JP2015000376A - Requirement determination apparatus for heavy-metal processing agent - Google Patents

Requirement determination apparatus for heavy-metal processing agent Download PDF

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JP2015000376A
JP2015000376A JP2013126147A JP2013126147A JP2015000376A JP 2015000376 A JP2015000376 A JP 2015000376A JP 2013126147 A JP2013126147 A JP 2013126147A JP 2013126147 A JP2013126147 A JP 2013126147A JP 2015000376 A JP2015000376 A JP 2015000376A
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heavy metal
heavy
solution
treatment agent
turbidity
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英樹 疋田
Hideki Hikita
英樹 疋田
義則 阿山
Yoshinori Ayama
義則 阿山
長井 康行
Yasuyuki Nagai
康行 長井
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Tosoh Corp
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Tosoh Corp
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Abstract

PROBLEM TO BE SOLVED: To determine a requirement of a heavy-metal processing agent simply, rapidly, inexpensively, and accurately when a heavy metal in a heavy-metal containing material such as fly ash is to be insolubilized.SOLUTION: For a requirement determination apparatus for a heavy-metal processing agent having a detector that can detect a turbidity change of a solution where heavy metals have been eluted out of a heavy-metal containing material and the function of calculating a requirement of the heavy-metal containing material from an addition amount of the heavy-metal processing agent at an end point where the turbidity change turns constant or at an inflection point of the turbidity change, an apparatus is used which has a transparence measurement container for supplying a heavy-metal solution, a mixer having the function of mixing the heavy-metal solution, a chemical agent injection part for supplying a heavy-metal processing agent for turbidity measurement from above the mixer, and a laser light source and light receiving part on a lateral part of the transparence measurement container.

Description

本発明は、重金属含有物質に重金属処理剤を加えて重金属を不溶化処理する際に、重金属処理剤の必要量の決定に用いる装置に関するものである。   The present invention relates to an apparatus used for determining a necessary amount of a heavy metal treatment agent when a heavy metal treatment agent is added to a heavy metal-containing substance to insolubilize the heavy metal.

都市ゴミ焼却工場などから排出される飛灰は重金属含有率が高く、重金属の溶出を抑制する処理を施すことが必要である。その様な処理方法のひとつとして薬剤処理法があり、キレート系薬剤などの重金属処理剤を添加して重金属を不溶化する方法が用いられている。このような薬剤処理方法において、確実に重金属の不溶化処理を行うためには重金属処理剤の必要量を把握することが重要である。   Fly ash discharged from municipal waste incineration plants and the like has a high heavy metal content and needs to be treated to suppress elution of heavy metals. As one of such treatment methods, there is a drug treatment method, and a method of insolubilizing heavy metals by adding a heavy metal treatment agent such as a chelate-based drug is used. In such a chemical treatment method, it is important to grasp the necessary amount of the heavy metal treatment agent in order to reliably perform the insolubilization treatment of the heavy metal.

これまで重金属処理剤の必要量を決定する方法としては、机上試験にて飛灰に重金属処理剤を添加して、加湿水添加、混練等の前処理を施し、さらに昭和48年2月17日環境庁告示第13号法で定められる方法で重金属の溶出試験を行い、その溶出液中の重金属濃度を測定する方法が用いられてきた。しかし、環境庁告示第13号法(以下、「13号試験」と表記する)で重金属処理剤の必要量を決定する方法では、時間がかかり、刻々と変化する飛灰に迅速に対応することは困難であった。   Until now, as a method of determining the required amount of heavy metal treatment agent, a heavy metal treatment agent is added to fly ash in a desktop test, pretreatment such as addition of humidified water and kneading is performed, and February 17, 1973 A method has been used in which a heavy metal elution test is performed by the method stipulated by the Environmental Agency Notification No. 13 and the concentration of heavy metal in the eluate is measured. However, the method of determining the required amount of heavy metal treatment agent by the Environmental Agency Notification No. 13 (hereinafter referred to as “No. 13 Test”) takes time and responds quickly to the changing fly ash. Was difficult.

その様な中で、重金属飛灰中の重金属濃度をICPや原子吸光法、蛍光エックス線等で測定し、重金属処理剤の必要量を決定する方法が提案されている(例えば、特許文献1参照)。しかし、これらの方法では、重金属濃度を測定する装置が大型で、かつ高価なため、オンサイトで安価に測定することは困難であった。   Under such circumstances, a method has been proposed in which the heavy metal concentration in heavy metal fly ash is measured by ICP, atomic absorption, fluorescent X-ray, etc., and the necessary amount of heavy metal treating agent is determined (see, for example, Patent Document 1). . However, in these methods, since the apparatus for measuring the heavy metal concentration is large and expensive, it is difficult to measure on-site at a low cost.

