIGS. 2 and 3,
The wavelength may be arbitrarily selected from a wavelength range of 200 nm to 235 nm, and the second wavelength is 29 nm as can be seen from FIGS.
It may be arbitrarily selected from a wavelength range of 5 nm to 300 nm.
The optical power meter 53 separately measures the ultraviolet intensity of the first wavelength and the second wavelength transmitted through the spectroscope 52,
The control unit 54 is notified. The control unit 54 determines the end of the decomposition from the two measured values of the optical power meter 53.
【００２８】分解終了判定は、つぎのようにして行う。
まず、あらかじめ測定し記憶していた超臨界水のみを検
出室４２の分光セルに満たしたときの光パワーメーター
５３の測定値を参照して、ＰＣＢと分解生成物を含んだ
超臨界水６０が検出室４２の分光セルを流れたときの光
パワーメーター５３の２つ測定値からこの超臨界水６０
の第１の波長と第２の波長の透過率を計算する。The determination of the completion of disassembly is performed as follows.
First, referring to the measured value of the optical power meter 53 when only the pre-measured and stored supercritical water is filled in the spectroscopic cell of the detection chamber 42, the supercritical water 60 containing the PCB and the decomposition products is obtained. From the two measured values of the optical power meter 53 flowing through the spectroscopic cell of the detection chamber 42, the supercritical water 60
Is calculated for the first wavelength and the second wavelength.
【００２９】次に、これら波長の透過率を所定の時間間
隔で監視することにより、第１の波長でＰＣＢの分解と
ビフェニルの生成を確認し、第２の波長で残留ＰＣＢの
濃度を確認する。ＰＣＢの分解とビフェニルの生成が確
認され、残留ＰＣＢの濃度が規制値以下となったら分解
処理の終了を通知する。この場合、第１の波長の透過率
は、最初、各種ＰＣＢの脱塩素化により塩素の多いＰＣ
Ｂが減少することにより吸収が減って透過率が上昇す
る。その後、脱塩素化によるＰＣＢ分解反応はさらに進
み、ＰＣＢがビフェニルに変化し始める。生成されたビ
フェニルの濃度は、時間経過とともに上昇し、ビフェニ
ルの吸収により透過率が減少する。Next, by monitoring the transmittance at these wavelengths at predetermined time intervals, the decomposition of PCB and the formation of biphenyl are confirmed at the first wavelength, and the concentration of residual PCB is confirmed at the second wavelength. . Decomposition of PCB and generation of biphenyl are confirmed, and when the concentration of residual PCB becomes lower than the regulation value, the end of decomposition processing is notified. In this case, the transmittance of the first wavelength is initially determined by dechlorinating various PCBs to increase the chlorine-rich PC.
As B decreases, the absorption decreases and the transmittance increases. Thereafter, the PCB decomposition reaction by dechlorination proceeds further, and the PCB starts to change to biphenyl. The concentration of the generated biphenyl increases with time, and the transmittance decreases due to the absorption of the biphenyl.
【００３０】例えば、生成されるビフェニルの濃度が１
６ｐｐｍとなるときに波長２０７ｎｍで測定すると、そ
の透過率は、脱塩素化による分解反応開始後５分で７５
％に達したのち減少に向かい、１２０分で４３％に低下
した。また、第２の波長の透過率は、ビフェニルによる
吸収がないことから、脱塩素化によるＰＣＢ分解反応が
進むに従いビフェニルが生成されるようになっても、透
過率は単調に増加する。例えば、波長２９８ｎｍで測定
すると、その透過率は８２％から単調に増加し、分解開
始後１２０分で９９．５％以上になった。For example, if the concentration of biphenyl formed is 1
When measured at a wavelength of 207 nm at 6 ppm, the transmittance is 75 minutes after the start of the decomposition reaction by dechlorination.
% And then headed for a decrease, falling to 43% in 120 minutes. Further, since the transmittance of the second wavelength does not absorb by biphenyl, the transmittance monotonously increases even if biphenyl is generated as the PCB decomposition reaction by dechlorination proceeds. For example, when measured at a wavelength of 298 nm, the transmittance monotonically increased from 82%, and became 99.5% or more 120 minutes after the start of decomposition.
【００３１】以上説明したように、この実施の形態によ
れば、塩素の数が少ないＰＣＢほど透過率が高くなり、
かつビフェニルの吸収が０でなく透過率がこれらＰＣＢ
の透過率よりも高い波長域から選択した第１の波長と、
塩素の数が少ないＰＣＢほど透過率が高くなり、かつビ
フェニルの吸収が０となる波長域から選択した第２の波
長とをそれぞれ別に監視することにより、ＰＣＢの分解
及びビフェニル生成の確認と残留ＰＣＢ濃度の確認が可
能となり、分解生成物の影響を受けずに分解処理の終了
判定を行うことができる。As described above, according to this embodiment, the transmittance of a PCB having a smaller number of chlorines becomes higher,
And the biphenyl absorption is not zero and the transmittance is
A first wavelength selected from a wavelength range higher than the transmittance of
By monitoring separately the second wavelength selected from the wavelength region where the PCB with a smaller number of chlorine has a higher transmittance and the absorption of biphenyl is zero, it is possible to confirm the decomposition of the PCB and the formation of biphenyl and the residual PCB. The concentration can be confirmed, and the end of the decomposition process can be determined without being affected by the decomposition products.
