JP2014091115A - Method and device of treating heavy metal-containing waste fluid - Google Patents
Method and device of treating heavy metal-containing waste fluid Download PDFInfo
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Abstract
【課題】錯化剤を含む重金属含有廃液から重金属類を分離・除去し、良好な水質の処理水を得る重金属含有廃液の処理方法及び装置を提供する。
【解決手段】重金属類および重金属類と錯体を形成する錯化剤を含有する廃液の処理方法であって、当該廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に第一の凝集剤を添加して析出物を沈殿・分離する。
【選択図】図１Disclosed is a heavy metal-containing waste liquid treatment method and apparatus for separating and removing heavy metals from a heavy metal-containing waste liquid containing a complexing agent to obtain treated water of good quality.
A method for treating a waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals, wherein an acid is added to the waste liquid to adjust the pH to about 6 or more, and then the first Add a flocculant to precipitate and separate the precipitate.
[Selection] Figure 1
Description
本発明は、重金属類および重金属類と錯体を形成する錯化剤を含有する重金属含有廃液
の処理方法及び装置に関し、より詳細には、銅および銅と錯体を形成するアミン類を含有する廃液から、銅を分離・除去する方法及び装置に関する。
The present invention relates to a method and apparatus for treating heavy metal-containing waste liquids containing heavy metals and complexing agents that form complexes with heavy metals, and more particularly, from waste liquids containing copper and amines that form complexes with copper. The present invention relates to a method and apparatus for separating and removing copper.
銅等の重金属類を含む廃液から重金属類を除去する方法として、重金属類がアルカリ性条件の下、不溶性の重金属の水酸化物を形成することを利用し、生成した重金属水酸化物を固液分離することで、重金属類を除去することが広く実施されている。
一方、重金属類を含む廃液から重金属類を除去する別の方法として、例えば特開昭６３−２９４９８６号公報（特許文献１）では、一段目の処理で酸性の重金属含有廃液をアルカリ性に調整し、金属水酸化物を不溶化して分離させた後、二段日の処理として重金属捕集剤を添加し、残存した重金属類や重金属の錯塩を不溶化して分離させる処理が開示されている。
As a method for removing heavy metals from waste liquids containing heavy metals such as copper, the formation of insoluble heavy metal hydroxides under alkaline conditions is used for solid metal-liquid separation. Thus, it is widely practiced to remove heavy metals.
On the other hand, as another method for removing heavy metals from waste liquid containing heavy metals, for example, in Japanese Patent Application Laid-Open No. 63-294986 (Patent Document 1), an acidic heavy metal-containing waste liquid is adjusted to be alkaline in the first stage treatment, After the metal hydroxide is insolubilized and separated, a treatment for adding a heavy metal scavenger as a two-day treatment and insolubilizing and separating the remaining heavy metals and heavy metal complex salts is disclosed.
ところで、重金属類を含有する廃液の中には、重金属と錯体を形成する錯化剤を含有する廃液がある。これらの廃液の例として、銅とモノエタノールアミンを含有する廃液が挙げられる。
このような錯化剤を含有する廃液は重金属イオンが錯化剤と錯体を形成するため、アルカリ条件下でも重金属イオンは水酸化物を形成せず、特許文献１による方法で単純に廃液をアルカリ条件にするだけでは、廃液中で重金属イオン（錯イオン）の状態のまま溶存した状態で存在するため、二段目の処理での重金属捕集剤の添加量が過大になる問題点があった。
By the way, among waste liquids containing heavy metals, there is a waste liquid containing a complexing agent that forms a complex with heavy metals. Examples of these waste liquids include waste liquids containing copper and monoethanolamine.
In the waste liquid containing such a complexing agent, heavy metal ions form a complex with the complexing agent, so that the heavy metal ions do not form a hydroxide even under alkaline conditions. There is a problem that the amount of heavy metal scavenger added in the second stage treatment becomes excessive because it exists in a state of being dissolved in the state of heavy metal ions (complex ions) in the waste liquid only by using the conditions. .