また、用いるキレート剤が有する特有な吸収波長の吸光度を測定する方法が提案されている(例えば、特許文献2参照)。しかし、キレート剤特有の吸収波長を測定するためには、キレート剤が有する特有かつ特定の吸収波長に制御できる光学装置が必要なため、装置が高価なものとなる。また、これらの方法は遊離したキレート剤を測定する方法であり、直接重金属類の量を検出する方法ではないため、必ずしも十分な方法とは言えなかった。   In addition, a method for measuring the absorbance at a specific absorption wavelength of the chelating agent used has been proposed (see, for example, Patent Document 2). However, in order to measure the absorption wavelength peculiar to the chelating agent, an optical device that can be controlled to a peculiar and specific absorption wavelength that the chelating agent has is necessary, so that the apparatus becomes expensive. In addition, these methods are methods for measuring a released chelating agent, and are not methods for directly detecting the amount of heavy metals, and thus are not necessarily sufficient methods.

さらに、飛灰と水のスラリーに重金属処理剤を加え、酸化還元電位(ORP)を測定する方法(例えば、特許文献3参照)、あるいはORPとは異なる電位を検知する金属イオン電極により測定する方法(例えば、特許文献4参照)が提案されている。しかし、これらの電位測定は妨害イオンの影響を強く受けるため、必ずしも十分な方法とは言えなかった。   Further, a method of measuring a redox potential (ORP) by adding a heavy metal treatment agent to a slurry of fly ash and water (for example, see Patent Document 3) or a method of measuring by a metal ion electrode that detects a potential different from the ORP (See, for example, Patent Document 4). However, these potential measurements are strongly influenced by interfering ions, and are not necessarily sufficient methods.

これらの課題に対して、濁度を測定する方法(例えば、特許文献5参照)が提案されている。しかしながら、従来の濁度を測定する方法では、重金属濃度が低濃度の場合、必ずしも十分な方法とは言えなかった。   For these problems, a method of measuring turbidity (for example, see Patent Document 5) has been proposed. However, the conventional method for measuring turbidity is not always sufficient when the heavy metal concentration is low.

特開平11−70374号公報Japanese Patent Application Laid-Open No. 11-70374 特開平10−337550号公報JP-A-10-337550 特開平8−309312号公報JP-A-8-309912 特開2003−334513公報JP 2003-334513 A 特許第4599913号公報Japanese Patent No. 4599913

本発明は、飛灰等の重金属含有物質中の重金属を不溶化する際に、重金属処理剤の必要量を簡便、迅速、安価かつ正確に決定するための装置を提供するものである。   The present invention provides an apparatus for simply, quickly, inexpensively and accurately determining the required amount of a heavy metal treating agent when insolubilizing heavy metals in a heavy metal-containing substance such as fly ash.

本発明者等は、飛灰等の重金属含有物質中の重金属を不溶化するために必要な重金属処理剤量を決定する方法について鋭意検討を重ねた結果、
(1)重金属含有物質から重金属を溶出した溶液(以下、「重金属溶液」と表記する)の濁度変化を検出可能な検出器及び濁度変化が一定となる終点もしくは濁度変化の変曲点における重金属処理剤の添加量から重金属処理剤の必要量を算出する機能を有する重金属処理剤の必要量決定装置において、重金属溶液を供給する透明測定容器、重金属溶液を混合する機能を有する攪拌機、その上部から濁度測定用重金属処理剤溶液を供給する薬剤注入部、及び透明測定容器の側方部にレーザー光源部と受光部を有することを特徴とする重金属処理剤の必要量決定装置。
As a result of intensive studies on a method for determining the amount of heavy metal treatment agent necessary for insolubilizing heavy metals in heavy metal-containing materials such as fly ash,
(1) Detector capable of detecting turbidity change of a solution eluting heavy metal from a heavy metal-containing substance (hereinafter referred to as “heavy metal solution”) and end point at which the turbidity change becomes constant or inflection point of turbidity change In a heavy metal treatment agent necessary amount determination device having a function of calculating a required amount of a heavy metal treatment agent from the amount of addition of the heavy metal treatment agent, a transparent measuring container for supplying a heavy metal solution, a stirrer having a function of mixing the heavy metal solution, An apparatus for determining a necessary amount of a heavy metal treatment agent, comprising: a drug injection part for supplying a heavy metal treatment agent solution for turbidity measurement from above; and a laser light source part and a light receiving part at a side part of the transparent measurement container.