【００３２】次に、この発明の第３の実施の形態につい
て説明する。図７は、この発明の検出方法に係る第３の
実施の形態で用いられる分解装置の概略図であり、同図
において図６と同じ部分には同一符号を付してある。こ
の実施の形態が第２の実施の形態と異なる点は、塩素化
有機物の検出を紫外線励起による発光スペクトルで行う
ようにしたことである。図７において、この分解装置
は、反応槽４１、検出室４２、取り出し室４３及び塩素
化有機物の検出装置７０を備えており、反応槽４１と検
出室４２が配管接続され、検出室４２が三方弁４４を介
して取り出し室４３と反応槽４１とに配管接続されてい
る。また、塩素化有機物の検出装置７０は、検出室４２
周りに取り付けられている。なお、図７において、塩素
化有機物の検出装置７０以外は、図６と同じであるので
説明を省略する。Next, a third embodiment of the present invention will be described. FIG. 7 is a schematic diagram of a decomposition apparatus used in the third embodiment according to the detection method of the present invention. In FIG. 7, the same parts as those in FIG. 6 are denoted by the same reference numerals. This embodiment is different from the second embodiment in that the detection of chlorinated organic substances is performed using an emission spectrum excited by ultraviolet light. In FIG. 7, this decomposition apparatus includes a reaction tank 41, a detection chamber 42, an extraction chamber 43, and a chlorinated organic substance detection apparatus 70. The reaction tank 41 and the detection chamber 42 are connected by piping, and the detection chamber 42 is three-way. A pipe is connected to the take-out chamber 43 and the reaction tank 41 via a valve 44. Further, the chlorinated organic matter detection device 70 is provided in the detection chamber 42.
Attached around. 7 is the same as FIG. 6 except for the chlorinated organic matter detection device 70, and therefore the description is omitted.
【００３３】この実施の形態の検出装置７０は、検出室
４２の分光セルに励起用紫外線６８を照射する紫外線光
源７１、分光器７２、検出室４２と分光器７２の間に配
置された検出室４２の分光セルから出る光６９を分光器
７２に収束させる２つのレンズ７７，７８、分光器７２
の出力光の強度を計測する光パワーメーター７３及び光
パワーメーター７３の信号出力が入力され、濃度を算出
する制御部７４で構成されている。ここで、紫外線光源
７１には、出力波長２４７ｎｍのレーザ光源を用い、レ
ンズ７７，７８には、紫外光を吸収しない石英製を用い
る。分光器７２は、塩素の数が少ないＰＣＢほど発光量
が多くなり、かつビフェニルの発光がない波長域から選
択した所定波長だけを透過するように構成されている。
光パワーメーター７３は、分光器７２を透過した光の強
度を測定し、制御部７４に通知する。制御部７４は、光
パワーメーター７３の測定値から分解終了判定を行う。The detection device 70 of this embodiment includes an ultraviolet light source 71 for irradiating the ultraviolet ray 68 for excitation to the spectral cell of the detection chamber 42, a spectroscope 72, and a detection chamber disposed between the detection chamber 42 and the spectroscope 72. The two lenses 77 and 78 for converging the light 69 emitted from the 42 spectroscopic cell to the spectroscope 72,
An optical power meter 73 for measuring the intensity of the output light of the optical power meter 73 and a signal output from the optical power meter 73 are input, and the control unit 74 is configured to calculate the density. Here, a laser light source having an output wavelength of 247 nm is used as the ultraviolet light source 71, and quartz lenses that do not absorb ultraviolet light are used as the lenses 77 and 78. The spectrometer 72 is configured such that the light emission amount increases as the number of chlorine atoms in the PCB decreases, and the spectrometer 72 transmits only a predetermined wavelength selected from a wavelength range in which biphenyl does not emit light.
The optical power meter 73 measures the intensity of the light transmitted through the spectroscope 72 and notifies the control unit 74 of the intensity. The control unit 74 determines the end of decomposition from the measured value of the optical power meter 73.
【００３４】次に、この実施の形態の検出方法をＰＣＢ
の分解に適用した場合を例に説明する。ＰＣＢのように
複数の種類が存在する場合は、分解後の残留濃度が規制
値以下であることを保証するため、種類によって検出感
度が異なる可能性を考慮する必要がある。この実施の形
態のように、紫外線励起されたＰＣＢの発光量で濃度を
検出する場合は、塩素の数によって発光量が変化すると
考えられるため、分解生成物のビフェニル、ＫＣ３００
及びＫＣ６００について紫外線励起による発光スペクト
ルを測定した。ここでビフェニルの測定を行ったのは、
分解生成物とＰＣＢの発光スペクトルが同じ場合、残留
濃度の測定ができなくなるため、ＰＣＢが発光しビフェ
ニルが発光しない波長領域を見いだすためである。Next, the detection method of this embodiment is
An example in which the present invention is applied to the decomposition will be described. When there are a plurality of types such as PCBs, it is necessary to consider the possibility that the detection sensitivity differs depending on the types in order to guarantee that the residual concentration after decomposition is below the regulation value. When the concentration is detected based on the amount of light emitted from the PCB excited by ultraviolet light as in this embodiment, it is considered that the amount of light emitted changes depending on the number of chlorine atoms.