また、本発明者らの試験では重金属捕集剤の添加量が過大になると、不溶化した重金属類と重金属捕集剤の混合物は凝集剤を添加しても凝集しにくく、処理水を得ることが困難になる問題点もあった。 In addition, when the amount of the heavy metal scavenger added is excessive in the tests of the present inventors, the mixture of insolubilized heavy metals and the heavy metal scavenger is not easily aggregated even if a flocculant is added, and treated water can be obtained. There was also a problem that became difficult.
本発明は、上述の事情に鑑みなされたもので、錯化剤を含む重金属含有廃液から重金属類を分離・除去し、良好な水質の処理水を得る重金属含有廃液の処理方法及び装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a heavy metal-containing waste liquid treatment method and apparatus for separating and removing heavy metals from a heavy metal-containing waste liquid containing a complexing agent and obtaining treated water of good water quality. For the purpose.
上述の目的を達成するため、本発明の重金属含有廃液の処理方法は、重金属類および重金属類と錯体を形成する錯化剤を含有する廃液の処理方法であって、当該廃液に酸を添加しｐＨを６以上の中性付近に調整し、次に第一の凝集剤を添加して析出物を沈殿・分離する。
また、本発明の重金属含有廃液の処理方法は、重金属類および重金属類と錯体を形成する錯化剤を含有する廃液の処理方法であって、当該廃液に酸を添加しｐＨ６以上の中性付近に調整し、第一の凝集剤を添加し、析出物を沈殿・分離した後、さらに重金属捕集剤を添加し、第二の凝集剤を添加し、析出物を沈殿・分離することで、当該廃液より重金属類を分離・除去することを特徴とする。
In order to achieve the above object, the method for treating a heavy metal-containing waste liquid according to the present invention is a method for treating a waste liquid containing a heavy metal and a complexing agent that forms a complex with the heavy metal, wherein an acid is added to the waste liquid. The pH is adjusted to around 6 or more, and then the first flocculant is added to precipitate and separate the precipitate.
Further, the heavy metal-containing waste liquid treatment method of the present invention is a waste liquid treatment method containing a heavy metal and a complexing agent that forms a complex with heavy metals, and an acid is added to the waste liquid so that the pH is about 6 or more neutral. After adding the first flocculant and precipitating and separating the precipitate, further adding a heavy metal scavenger, adding the second flocculant, and precipitating and separating the precipitate, It is characterized by separating and removing heavy metals from the waste liquid.
本発明によれば、重金属類を含む廃液であり、重金属と錯体を形成する錯化剤が共存している廃液を処理することができる。重金属としては、銅、クロム、亜鉛、ニッケル、マンガンなどが挙げられる。廃液に含まれている錯化剤としては、モノエタノールアミン、トリエタノールアミンなどのアミン類が挙げられる。このような廃液の例として、アルカリ性で溶解性の銅を含む無電解めっき廃液が挙げられる。 ADVANTAGE OF THE INVENTION According to this invention, it is a waste liquid containing heavy metals and the waste liquid in which the complexing agent which forms a complex with a heavy metal can coexist. Examples of heavy metals include copper, chromium, zinc, nickel, and manganese. Examples of the complexing agent contained in the waste liquid include amines such as monoethanolamine and triethanolamine. An example of such a waste liquid is an electroless plating waste liquid containing alkaline and soluble copper.
本発明において、各処理で用いる凝集剤は実際に小スケールで廃液を処理し適切な凝集剤を選定すれば良いが、例えば第一の凝集剤には、アニオン性高分子凝集剤や両性高分子凝集剤、ポリ塩化アルミニウム、硫酸アルミニウム、活性ケイ酸、アルギン酸ナトリウム、活性化でんぷんなどを用いることができる。第二の凝集剤には、例えばカチオン性又は両性の高分子凝集剤を用いるが、この時凝集状態を改善するために金属塩、例えば塩化鉄（ＩＩＩ）を添加することも可能である。また、重金属捕集剤には、例えばジチオカルバミン酸基を持つキレート剤を用いる。 In the present invention, the flocculant used in each treatment may actually be a waste liquid treated on a small scale and an appropriate flocculant may be selected. For example, the first flocculant includes an anionic polymer flocculant and an amphoteric polymer. Flocculants, polyaluminum chloride, aluminum sulfate, activated silicic acid, sodium alginate, activated starch and the like can be used. As the second aggregating agent, for example, a cationic or amphoteric polymer aggregating agent is used. At this time, a metal salt such as iron (III) chloride can be added in order to improve the aggregation state. For the heavy metal scavenger, for example, a chelating agent having a dithiocarbamic acid group is used.