(2)薬剤注入部の注入口が重金属溶液の液面より上であることを特徴とする上記(1)に記載の重金属処理剤の必要量決定装置。   (2) The required amount determination device for a heavy metal treatment agent as described in (1) above, wherein the injection port of the drug injection part is above the liquid surface of the heavy metal solution.

(3)透明測定容器の上部が密閉又は半密閉されていることを特徴とする上記(1)又は(2)に記載の重金属処理剤の必要量決定装置。   (3) The required amount determination device for heavy metal treatment agent according to (1) or (2) above, wherein the upper part of the transparent measurement container is sealed or semi-sealed.

(4)上記(1)〜(3)に記載の装置を用い、透明測定容器中の重金属溶液を攪拌し、そこに重金属処理剤溶液を連続的又は断続的に供給し、透明測定容器の側方部からレーザー光を照射して透過光強度を測定し、光透過率の低下(濁度の上昇)度合いから、重金属処理剤の必要量を決定する方法。
とすることで、オンサイトで短時間、かつ簡便に、さらには重金属含有量が低濃度の場合においても正確に、重金属処理剤の必要量を決定できることを見出し、本発明を完成するに至った。
(4) Using the apparatus described in (1) to (3) above, stir the heavy metal solution in the transparent measurement container and supply the heavy metal treating agent solution continuously or intermittently to the transparent measurement container side. A method of measuring the transmitted light intensity by irradiating laser light from the side, and determining the necessary amount of the heavy metal treating agent from the degree of decrease in light transmittance (increase in turbidity).
As a result, it was found that the required amount of the heavy metal treating agent can be determined on-site in a short time and simply, and even when the heavy metal content is low, and the present invention has been completed. .

以下、本発明の装置について詳細に説明する。   Hereinafter, the apparatus of the present invention will be described in detail.

本発明は、重金属溶液の濁度変化を検出可能な検出器及び濁度変化が一定となる終点もしくは濁度変化の変曲点における重金属処理剤の添加量から重金属処理剤の必要量を算出する機能を有する重金属処理剤の必要量決定装置において、重金属溶液を供給する透明測定容器、重金属溶液を混合する機能を有する攪拌機、その上部から濁度測定用重金属処理剤溶液を供給する薬剤注入部、及び透明測定容器の側方部にレーザー光源部と受光部を有する重金属処理剤の必要量決定装置に関するものである。   The present invention calculates a necessary amount of a heavy metal treatment agent from a detector capable of detecting a turbidity change of a heavy metal solution and an addition amount of the heavy metal treatment agent at an end point at which the turbidity change is constant or an inflection point of the turbidity change. In the apparatus for determining the necessary amount of heavy metal treatment agent having a function, a transparent measurement container for supplying a heavy metal solution, a stirrer having a function of mixing the heavy metal solution, a drug injection unit for supplying a heavy metal treatment agent solution for turbidity measurement from the top thereof, Further, the present invention relates to an apparatus for determining the necessary amount of heavy metal processing agent having a laser light source part and a light receiving part at the side part of the transparent measuring container.

本発明では濁度変化を検出可能な検出器として赤外光レーザー又は可視光レーザーを用いる。特に可視光レーザーを使用することにより、重金属含有物質から溶出した重金属と重金属処理剤が反応することによって生じる濁度を高感度に検出することができ、より低濃度の重金属を検出することが可能となり、従来困難であった、重金属含有量が低濃度の重金属含有物質に対しても、オンサイトで短時間、かつ簡便に、さらには高精度に重金属処理剤の必要量を決定することができる。   In the present invention, an infrared laser or a visible laser is used as a detector capable of detecting a change in turbidity. In particular, by using a visible light laser, it is possible to detect turbidity caused by the reaction of a heavy metal eluted from a heavy metal-containing substance and a heavy metal treatment agent with high sensitivity, and it is possible to detect a lower concentration of heavy metal. Therefore, it is possible to determine the required amount of the heavy metal treating agent on-site in a short time, easily and with high accuracy even for a heavy metal-containing substance having a low concentration of heavy metal, which has been difficult in the past. .