And KC600 was measured for the emission spectrum by ultraviolet excitation. The measurement of biphenyl here was
This is because if the emission spectrum of the decomposition product is the same as that of the PCB, the residual concentration cannot be measured, so that a wavelength region where the PCB emits light and biphenyl does not emit light is found.
【００３５】図８は、波長２４７ｎｍの紫外線で励起さ
れたＰＣＢとビフェニルの発光スペクトルを示すグラフ
であり、ａがＫＣ３００、ｂがＫＣ６００、ｃがビフェ
ニルを示し、横軸が発光スペクトルの波長、左側の縦軸
がＫＣ３００とＫＣ６００の信号強度、右側の縦軸がビ
フェニルの信号強度を示す。この実験では、相互作用長
１ｃｍの分光セルを用い、ＫＣ３００とＫＣ６００の濃
度を０．５ｐｐｍとし、ビフェニルの濃度を５０ｐｐｍ
とした。この実験結果から、３８０ｎｍ〜４００ｎｍの
領域でビフェニルによる発光がなく、塩素の数が少ない
ほど発光量が多くなることが分かった。FIG. 8 is a graph showing the emission spectra of PCB and biphenyl excited by ultraviolet light having a wavelength of 247 nm, wherein a represents KC300, b represents KC600, c represents biphenyl, the horizontal axis represents the wavelength of the emission spectrum, and the left side represents the wavelength. The vertical axis indicates the signal strength of KC300 and KC600, and the right vertical axis indicates the signal strength of biphenyl. In this experiment, a spectroscopic cell having an interaction length of 1 cm was used, the concentrations of KC300 and KC600 were 0.5 ppm, and the concentration of biphenyl was 50 ppm.
And From this experimental result, it was found that there was no light emission from biphenyl in the region of 380 nm to 400 nm, and the light emission amount increased as the number of chlorines decreased.
【００３６】すなわち、この領域においては、ＰＣＢ分
解反応の進行によって、各種ＰＣＢの脱塩素化により塩
素の多いＰＣＢが塩素基の少ないＰＣＢに変わることに
より発光量が増加した後、さらに脱塩素化が進んでビフ
ェニルが生成されることによりＰＣＢの量が減少して発
光量が減少する。この場合、残留しているＰＣＢは、塩
素の少ないＰＣＢであると見なせるので、分解終了と判
定する発光量は、塩素の少ないＰＣＢのものでよい。こ
れにより、塩素の多いＰＣＢの発光量になるまで待つ必
要がないので、処理時間を短くすることができる。That is, in this region, as the PCB decomposition reaction progresses, the PCB containing a large amount of chlorine is changed to a PCB containing a small amount of chlorine by dechlorination of various PCBs, so that the luminescence amount increases. As the biphenyl is produced, the amount of PCB decreases and the amount of light emission decreases. In this case, since the remaining PCB can be regarded as a PCB with a small amount of chlorine, the amount of light emitted to determine that the decomposition is completed may be a PCB with a small amount of chlorine. As a result, it is not necessary to wait until the light emission amount of the PCB containing a large amount of chlorine is reached, so that the processing time can be shortened.
【００３７】次に、この実施の形態の検出装置７０の動
作について説明する。なお、ＰＣＢの分解処理の過程
は、第２の実施の形態と同じであるので説明を省略す
る。検出室４２の分光セルに紫外線光源７１から波長２
４７ｎｍの励起用紫外線６８が照射され、超臨界水中の
ＰＣＢが励起発光される。この発光は、レンズ７７，７
８により分光器７２に集光される。分光器７２は、波長
３８０ｎｍの光だけを透過させるように構成されてお
り、分光器７２を透過した光は光パワーメーター７３に
入射して発光量が測定される。光パワーメーター７３
は、制御部７４に測定結果を通知する。制御部７４は、
光パワーメーター７３の測定値から分解終了判定を行
う。Next, the operation of the detecting device 70 of this embodiment will be described. Note that the process of disassembling the PCB is the same as in the second embodiment, and a description thereof will be omitted. The wavelength 2 from the ultraviolet light source 71 is applied to the spectral cell of the detection chamber 42.
Ultraviolet rays 68 for excitation of 47 nm are irradiated, and the PCB in the supercritical water is excited and emits light. This light is emitted by the lenses 77 and 7
The light is condensed on the spectroscope 72 by 8. The spectrometer 72 is configured to transmit only light having a wavelength of 380 nm, and the light transmitted through the spectrometer 72 enters the optical power meter 73 and measures the amount of light emission. Optical power meter 73
Notifies the control unit 74 of the measurement result. The control unit 74
From the measured value of the optical power meter 73, the end of decomposition is determined.