図４（定性分析化学ＩＩ，共立出版，１９７４年発行，３７６頁より引用）に示すように、銅の溶解性はｐＨ６以下になると急激に増加することが知られている。そのため、銅を水酸化物として沈殿させるためにはｐＨ６以上のアルカリ条件にすることが望ましい。
一方、重金属と錯体を形成するアミン類は、水中では以下のような平衡状態にあると考えられる。
ＨＯ−Ｒ−ＮＨ２ ＋ Ｈ＋ ←→ ＨＯ−Ｒ−Ｎ＋Ｈ３
（Ｒ：炭化水素鎖）
錯化剤含有廃液がアルカリ性であれば、この反応の平衡は左に進み、廃液中でのＨＯ−Ｒ−ＮＨ２の形態の分子の割合が多くなると考えられる。一方、廃液が酸性になると廃液中に水素イオン（Ｈ＋）が増えるため、この平衡は右に進み、ＨＯ−Ｒ−Ｎ＋Ｈ３の割合が多くなると考えられる。
ここでアミン類と重金属である銅イオンの錯体を考えると、アミン類が陽電荷をもたないＨＯ−Ｒ−ＮＨ２の形態では、銅イオンＣｕ２＋と安定した錯体を形成できるが、陽電荷をもつＨＯ−Ｒ−Ｎ＋Ｈ３の形態では、銅イオンの陽電荷とアミノ基の陽電荷が反発し、錯体が不安定になると考えられる。従って、銅−アミン錯体から銅イオンを遊離させ、分離・除去しやすくするためには廃液のｐＨを下げることが有効と考えられる。
銅−アミン錯体からの銅イオンの遊離のためにはｐＨが低い方が良いが、遊離した銅イオンが沈殿するためにはｐＨ６以上であることが望ましい。このため、処理対象の廃液の重金属類の濃度が高い場合には、重金属捕集剤を添加する前に、塩酸などの酸を添加し、あらかじめ廃液のｐＨを６〜７の中性程度まで低下させ、ある程度の重金属類を析出させる。これを分離・除去することにより、廃液中の重金属類がある程度除去される。
As shown in FIG. 4 (Qualitative Analytical Chemistry II, Kyoritsu Shuppan, published in 1974, cited from page 376), it is known that the solubility of copper rapidly increases when the pH is 6 or less. Therefore, in order to precipitate copper as a hydroxide, it is desirable to use alkaline conditions of
On the other hand, amines that form complexes with heavy metals are considered to be in the following equilibrium state in water.
HO-R-NH 2 + H + ← → HO-R-N + H 3
(R: hydrocarbon chain)
If the complexing agent-containing waste liquid is alkaline, the equilibrium of this reaction proceeds to the left, and it is considered that the proportion of molecules in the form of HO—R—NH 2 in the waste liquid increases. On the other hand, when the waste liquid becomes acidic, hydrogen ions (H + ) increase in the waste liquid. Therefore, this equilibrium proceeds to the right, and it is considered that the ratio of HO—R—N + H 3 increases.
Here, considering a complex of amines and a heavy metal copper ion, in the form of HO—R—NH 2 in which amines do not have a positive charge, a stable complex can be formed with copper ion Cu 2+. In the form of HO—R—N + H 3 having a cation, the positive charge of the copper ion and the positive charge of the amino group are repelled, and the complex is considered to be unstable. Therefore, it is considered effective to lower the pH of the waste liquid in order to liberate copper ions from the copper-amine complex and facilitate separation and removal.
The pH should be lower for the liberation of copper ions from the copper-amine complex, but the pH is preferably 6 or more for the liberated copper ions to precipitate. For this reason, when the concentration of heavy metals in the waste liquid to be treated is high, an acid such as hydrochloric acid is added before adding the heavy metal scavenger, and the pH of the waste liquid is lowered to about 6 to 7 neutral in advance. To deposit some heavy metals. By separating and removing this, heavy metals in the waste liquid are removed to some extent.