本発明で使用する光の波長は、濁度変化を検出可能であれば特に限定されるものではないが、600〜760nmの範囲であることが好ましい。600nm未満の波長を使用した場合、添加する重金属処理剤によっては、透過率に影響が出ることがある。   The wavelength of light used in the present invention is not particularly limited as long as a change in turbidity can be detected, but is preferably in the range of 600 to 760 nm. When a wavelength of less than 600 nm is used, the transmittance may be affected depending on the heavy metal treatment agent to be added.

また、本発明において透明測定容器の側方部にレーザー光源部と受光部を有するとは、レーザー光の光源部(照射部)と受光部とが透明測定容器の横に位置することを意味しており、レーザー光が光源部を発し、透明測定容器を通過して測定媒体(重金属溶液)を通り、また反対側の透明測定容器を通過して受光部に到達する形態を示している。   Further, in the present invention, having the laser light source part and the light receiving part at the side part of the transparent measuring container means that the light source part (irradiating part) and the light receiving part of the laser light are located beside the transparent measuring container. The laser light is emitted from the light source part, passes through the transparent measurement container, passes through the measurement medium (heavy metal solution), and passes through the opposite transparent measurement container to reach the light receiving part.

本発明では、重金属溶液に重金属処理剤を添加し、該溶液の濁度を測定して重金属含有物質の不溶化に必要な重金属処理剤の必要量を決定する。   In the present invention, a heavy metal treating agent is added to the heavy metal solution, and the turbidity of the solution is measured to determine the necessary amount of the heavy metal treating agent necessary for insolubilizing the heavy metal-containing substance.

本発明における濁度とは、溶液中に存在する懸濁物量を溶液の単位容量又は単位重量当たりで表す一般的な指標である。   The turbidity in the present invention is a general index representing the amount of suspension present in a solution per unit volume or unit weight of the solution.

濁度は、重金属が溶出した溶液に重金属処理剤を添加して測定するが、その添加は連続的でも良く、また断続的でも良い。特に、段階的に添加し、添加した重金属処理剤による懸濁物の生成が安定化してから測定することが好ましい。添加時間の間隔としては数分、特に1〜10分程度の間隔で添加し、攪拌をすることが好ましい。   The turbidity is measured by adding a heavy metal treating agent to a solution from which heavy metals are eluted, but the addition may be continuous or intermittent. In particular, it is preferable to measure in a stepwise manner after the suspension is stabilized by the added heavy metal treatment agent. The addition time interval is preferably several minutes, particularly 1 to 10 minutes, and the mixture is stirred.

また、本発明の方法では必ずしも濁度の絶対値を測定する必要はなく、溶液中の濁度の変化が測定できれば良い。   In the method of the present invention, it is not always necessary to measure the absolute value of turbidity, as long as the change in turbidity in a solution can be measured.

本発明で用いる透明測定容器とは、内容物である重金属溶液を撹拌できる透明な容器であれば特に限定されるものではないが、撹拌手段としては電磁式スターラー、機械式撹拌翼等が例示され、透明な容器としては透明ガラス製の容器や透明プラスチック製の容器が例示される。破損が起きにくい点で透明プラスチック製の容器が好ましい。さらに、透明測定容器は、重金属溶液の蒸発又は飛散を防ぐ目的で、その上部が密閉又は半密閉されていることが好ましい。ここで、半密閉とは、透明測定容器の上部解放部の一部が蓋等により覆われていることを意味する。   The transparent measuring container used in the present invention is not particularly limited as long as it is a transparent container that can stir the content heavy metal solution, but examples of the stirring means include an electromagnetic stirrer, a mechanical stirring blade, and the like. Examples of the transparent container include a transparent glass container and a transparent plastic container. A transparent plastic container is preferred because it is less likely to break. Furthermore, it is preferable that the upper part of the transparent measurement container is sealed or semi-sealed for the purpose of preventing evaporation or scattering of the heavy metal solution. Here, semi-sealed means that a part of the upper open part of the transparent measuring container is covered with a lid or the like.