【００３８】分解終了判定は、つぎのようにして行う。
まず、光パワーメーター７３の測定値とあらかじめ測定
し記憶していたＰＣＢで最も塩素の数が少ないＰＣＢの
濃度０．５ｐｐｍでの発光量とを比較する。光パワーメ
ーター７３の測定値が記憶していた発光量以下になるま
で所定時間ごとに分解終了判定を行い、測定値が記憶し
ていた発光量以下になったら分解処理の終了を通知す
る。The determination of the completion of disassembly is performed as follows.
First, the measured value of the optical power meter 73 is compared with the amount of light emission at a concentration of 0.5 ppm of the PCB having the smallest number of chlorines among the PCBs measured and stored in advance. Until the measured value of the optical power meter 73 becomes equal to or less than the stored light emission amount, the end of decomposition is determined at predetermined time intervals, and when the measured value becomes equal to or less than the stored light emission amount, the end of the decomposition process is notified.
【００３９】この場合、励起波長を２４７ｎｍとした
が、これに限られるものではなく、ＰＣＢの吸収領域で
ある２００ｎｍ〜３００ｎｍの波長領域で任意に選んで
よい。また、測定波長を３８０ｎｍとしたが、これに限
られるものではなく、３８０ｎｍ〜４００ｎｍの波長領
域で任意に選んでよい。また、超臨界水の吸収や発光と
ビフェニルによる発光がなく、塩素の数が少ないほど発
光量が多くなる波長領域であれば、３８０ｎｍ〜４００
ｎｍの波長領域に限られるものではない。In this case, the excitation wavelength is set to 247 nm. However, the present invention is not limited to this. The excitation wavelength may be arbitrarily selected in the wavelength region of 200 nm to 300 nm which is the absorption region of PCB. Further, the measurement wavelength is 380 nm, but is not limited to this, and may be arbitrarily selected in a wavelength range of 380 nm to 400 nm. In addition, in a wavelength region where there is no absorption or emission of supercritical water and no emission due to biphenyl, and the emission amount increases as the number of chlorines decreases, the wavelength range is 380 nm to 400 nm.
It is not limited to the wavelength region of nm.
【００４０】以上説明したように、この実施の形態によ
れば、塩素の数が少ないＰＣＢほど発光量が多くなり、
かつビフェニルの発光量が０となる波長域から選択した
波長の励起発光量を測定することにより、超臨界水によ
るＰＣＢの分解の過程を励起発光量の変化により知るこ
とができる。また、測定した発光量が最も塩素の数が少
ないＰＣＢの規制値濃度の発光量以下になったときに分
解処理終了と判定することができるので、余分な処理時
間をかけずにすみ、処理時間を短縮できる。As described above, according to this embodiment, the light emission amount increases as the number of chlorines in the PCB decreases.
In addition, by measuring the amount of excitation light emission at a wavelength selected from a wavelength range in which the amount of light emission of biphenyl is 0, the process of decomposition of PCB by supercritical water can be known from the change in the amount of excitation light emission. Further, when the measured light emission amount becomes equal to or less than the light emission amount of the regulated value concentration of the PCB having the smallest number of chlorines, it is possible to determine that the decomposition process is completed, so that no extra processing time is required and the processing time is reduced. Can be shortened.
【００４１】[0041]
【発明の効果】以上説明したように、この発明の塩素化
有機物の検出方法は、光の吸収や励起発光を用いて非接
触で測定できるので、有害な塩素化有機物を環境に放出
する恐れがなく、分解工程や洗浄工程の終了時点を確認
することができる効果を有する。また、結合している塩
素の数が少ない塩素化有機物ほど高い透過率や発光量を
示す波長域から選択した波長の測定値と、結合している
塩素の数が最も少ない塩素化有機物の所定値の濃度にお
ける透過率や発光量とを比較して処理終了を判定するの
で、結合している塩素の数が異なる混合物からなる塩素
化有機物であっても分解工程や洗浄工程の進行状況や終
了時点を確認することができるという効果を有する。As described above, the method for detecting a chlorinated organic substance according to the present invention can be measured in a non-contact manner by using light absorption or excitation light emission, so that harmful chlorinated organic substances may be released to the environment. In addition, there is an effect that the end point of the decomposition step and the cleaning step can be confirmed. In addition, a measured value of a wavelength selected from a wavelength region showing a higher transmittance and an emission amount as the chlorinated organic material having a smaller number of bound chlorine, and a predetermined value of the chlorinated organic material having the smallest number of bound chlorine. The end of the process is determined by comparing the transmittance and the amount of light emitted at the concentration of chlorinated organic compounds. Can be confirmed.
【図１】 第１の実施の形態で用いる洗浄装置の概略図
である。FIG. 1 is a schematic diagram of a cleaning device used in a first embodiment.
【図２】 塩素の数が異なるＰＣＢとビフェニルによる
紫外線吸収量を示すグラフである。FIG. 2 is a graph showing ultraviolet absorption amounts of PCB and biphenyl having different numbers of chlorines.
【図３】 図２の一部を拡大したグラフである。FIG. 3 is a graph in which a part of FIG. 2 is enlarged.