本発明によれば、重金属類とアミン類を含有する廃液に酸を添加し、ｐＨを６以上の中性付近、すなわちｐＨを６〜７に調整し、第一の凝集剤を添加して析出物を沈殿・分離し、一段目の処理水を得る。この段階で十分重金属類が除去されていれば、ここで処理を終了することが可能である。しかし、一段目の処理水の重金属類が残留していれば、さらにここに重金属捕集剤を添加し、さらに第二の凝集剤を添加することで、析出物を沈殿・分離し二段目の処理水を得る。一段目の処理水に重金属捕集剤を添加することで、残留した重金属類を十分除去できると同時に、一段目の処理である程度の重金属類が除去されているため、重金属捕集剤の添加量を低減する効果が期待できる。
また、本発明の好ましい態様によれば、重金属捕集剤を添加する前に、前記廃液を希釈することを特徴とする。
According to the present invention, an acid is added to a waste liquid containing heavy metals and amines, the pH is adjusted to near neutrality, that is, the pH is adjusted to 6 to 7, and the first flocculant is added to cause precipitation. Precipitate and separate the product to obtain first-stage treated water. If the heavy metals are sufficiently removed at this stage, the process can be terminated here. However, if heavy metals remain in the first-stage treated water, a heavy metal scavenger is further added here, and then a second flocculant is added to precipitate and separate the precipitate. Get treated water. By adding a heavy metal scavenger to the first-stage treated water, the remaining heavy metals can be sufficiently removed, and at the same time, a certain amount of heavy metal has been removed by the first-stage treatment, so the amount of heavy metal scavenger added The effect which reduces can be expected.
According to a preferred aspect of the present invention, the waste liquid is diluted before adding the heavy metal scavenger.
本発明の別の態様によれば、重金属類および重金属類と錯体を形成する錯化剤を含有する廃液に酸を添加し、ｐＨを６以上の中性付近に調整し、次に重金属捕集剤を添加し、次に凝集剤を添加して重金属類を含む固形物を沈殿することを特徴とする。
本方式では、一つの反応槽で処理を完結できるため、設備を小型化することが可能である。また、重金属類とアミン類を含有する廃液に酸を添加し、最初にｐＨを６以上の中性付近、すなわちｐＨを６〜７に調整しているため、この時点である程度の重金属類が沈殿するため、重金属捕集剤の添加量を低減する効果が期待できる。
According to another aspect of the present invention, an acid is added to a waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals, the pH is adjusted to around 6 or more, and then heavy metal collection is performed. An agent is added, and then a flocculant is added to precipitate a solid containing heavy metals.
In this method, since the treatment can be completed in one reaction tank, the equipment can be downsized. In addition, acid is added to the waste liquid containing heavy metals and amines, and the pH is first adjusted to around 6 or more, that is, the pH is adjusted to 6 to 7, so that some heavy metals are precipitated at this point. Therefore, the effect of reducing the addition amount of the heavy metal scavenger can be expected.
本発明の好ましい態様によれば、廃液に酸を添加する前に、カルシウム化合物を添加することを特徴とする。
本発明の好ましい態様によれば、廃液に酸を添加する前に、廃液を希釈することを特徴とする。
本発明の好ましい態様によれば、廃液を希釈した後、カルシウム化合物を添加することを特徴とする。
本発明廃液の処理方法は、上記重金属含有廃液の処理方法により、前記廃液を処理した後、処理水を生物処理することを特徴とする。
According to a preferred aspect of the present invention, the calcium compound is added before the acid is added to the waste liquid.
According to a preferred aspect of the present invention, the waste liquid is diluted before the acid is added to the waste liquid.
According to a preferred embodiment of the present invention, the calcium compound is added after diluting the waste liquid.
The waste liquid treatment method of the present invention is characterized in that the waste water is treated by the above heavy metal-containing waste liquid treatment method, and then the treated water is biologically treated.