本発明において重金属処理剤溶液を供給する薬剤注入部は、透明測定容器の上部に設置されており、重金属処理剤は薬剤タンクからチューブ等を経由してポンプ等の注入手段により供給される。そして、薬剤注入部の注入口は重金属溶液の液面より上にあることが好ましい。重金属処理剤の添加方法は、精度向上の点で自動滴下方式が好ましい。自動滴下の場合、重金属処理剤を注入するポンプとして、シリンジポンプ、ベローズポンプ、ピストンポンプ、ギアポンプ、油圧式ポンプ等を例示することができる。特に1回の量を0.005〜0.200mgの範囲で調節添加でき、標準偏差が0.001g以下の高精度となるポンプが好ましく、例えば、パルスモーターによる送りねじ駆動方式シリンジポンプ等を例示することができる。   In the present invention, the drug injection part for supplying the heavy metal treatment agent solution is installed at the upper part of the transparent measurement container, and the heavy metal treatment agent is supplied from the drug tank via a tube or the like by injection means such as a pump. And it is preferable that the injection port of a chemical | medical agent injection | pouring part exists above the liquid level of a heavy metal solution. The method for adding the heavy metal treating agent is preferably the automatic dropping method in terms of improving accuracy. In the case of automatic dripping, a syringe pump, a bellows pump, a piston pump, a gear pump, a hydraulic pump, and the like can be exemplified as a pump for injecting the heavy metal treatment agent. In particular, a pump that can adjust and add a single dose in the range of 0.005 to 0.200 mg and has a high standard accuracy with a standard deviation of 0.001 g or less is preferable. For example, a feed screw drive type syringe pump using a pulse motor is exemplified. can do.

本発明の装置によれば、重金属溶液に、重金属処理剤を段階的に添加し、徐々に重金属の懸濁物を生成させ、その透過光強度をレーザー光により測定し、それ以上加えても懸濁物量が増加しない、即ち光透過率の低下(濁度の上昇)がなくなった時点の重金属処理剤の添加量から必要量を決定することができる。つまり、濁度変化が一定となる終点、もしくは濁度変化の変曲点における重金属処理剤の添加量をそのまま必要量とすることができる。   According to the apparatus of the present invention, a heavy metal treatment agent is added stepwise to a heavy metal solution, a heavy metal suspension is gradually formed, and the transmitted light intensity is measured with a laser beam. The required amount can be determined from the added amount of the heavy metal treating agent at the time when the amount of turbidity does not increase, that is, when the decrease in light transmittance (the increase in turbidity) disappears. That is, the addition amount of the heavy metal treatment agent at the end point at which the turbidity change becomes constant or at the inflection point of the turbidity change can be made the required amount as it is.

本発明において、重金属含有物質から重金属を溶出する溶液に特に限定はないが、例えば、硝酸、塩酸等の鉱酸水溶液、リンゴ酸、フタル酸等の有機酸水溶液、あるいはアンモニア、苛性等の塩基を例示することができる。重金属含有物質中に存在している重金属を溶出させる上で、カルボキシル基を一つ以上有し、非対称構造を有するカルボン酸及び/又はヒドロキシカルボン酸を用いることが好ましい。カルボキシル基を一つ以上有し、非対称構造を有するカルボン酸及び/又はヒドロキシカルボン酸としては、水に溶解するカルボキシル基を一つ以上有し、非対称構造を有するカルボン酸及び/又はヒドロキシカルボン酸であれば特に限定はなく、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、ヘキサン酸、ヘプタン酸、オキサロ酢酸、ピルビン酸、安息香酸等のカルボン酸の無水物、水和物、水溶液;グリコール酸、乳酸、グリセリン酸、ヒドロキシ酪酸、リンゴ酸、グルコン酸、マンデル酸等のヒドロキシカルボン酸の無水物、水和物、水溶液を挙げることができ、取り扱いの点でヒドロキシカルボン酸が好ましく、特に固体状であるグリコール酸、グリセリン酸、ヒドロキシ酪酸、リンゴ酸、グルコン酸、マンデル酸が好ましい。   In the present invention, the solution for eluting heavy metals from the heavy metal-containing substance is not particularly limited. For example, a mineral acid aqueous solution such as nitric acid and hydrochloric acid, an organic acid aqueous solution such as malic acid and phthalic acid, or a base such as ammonia and caustic is used. It can be illustrated. In order to elute the heavy metal present in the heavy metal-containing substance, it is preferable to use a carboxylic acid and / or hydroxycarboxylic acid having one or more carboxyl groups and having an asymmetric structure. The carboxylic acid and / or hydroxycarboxylic acid having at least one carboxyl group and having an asymmetric structure includes at least one carboxyl group dissolved in water and having an asymmetric structure and / or hydroxycarboxylic acid. There is no particular limitation as long as it is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, oxaloacetic acid, pyruvic acid, benzoic acid, etc. anhydride, hydrate, aqueous solution; glycolic acid, Examples include anhydrides, hydrates, and aqueous solutions of hydroxycarboxylic acids such as lactic acid, glyceric acid, hydroxybutyric acid, malic acid, gluconic acid, and mandelic acid. Hydroxycarboxylic acids are preferred in terms of handling, and particularly in solid form. Certain glycolic acids, glyceric acid, hydroxybutyric acid, malic acid, gluconic acid, and mandelic acid are preferred.