【図４】 図２の一部を拡大したグラフである。FIG. 4 is a graph in which a part of FIG. 2 is enlarged.
【図５】 塩素の数が異なるＰＣＢによる紫外線吸収量
を示すグラフである。FIG. 5 is a graph showing the amount of ultraviolet absorption by PCBs having different numbers of chlorines.
【図６】 第２の実施の形態で用いる分解装置の概略図
である。FIG. 6 is a schematic diagram of a decomposition apparatus used in the second embodiment.
【図７】 第３の実施の形態で用いる分解装置の概略図
である。FIG. 7 is a schematic diagram of a disassembly device used in a third embodiment.
【図８】 塩素の数が異なるＰＣＢとビフェニルによる
発光スペクトルを示すグラフである。FIG. 8 is a graph showing emission spectra of PCB and biphenyl having different numbers of chlorines.
１１…洗浄槽、１２，４２…検出室、１３…分離室、１
４…超臨界流体循環用圧縮装置、１５，１６，１７，１
８…開閉弁、１９…取り出し弁、２０，５０，７０…検
出装置、２１，５１…光源、２２，５２，７２…分光
器、２３，５３，７３…光パワーメーター、２４，５
４，７４…制御部、２５，２６，２７，２８，５５，５
６，５７，５８，７６，７７…レンズ、３０…ＰＣＢを
含んだ超臨界二酸化炭素、３１…気体状態の二酸化炭
素、３２…超臨界二酸化炭素、３３…ＰＣＢ、３５，３
６，６５，６６，７２…紫外光、４１…反応槽、４３…
取り出し室、４４…三方弁、６０…ＰＣＢと分解生成物
を含んだ超臨界水、６８…励起用紫外線、７１…紫外線
光源。11: washing tank, 12, 42: detection chamber, 13: separation chamber, 1
4. Supercritical fluid circulation compression device, 15, 16, 17, 1
8 open / close valve, 19 take-out valve, 20, 50, 70 detection device, 21 51 light source, 22, 52, 72 spectroscope, 23, 53, 73 light power meter, 24, 5
4, 74 ... control unit, 25, 26, 27, 28, 55, 5
6, 57, 58, 76, 77 ... lens, 30 ... supercritical carbon dioxide containing PCB, 31 ... gaseous carbon dioxide, 32 ... supercritical carbon dioxide, 33 ... PCB, 35, 3
6, 65, 66, 72 ... ultraviolet light, 41 ... reaction tank, 43 ...
Extraction chamber, 44: three-way valve, 60: supercritical water containing PCB and decomposition products, 68: ultraviolet rays for excitation, 71: ultraviolet light source.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2G043 AA01 BA06 BA14 CA03 EA01 EA13 HA01 HA08 JA01 KA03 LA01 2G059 AA01 BB04 CC12 EE01 EE07 EE11 HH03 HH06 JJ01 JJ11 4D056 AB20 AC24 BA16 CA13 CA21 CA22 DA01 DA02 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2G043 AA01 BA06 BA14 CA03 EA01 EA13 HA01 HA08 JA01 KA03 LA01 2G059 AA01 BB04 CC12 EE01 EE07 EE11 HH03 HH06 JJ01 JJ11 4D056 AB20 AC24 BA16 CA13 CA21 CA22 DA01 DA02
Claims (14)
素化有機物を含む物品からこれらの塩素化有機物を除去
する工程における前記塩素化有機物の残留濃度が所定値
以下となったことを検出する方法であって、 前記塩素化有機物を含む物品に所定の溶媒を接触させて
前記塩素化有機物を選択的に溶出させ、 前記塩素化有機物を含む前記溶媒に紫外線を照射して所
定波長の透過率を測定し、 この透過率が所定の透過率以上となったときに前記塩素
化有機物の残留濃度を前記所定値以下の濃度と判定する
ようにし、 前記所定波長を結合している塩素の数が少ない塩素化有
機物ほど高い透過率を示す波長域から選択し、 前記所定の透過率を結合している塩素の数が最も少ない
塩素化有機物の前記所定値の濃度における透過率とした
ことを特徴とする塩素化有機物の検出方法。1. detecting that the residual concentration of the chlorinated organic substance in a step of removing the chlorinated organic substance from an article containing a plurality of chlorinated organic substances having a different number of bound chlorine has become a predetermined value or less. A method of contacting a predetermined solvent with an article containing the chlorinated organic substance to selectively elute the chlorinated organic substance, and irradiating the solvent containing the chlorinated organic substance with ultraviolet light to transmit a predetermined wavelength. The residual concentration of the chlorinated organic substance is determined to be a concentration equal to or less than the predetermined value when the transmittance becomes equal to or more than a predetermined transmittance, and the number of chlorines binding the predetermined wavelength is determined. The chlorinated organic matter having a smaller number is selected from a wavelength region showing a higher transmittance, and the predetermined transmittance is the transmittance at a concentration of the predetermined value of the chlorinated organic material having the smallest number of chlorines bonded thereto. When Method of detecting that chlorinated organics.