本発明の重金属含有廃液の処理装置は、重金属類および重金属類と錯体を形成する錯化剤を含有する廃液の処理装置であって、当該廃液に酸を供給する手段と、当該廃液のｐＨ測定手段と、当該廃液を貯留・攪拌する反応槽を備え、前記反応槽において廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に第一の凝集剤を添加して重金属類を分離・除去することを特徴とする。
本発明の好ましい態様によれば、前記反応槽から送られた処理水に重金属捕集剤を供給する手段を有する第二の反応槽を備えることを特徴とする。
The heavy metal-containing waste liquid treatment apparatus of the present invention is a waste liquid treatment apparatus containing a heavy metal and a complexing agent that forms a complex with heavy metals, a means for supplying an acid to the waste liquid, and a pH measurement of the waste liquid Means and a reaction tank for storing and stirring the waste liquid. In the reaction tank, an acid is added to the waste liquid to adjust the pH to about 6 or more, and then a first flocculant is added to separate heavy metals. -It is characterized by removing.
According to a preferred aspect of the present invention, it is provided with a second reaction tank having means for supplying a heavy metal scavenger to the treated water sent from the reaction tank.
また、本発明の重金属含有廃液の処理装置は、重金属類および重金属類と錯体を形成する錯化剤を含有する廃液の処理装置であって、当該廃液に酸を供給する手段と、当該廃液のｐＨ測定手段と、当該廃液に重金属捕集剤を供給する手段とを有する反応槽を備え、前記反応槽において廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に重金属捕集剤を添加して析出物を沈殿・分離することを特徴とする。
本発明の好ましい態様によれば、前記反応槽から送られた処理水を脱水する脱水機を備えることを特徴とする。
本発明の廃液の処理装置は、上記の重金属含有廃液の処理装置と、前記重金属含有廃液の処理装置の後段に設置され、処理水を生物処理する手段を有する生物処理装置とを備えることを特徴とする。
Further, the heavy metal-containing waste liquid treatment apparatus of the present invention is a waste liquid treatment apparatus containing a heavy metal and a complexing agent that forms a complex with heavy metals, the means for supplying acid to the waste liquid, a reaction tank having a pH measurement means and a means for supplying a heavy metal scavenger to the waste liquid, wherein acid is added to the waste liquid in the reaction tank to adjust the pH to about 6 or more, and then a heavy metal scavenger To precipitate and separate the precipitate.
According to a preferred aspect of the present invention, a dehydrator for dehydrating the treated water sent from the reaction tank is provided.
The waste liquid treatment apparatus of the present invention comprises the above-described heavy metal-containing waste liquid treatment apparatus, and a biological treatment apparatus that is installed at a subsequent stage of the heavy metal-containing waste liquid treatment apparatus and has means for biologically treating treated water. And
本発明は以下に列挙する効果を奏する。
（１）重金属類を含む廃液の一般的な処理方法である水酸化物沈殿法の適用が困難である重金属類と錯化剤とを含有する廃液を処理することができる。本発明では、重金属捕集剤を添加することで、重金属類を分離・除去できる。
（２）重金属類および重金属類と錯体を形成する錯化剤を含有する廃液に酸を添加し、ｐＨを６以上の中性付近に調整し、析出物を分離・除去した後、重金属捕集剤を添加することで、重金属類を分離・除去すると同時に、重金属捕集剤の添加量を低減できる。
（３）重金属類および重金属類と錯体を形成する錯化剤を含有する廃液に酸を添加し、ｐＨを６以上の中性付近に調整し、次に重金属捕集剤を添加することで、重金属類を分離・除去すると同時に、重金属捕集剤の添加量を低減できる。
The present invention has the following effects.
(1) It is possible to treat a waste liquid containing heavy metals and a complexing agent, which are difficult to apply a hydroxide precipitation method, which is a general treatment method for waste liquids containing heavy metals. In the present invention, heavy metals can be separated and removed by adding a heavy metal scavenger.
(2) Add acid to waste liquid containing heavy metals and complexing agents that form complexes with heavy metals, adjust the pH to around 6 or more, isolate and remove precipitates, and then collect heavy metals By adding the agent, it is possible to separate and remove heavy metals and at the same time reduce the amount of heavy metal scavenger added.
(3) by adding an acid to the waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals, adjusting the pH to about 6 or more neutral, and then adding a heavy metal scavenger; At the same time as separating and removing heavy metals, the amount of heavy metal scavenger added can be reduced.