重金属の溶出溶液のpHは特に限定されないが、重金属含有物質から溶出する重金属を処理するのに必要な重金属処理剤の必要量を決定する上で、可能な限り溶出しやすいpHとすることが好ましい。また、当該溶液をpH7以上とした上で重金属処理剤を添加し、濁度を測定する。濁度を測定する溶液のpHは7以上、特に8以上、さらに10以上が好ましく、一方pH14を越えないことが好ましい。重金属処理剤を添加して濁度を測定する前に溶液は一旦濾過し、濁りをなくしておくことが好ましい。pH7以上とするために用いるアルカリは水に溶解するものであれば特に限定はなく、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム等の金属水酸化物の無水物、水和物、水溶液等を挙げることができる。   The pH of the elution solution of heavy metal is not particularly limited, but it is preferable to make the pH as easy to elute as much as possible in determining the necessary amount of the heavy metal treating agent necessary for treating the heavy metal eluted from the heavy metal-containing substance. . Moreover, after making the said solution into pH7 or more, a heavy metal processing agent is added and turbidity is measured. The pH of the solution for measuring turbidity is preferably 7 or more, particularly preferably 8 or more, and more preferably 10 or more, while it is preferable not to exceed pH14. Before adding a heavy metal treating agent and measuring turbidity, it is preferable to filter the solution once to eliminate turbidity. The alkali used for adjusting the pH to 7 or higher is not particularly limited as long as it is soluble in water. Anhydrides and hydrates of metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide And aqueous solutions.

本発明における重金属処理剤は特に限定されないが、重金属と反応して不溶化させる効果を有する薬剤一般を用いることができる。例えば、キレート系薬剤(アミンのカルボジチオ酸塩や酢酸塩等)、無機系の硫化物(硫化ソーダ、硫化鉄等)が例示でき、特に重金属不溶化能に優れたピペラジンのカルボジチオ酸塩(モノ体、ビス体、あるいはその混合物等)を用いることが好ましい。   Although the heavy metal processing agent in this invention is not specifically limited, The chemical | medical agent in general which has the effect made to react and insolubilize with a heavy metal can be used. Examples include chelating agents (amine carbodithioates and acetates), inorganic sulfides (sodium sulfide, iron sulfide, etc.), and piperazine carbodithioates (mono, It is preferable to use a bis body or a mixture thereof.

本発明で処理される重金属含有物質は特に限定されるものではないが、飛灰、土壌、その他廃棄物等を例示することができる。   Although the heavy metal containing material processed by this invention is not specifically limited, Fly ash, soil, other wastes, etc. can be illustrated.

本発明で処理される重金属の種類も特に限定されないが、例えば、鉛、銅、カドミウム、亜鉛、ニッケル、水銀、クロム、ひ素の他、環境保全上溶出が規制される金属成分を例示することができる。   The type of heavy metal to be treated in the present invention is not particularly limited. For example, in addition to lead, copper, cadmium, zinc, nickel, mercury, chromium, and arsenic, metal components whose elution is regulated for environmental conservation may be exemplified. it can.

本発明の装置を用いれば、重金属溶液に重金属処理剤を添加し、該溶液の濁度を測定することにより、オンサイトで短時間かつ簡便、高精度に重金属含有物質の不溶化処理に必要な重金属処理剤の添加量を決定することができる。   By using the apparatus of the present invention, by adding a heavy metal treating agent to a heavy metal solution and measuring the turbidity of the solution, the heavy metal necessary for the insolubilization treatment of heavy metal-containing substances in a short time, simply and with high accuracy. The amount of treatment agent added can be determined.