とを特徴とする請求項１記載の塩素化有機物の検出方
法。2. The method for detecting chlorinated organic matter according to claim 1, wherein the solvent is supercritical carbon dioxide.
であり、前記波長域を２００ｎｍ以上２４５ｎｍ以下、
あるいは２８０ｎｍ以上３００ｎｍ以下としたことを特
徴とする請求項２記載の塩素化有機物の検出方法。3. The chlorinated organic substance is polychlorinated biphenyl, and the wavelength range is from 200 nm to 245 nm,
3. The method for detecting chlorinated organic matter according to claim 2, wherein the wavelength is 280 nm or more and 300 nm or less.
素化有機物を含む物品からこれらの塩素化有機物を除去
する工程における前記塩素化有機物の残留濃度が所定値
以下となったことを検出する方法であって、 前記塩素化有機物を含む物品に所定の溶媒を接触させて
前記塩素化有機物を選択的に溶出、分解させ、 前記塩素化有機物と分解生成物とを含む前記溶媒に紫外
線を照射して、第１の波長の透過率と第２の波長の透過
率とをそれぞれ測定し、 前記第１の波長で前記分解生成物を検出し、 前記第２の波長の透過率が所定の透過率以上となったと
きに前記塩素化有機物の残留濃度を前記所定値以下の濃
度と判定するようにし、 前記第１の波長を結合している塩素の数が少ない塩素化
有機物ほど高い透過率を示し、かつ前記分解生成物の吸
収を受ける第１の波長域から選択し、 前記第２の波長を結合している塩素の数が少ない塩素化
有機物ほど高い透過率を示し、かつ前記分解生成物の吸
収を受けない第２の波長域から選択し、 前記所定の透過率を結合している塩素の数が最も少ない
塩素化有機物の前記所定値の濃度における透過率とした
ことを特徴とする塩素化有機物の検出方法。4. A method for detecting that a residual concentration of the chlorinated organic substance in a step of removing the chlorinated organic substance from an article containing a plurality of chlorinated organic substances having different numbers of bound chlorines is lower than a predetermined value. In a method, a predetermined solvent is brought into contact with an article containing the chlorinated organic substance to selectively elute and decompose the chlorinated organic substance, and the solvent containing the chlorinated organic substance and the decomposition product is irradiated with ultraviolet rays. Irradiating, measuring the transmittance of the first wavelength and the transmittance of the second wavelength, respectively, detecting the decomposition product at the first wavelength, the transmittance of the second wavelength is a predetermined The residual concentration of the chlorinated organic substance is determined to be less than or equal to the predetermined value when the transmittance is equal to or higher than the predetermined value, and the chlorinated organic substance having a smaller number of chlorines that couples the first wavelength has a higher transmittance. And the decomposition product A second wavelength which is selected from a first wavelength range that receives light, and wherein the chlorinated organic material having a smaller number of chlorines binding the second wavelength has a higher transmittance and does not receive absorption of the decomposition product. A method for detecting a chlorinated organic substance, wherein the transmittance is selected from a wavelength range, and the predetermined transmittance is the transmittance of the chlorinated organic substance having the smallest number of bound chlorine at the concentration of the predetermined value.
であり、前記第１の波長域を２００ｎｍ以上２３５ｎｍ
以下とし、前記第２の波長域を２９５ｎｍ以上３００ｎ
ｍ以下としたことを特徴とする請求項４記載の塩素化有
機物の検出方法。5. The chlorinated organic substance is polychlorinated biphenyl, and the first wavelength range is 200 nm or more and 235 nm.
And the second wavelength range is 295 nm or more and 300 n
5. The method for detecting chlorinated organic matter according to claim 4, wherein m is not more than m.
素化有機物を含む物品からこれらの塩素化有機物を除去
する工程における前記塩素化有機物の残留濃度が所定値
以下となったことを検出する方法であって、 前記塩素化有機物を含む物品に所定の溶媒を接触させて
前記塩素化有機物を選択的に溶出、分解させ、 前記塩素化有機物と分解生成物とを含む前記溶媒に紫外
線を照射して励起発光させて所定波長の発光量を測定
し、 この発光量が所定の発光量以下となったときに前記塩素
化有機物の残留濃度を前記所定値以下の濃度と判定する
ようにし、 前記所定波長を前記分解生成物の励起発光がなく、かつ
塩素基の数が少ない前記塩素化有機物ほど励起発光量が
多い波長域から選択し、 前記所定の発光量を結合している塩素の数が最も少ない
塩素化有機物の前記所定値の濃度における発光量とした
ことを特徴とする塩素化有機物の検出方法。6. A method for detecting that the residual concentration of the chlorinated organic substance in a step of removing the chlorinated organic substance from an article containing a plurality of chlorinated organic substances having a different number of bound chlorines is less than a predetermined value. In a method, a predetermined solvent is brought into contact with an article containing the chlorinated organic substance to selectively elute and decompose the chlorinated organic substance, and the solvent containing the chlorinated organic substance and the decomposition product is irradiated with ultraviolet rays. Irradiation and excitation to emit light to measure the amount of light emission of a predetermined wavelength, and when the amount of light emission becomes equal to or less than a predetermined amount of light, the residual concentration of the chlorinated organic substance is determined to be a concentration equal to or less than the predetermined value, The predetermined wavelength is selected from a wavelength range in which the chlorinated organic substance has no excitation light emission of the decomposition product, and the number of chlorine groups is small, and the amount of excitation light emission is large as the chlorinated organic substance, and the number of chlorines binding the predetermined light emission amount Is the least Method of detecting chlorinated organic substances, characterized in that the light emission amount at a concentration of the predetermined value of the chlorinated organics.