以下に、本発明を実施例によって説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

参考例1
飛灰A(Pb=6400ppm、Cu=2200ppmを含む)0.2gとDL−リンゴ酸(和光純薬工業(株)製)3.5gを純水200gに添加し、1分間撹拌し、飛灰中の重金属を溶出させた。当該スラリーをメンブレンフィルター(ADVANTEC社製:メンブレンフィルター孔径0.45μm)で濾過した後、20%水酸化ナトリウム溶液を添加し、pH12に調整した。次に、当該溶出液に重金属処理剤TS−275(東ソー(株)製)の25倍希釈液をパルスモーターによる送りねじ駆動方式シリンジポンプにて0.58g添加し、30分間撹拌し、懸濁物を生成させた。懸濁物の含有液3gを石英セル(1mm×1mm×45mm)に写し、UV−3100((株)島津製作所製)にて、可視光波長である650nmにおける透過率を測定した結果、70%であった。
Reference example 1
0.2 g of fly ash A (including Pb = 6400 ppm, Cu = 2200 ppm) and 3.5 g of DL-malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 200 g of pure water and stirred for 1 minute. The heavy metal inside was eluted. The slurry was filtered through a membrane filter (manufactured by ADVANTEC: membrane filter pore size 0.45 μm), and then 20% sodium hydroxide solution was added to adjust the pH to 12. Next, 0.58 g of a 25-fold diluted solution of heavy metal treatment agent TS-275 (manufactured by Tosoh Corporation) is added to the eluate with a feed screw drive type syringe pump using a pulse motor, and the mixture is stirred for 30 minutes and suspended. Product was produced. As a result of copying 3 g of the suspension-containing liquid onto a quartz cell (1 mm × 1 mm × 45 mm) and measuring the transmittance at 650 nm which is a visible light wavelength with UV-3100 (manufactured by Shimadzu Corporation), 70% Met.

参考例2
測定波長を780nm(赤外領域)とした以外は参考例1と同様の操作を行った、その結果、透過率は79%であった。同濃度の懸濁物を含有するにもかかわらず、可視光の650nmに比べ透過率が9%も高く、濁度としては低く検出された。
Reference example 2
The same operation as in Reference Example 1 was performed except that the measurement wavelength was 780 nm (infrared region). As a result, the transmittance was 79%. Despite containing a suspension with the same concentration, the transmittance was 9% higher than that of visible light at 650 nm, and the turbidity was detected as low.

実施例1
飛灰B(未知試料)0.2gと、DL−リンゴ酸(和光純薬工業(株)製)3.5gを純水200gに添加し、1分間攪拌し、飛灰中の重金属を溶出させた。当該スラリーをメンブレンフィルター(ADVANTEC社製:メンブレンフィルター孔径0.45μm)で濾過した後、該溶出液を200mLのガラスビーカーに入れ、20%水酸化ナトリウム溶液を添加し、pH12に調整した。次に、そのガラスビーカーを図1のように投光器と受光器よりなる可視光レーザーセンサを備えた攪拌機に設置した。レーザーセンサはセンサヘッドとしてIB−10(キーエンス社製)、アンプユニットとしてIB−1000(キーエンス社製)、攪拌機としてHS−30D(アズワン社製)、撹拌子として全長25mm、径φ8mm(アズワン社製)を使用した。その溶液を攪拌しながら、液面より上部から重金属処理剤TS−275(東ソー(株)製)の25倍希釈液をパルスモーターによる送りねじ駆動方式のシリンジポンプにて3分間隔で0.038gずつ10回滴下していき、その懸濁物量の変化をセンサ部の受光量より検出した。結果を表1、図2に示す。3回滴下した時点で明確な変曲点が観測された。変曲点における滴下量の総量は0.038g×3=0.114であり、飛灰0.2gに対して重金属処理剤TS−275は0.114g/25=4.56mg必要、すなわち、飛灰に対して、2.28wt%(4.56mg/0.2g×100)であった。
Example 1
0.2 g of fly ash B (unknown sample) and 3.5 g of DL-malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) are added to 200 g of pure water and stirred for 1 minute to elute heavy metals in the fly ash. It was. The slurry was filtered through a membrane filter (manufactured by ADVANTEC: membrane filter pore size 0.45 μm), and then the eluate was placed in a 200 mL glass beaker, and 20% sodium hydroxide solution was added to adjust the pH to 12. Next, the glass beaker was placed in a stirrer equipped with a visible light laser sensor composed of a projector and a light receiver as shown in FIG. The laser sensor is IB-10 (manufactured by Keyence) as a sensor head, IB-1000 (manufactured by Keyence) as an amplifier unit, HS-30D (manufactured by ASONE) as a stirrer, total length 25 mm, diameter 8 mm (manufactured by ASONE) )It was used. While stirring the solution, 0.038 g of a 25-fold diluted solution of the heavy metal treatment agent TS-275 (manufactured by Tosoh Corporation) from above the liquid surface with a pulse screw-driven syringe pump at a 3-minute interval. It was dripped 10 times at a time, and the change in the amount of suspension was detected from the amount of light received by the sensor unit. The results are shown in Table 1 and FIG. A clear inflection point was observed at the point of dropping three times. The total amount of dripping at the inflection point is 0.038 g × 3 = 0.114, and the heavy metal treatment agent TS-275 needs 0.114 g / 25 = 4.56 mg with respect to 0.2 g of fly ash. It was 2.28 wt% (4.56mg / 0.2gx100) with respect to ash.