であり、前記波長域を３８０ｎｍ以上４００ｎｍ以下と
したことを特徴とする請求項６記載の塩素化有機物の検
出方法。7. The method for detecting a chlorinated organic substance according to claim 6, wherein the chlorinated organic substance is polychlorinated biphenyl, and the wavelength range is 380 nm or more and 400 nm or less.
とする請求項４〜７のいずれかに記載の塩素化有機物の
検出方法。8. The method for detecting chlorinated organic matter according to claim 4, wherein the solvent is supercritical water.
素化有機物を含む物品からこれらの塩素化有機物を除去
する工程における前記塩素化有機物の残留濃度が所定値
以下となったことを検出する検出装置であって、 紫外線光源と、 紫外線が透過可能に構成され前記物品から溶出された前
記塩素化有機物を含む溶媒が通過する分光セルと、 結合している塩素の数が少ない塩素化有機物ほど高い透
過率を示す波長域から選択した波長の紫外線を透過させ
る分光器と、 前記分光器を透過した光量を測定する光パワーメーター
と、 前記光パワーメーターの測定値が入力されて透過率を算
出し、前記透過率が結合している塩素の数が最も少ない
塩素化有機物の前記所定値に対応する透過率以上となっ
たときに前記所定値以下の濃度と判定し、通知するよう
に構成された制御部とを備えたことを特徴とする塩素化
有機物の検出装置。9. Detecting that the residual concentration of the chlorinated organic substance in a step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of chlorines bonded thereto is lower than a predetermined value. An ultraviolet light source, a spectroscopic cell configured to transmit ultraviolet light and passing a solvent containing the chlorinated organic substance eluted from the article, and a chlorinated organic substance having a small number of chlorines bound thereto. A spectroscope that transmits ultraviolet light having a wavelength selected from a wavelength range that exhibits a higher transmittance, an optical power meter that measures the amount of light transmitted through the spectrometer, and a transmittance that is obtained by inputting a measurement value of the optical power meter. When the calculated transmittance is equal to or higher than the transmittance corresponding to the predetermined value of the chlorinated organic substance having the smallest number of chlorines bonded thereto, the concentration is determined to be equal to or lower than the predetermined value, and a notification is made. Detector of chlorinated organic substances, characterized in that a configured controlled unit such.
ルであり、前記波長域は２００ｎｍ以上２４５ｎｍ以
下、あるいは２８０ｎｍ以上３００ｎｍ以下であること
を特徴とする請求項９記載の塩素化有機物の検出装置。10. The chlorinated organic substance detection device according to claim 9, wherein the chlorinated organic substance is polychlorinated biphenyl, and the wavelength range is from 200 nm to 245 nm, or from 280 nm to 300 nm.
塩素化有機物を含む物品からこれらの塩素化有機物を除
去する工程における前記塩素化有機物の残留濃度が所定
値以下となったことを検出する検出装置であって、 紫外線光源と、 紫外線が透過可能に構成され前記物品から溶出された前
記塩素化有機物と前記塩素化有機物の分解生成物とを含
む溶媒が通過する分光セルと、 結合している塩素の数が少ない前記塩素化有機物ほど高
い透過率を示し、かつ前記分解生成物の吸収を受ける第
１の波長域から選択した第１の波長と、結合している塩
素の数が少ない前記塩素化有機物ほど高い透過率を示
し、かつ前記分解生成物の吸収を受けない第２の波長域
から選択した第２の波長とをそれぞれ別に透過させる分
光器と、 前記分光器を透過した２つの波長の光量をそれぞれ別に
測定する光パワーメーターと、 前記光パワーメーターの２つの測定値が入力されてそれ
ぞれの透過率を算出し、前記第１の波長で前記分解生成
物を検出し、前記第２の波長の透過率が結合している塩
素の数が最も少ない前記塩素化有機物の前記所定値の濃
度における透過率以上となったときに前記所定値以下の
濃度と判定し、通知するように構成された制御部とを備
えたことを特徴とする塩素化有機物の検出装置。11. Detecting that the residual concentration of the chlorinated organic substance in the step of removing these chlorinated organic substances from an article containing a plurality of chlorinated organic substances having different numbers of chlorine bonded thereto has become a predetermined value or less. An ultraviolet light source, a spectroscopic cell configured to allow ultraviolet light to pass therethrough and through which a solvent containing the chlorinated organic substance eluted from the article and a decomposition product of the chlorinated organic substance passes. The chlorinated organic substance having a small number of chlorines exhibits a higher transmittance, and has a first wavelength selected from a first wavelength range in which the decomposition product is absorbed, and a small number of chlorines bonded thereto. A spectrometer that transmits a second wavelength selected from a second wavelength range that does not receive the absorption of the decomposition product, showing a higher transmittance as the chlorinated organic substance is separately transmitted; An optical power meter that separately measures the light amounts of two wavelengths, and two measured values of the optical power meter are input to calculate respective transmittances, and the decomposition products are detected at the first wavelength, When the transmittance of the second wavelength is equal to or higher than the transmittance at the concentration of the predetermined value of the chlorinated organic substance having the smallest number of chlorines bonded thereto, it is determined that the concentration is equal to or lower than the predetermined value, and the notification is performed. An apparatus for detecting a chlorinated organic substance, comprising: a control unit configured as described above.