飛灰B50gに対して、重金属処理剤の必要量2.28wt%(1.14g)及び水12.5gを添加し、環境庁告示13号試験を実施した結果、重金属の溶出は確認されず、本装置によって重金属含有量が未知である飛灰を不溶化処理するために必要な重金属処理剤の必要量を決定することができた。   As a result of adding the required amount of heavy metal treatment agent 2.28 wt% (1.14 g) and 12.5 g of water to 50 g of fly ash B and carrying out the Environmental Agency Notification No. 13 test, elution of heavy metals was not confirmed, With this device, the necessary amount of the heavy metal treatment agent necessary for insolubilizing fly ash having an unknown heavy metal content could be determined.

Figure 2015000376
Figure 2015000376

重金属処理剤必要量決定装置の概略図である。It is the schematic of a heavy metal processing agent required amount determination apparatus. 飛灰Bにおける重金属処理剤必要量決定装置を用いた試験結果である。It is a test result using the heavy metal processing agent required amount determination apparatus in the fly ash B.

1 受光部
2 レーザー光源部
3 アンプユニット
4 攪拌機
5 透明測定容器
6 攪拌子
7 薬剤注入部
8 薬剤注入ノズル
9 容器上蓋
DESCRIPTION OF SYMBOLS 1 Light-receiving part 2 Laser light source part 3 Amplifier unit 4 Stirrer 5 Transparent measuring container 6 Stirrer 7 Drug injection part 8 Drug injection nozzle 9 Container top cover

Claims (4)

重金属含有物質から重金属を溶出した溶液(以下、「重金属溶液」と表記する)の濁度変化を検出可能な検出器及び濁度変化が一定となる終点もしくは濁度変化の変曲点における重金属処理剤の添加量から重金属処理剤の必要量を算出する機能を有する重金属処理剤の必要量決定装置において、重金属溶液を供給する透明測定容器、重金属溶液を混合する機能を有する攪拌機、その上部から濁度測定用重金属処理剤溶液を供給する薬剤注入部、及び透明測定容器の側方部にレーザー光源部と受光部を有することを特徴とする重金属処理剤の必要量決定装置。 A detector capable of detecting turbidity change in a solution in which heavy metal is eluted from a heavy metal-containing substance (hereinafter referred to as “heavy metal solution”), and heavy metal treatment at the end point where the turbidity change is constant or the inflection point of the turbidity change In the device for determining the required amount of heavy metal treatment agent having the function of calculating the required amount of the heavy metal treatment agent from the added amount of the agent, a transparent measuring container for supplying the heavy metal solution, an agitator having the function of mixing the heavy metal solution, and turbidity from above A device for determining a necessary amount of a heavy metal treatment agent, comprising: a drug injection part that supplies a heavy metal treatment agent solution for measuring a degree of measurement; and a laser light source part and a light receiving part at a side part of the transparent measurement container. 薬剤注入部の注入口が重金属溶液の液面より上であることを特徴とする請求項1に記載の重金属処理剤の必要量決定装置。 The apparatus for determining a necessary amount of a heavy metal treatment agent according to claim 1, wherein the injection port of the drug injection part is above the liquid level of the heavy metal solution. 透明測定容器の上部が密閉又は半密閉されていることを特徴とする請求項1又は2に記載の重金属処理剤の必要量決定装置。 The apparatus for determining the necessary amount of heavy metal treatment agent according to claim 1 or 2, wherein the upper part of the transparent measuring container is sealed or semi-sealed. 請求項1〜3に記載の装置を用い、透明測定容器中の重金属溶液を攪拌し、そこに重金属処理剤溶液を連続的又は断続的に供給し、透明測定容器の側方部からレーザー光を照射して透過光強度を測定し、光透過率の低下(濁度の上昇)度合いから、重金属処理剤の必要量を決定する方法。 Using the apparatus according to claims 1 to 3, the heavy metal solution in the transparent measurement container is agitated, and the heavy metal treatment agent solution is continuously or intermittently supplied thereto, and laser light is emitted from the side of the transparent measurement container. A method of measuring the transmitted light intensity by irradiation and determining the required amount of heavy metal treatment agent from the degree of decrease in light transmittance (increase in turbidity).
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