ルであり、前記第１の波長域は２００ｎｍ以上２３５ｎ
ｍ以下であり、前記第２の波長域は２９５ｎｍ以上３０
０ｎｍ以下であることを特徴とする請求項１１記載の塩
素化有機物の検出装置。12. The chlorinated organic substance is polychlorinated biphenyl, and the first wavelength range is 200 nm or more and 235 n.
m or less, and the second wavelength range is 295 nm or more and 30
The chlorinated organic substance detection device according to claim 11, wherein the thickness is 0 nm or less.
塩素化有機物を含む物品からこれらの塩素化有機物を除
去する工程における前記塩素化有機物の残留濃度が所定
値以下となったことを検出する検出装置であって、 紫外線光源と、 紫外線が透過可能に構成され前記物品から溶出された前
記塩素化有機物と前記塩素化有機物の分解生成物とを含
む溶媒が通過する分光セルと、 前記分解生成物の励起発光がなく、かつ塩素基の数が少
ない前記塩素化有機物ほど励起発光量が多い波長域から
選択した波長を透過させる分光器と、 前記分光器を透過した光量を測定する光パワーメーター
と、 前記光パワーメーターの測定値が入力されて発光量を算
出し、前記発光量が結合している塩素の数が最も少ない
前記塩素化有機物の前記所定値の濃度における発光量以
下となったときに前記所定値以下の濃度と判定し、通知
するように構成された制御部とを備えたことを特徴とす
る塩素化有機物の検出装置。13. A method for detecting that a residual concentration of the chlorinated organic substance in a step of removing the chlorinated organic substance from an article containing a plurality of chlorinated organic substances having different numbers of bound chlorines is lower than a predetermined value. An ultraviolet light source; a spectroscopic cell configured to transmit ultraviolet light and passing a solvent containing the chlorinated organic substance eluted from the article and a decomposition product of the chlorinated organic substance; and A spectroscope that transmits a wavelength selected from a wavelength range in which the chlorinated organic substance has no excitation light emission of the product and has a small number of chlorine groups and has a large amount of excitation light emission as the chlorinated organic substance, and an optical power for measuring the amount of light transmitted through the spectrometer. A meter and a measured value of the optical power meter are input to calculate a light emission amount, and the light emission amount is set to a concentration of the predetermined value of the chlorinated organic substance having the smallest number of chlorines bonded thereto. That said determining the predetermined value or less of the concentration when it becomes a light emission amount below detection device chlorinated organic matter characterized by comprising a control unit configured to notify.
ルであり、前記波長域は３８０ｎｍ以上４００ｎｍ以下
であることを特徴とする請求項１３記載の塩素化有機物
の検出装置。14. The apparatus for detecting a chlorinated organic substance according to claim 13, wherein the chlorinated organic substance is polychlorinated biphenyl, and the wavelength range is from 380 nm to 400 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000081412A JP2001264248A (en) | 2000-03-23 | 2000-03-23 | Detection method of chlorinated organic matter and detection device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000081412A JP2001264248A (en) | 2000-03-23 | 2000-03-23 | Detection method of chlorinated organic matter and detection device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001264248A true JP2001264248A (en) | 2001-09-26 |
Family
ID=18598354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000081412A Pending JP2001264248A (en) | 2000-03-23 | 2000-03-23 | Detection method of chlorinated organic matter and detection device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001264248A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7807025B2 (en) * | 2004-05-25 | 2010-10-05 | Toyo University Educational Foundation | Method of decomposing carbon dioxide and method of forming carbon-particle structure |
| CN111693526A (en) * | 2020-05-19 | 2020-09-22 | 西安交通大学 | Crude oil dissolution observation device in supercritical water and dissolution degree detection method |
-
2000
- 2000-03-23 JP JP2000081412A patent/JP2001264248A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7807025B2 (en) * | 2004-05-25 | 2010-10-05 | Toyo University Educational Foundation | Method of decomposing carbon dioxide and method of forming carbon-particle structure |
| US8038849B2 (en) | 2004-05-25 | 2011-10-18 | Toyo University Educational Foundation | Process for producing a carbon-particle structure |
| CN111693526A (en) * | 2020-05-19 | 2020-09-22 | 西安交通大学 | Crude oil dissolution observation device in supercritical water and dissolution degree detection method |
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