本発明の処理対象となる廃液は、重金属類を含む廃液であり、さらに重金属と錯体を形成する錯化剤が共存している廃液である。処理対象となる重金属としては、銅、クロム、亜鉛、ニッケル、マンガンなどが挙げられる。廃液に含まれている錯化剤としては、モノエタノールアミン、トリエタノールアミンなどのアミン類が挙げられる。このような廃液の具体例として、アルカリ性で溶解性の銅を含む無電解めっき廃液が挙げられる。 The waste liquid to be treated in the present invention is a waste liquid containing heavy metals, and is a waste liquid in which a complexing agent that forms a complex with heavy metals coexists. Examples of the heavy metal to be treated include copper, chromium, zinc, nickel, and manganese. Examples of the complexing agent contained in the waste liquid include amines such as monoethanolamine and triethanolamine. A specific example of such a waste liquid is an electroless plating waste liquid containing alkaline and soluble copper.
本発明による処理方法においては、最初に当該廃液に塩酸等の酸を添加しｐＨを下げるが、酸の添加は当該廃液のｐＨが６以上の中性付近になるように調整する。錯化剤がアミン類の場合、ｐＨを低下させることで錯化剤中のアミノ基に水素イオンが配位しプラスの荷電状態となるため、配位したプラスの電荷をもつ重金属イオンは遊離しやすくなる。
一方、重金属の一種である銅イオンの溶解度はｐＨが６未満となると急激に増加することが知られている。このため、廃液のｐＨを６〜７の中性付近に調整することで銅−アミン錯体からの銅イオンをある程度遊離させつつ、遊離した銅を水酸化物として析出させ、分離・除去することが可能となる。
このように重金属類の溶解度とアミン類の性質を利用し、適切なｐＨに調整することで廃液中の重金属類濃度を低減することが可能となる。
析出物が生成したところで第一の凝集剤を添加し、析出物を凝集沈殿させる。この段階で十分重金属類が除去されていれば、処理を完了することも可能である。
実際の装置では槽内の廃液のｐＨ測定手段と酸供給設備を備え、槽内の廃液がｐＨ６以上の中性付近、すなわちｐＨが６〜７を維持するように酸の添加量を制御することが望ましい。
In the treatment method according to the present invention, an acid such as hydrochloric acid is first added to the waste liquid to lower the pH, but the addition of the acid is adjusted so that the pH of the waste liquid is around 6 or more neutral. When the complexing agent is an amine, the hydrogen ion is coordinated to the amino group in the complexing agent by reducing the pH, resulting in a positive charge state. Therefore, the heavy metal ion having the coordinated positive charge is released. It becomes easy.
On the other hand, it is known that the solubility of copper ions, which are a kind of heavy metal, rapidly increases when the pH is less than 6. For this reason, by adjusting the pH of the waste liquid to about 6 to 7 neutrality, copper ions from the copper-amine complex are liberated to some extent, and the liberated copper is precipitated as hydroxide and separated and removed. It becomes possible.
Thus, it is possible to reduce the concentration of heavy metals in the waste liquid by using the solubility of heavy metals and the properties of amines and adjusting to an appropriate pH.
When the precipitate is generated, the first flocculant is added to cause the precipitate to aggregate. If the heavy metals are sufficiently removed at this stage, the treatment can be completed.
The actual apparatus is equipped with a means for measuring the pH of waste liquid in the tank and an acid supply facility, and the amount of acid added is controlled so that the waste liquid in the tank is near
重金属と錯化剤との錯体は一般に濃度が低下すると不安定になることが知られている。このため、酸を添加してｐＨを調整する前にあらかじめ当該廃液を希釈すると、重金属の除去率が高くなる場合がある。一方、廃液を希釈すると液量が増加し、処理水量の増加や処理設備の大型化の原因ともなる。このため、あらかじめ小スケールでの試験により、希釈の効果と問題点を検討し、適切な条件を設定することが望ましい。 It is known that complexes of heavy metals and complexing agents generally become unstable as the concentration decreases. For this reason, if the waste liquid is diluted in advance before adjusting the pH by adding an acid, the removal rate of heavy metals may increase. On the other hand, when the waste liquid is diluted, the liquid volume increases, which causes an increase in the amount of treated water and an increase in the size of the treatment equipment. For this reason, it is desirable to examine the effects and problems of dilution by a small-scale test in advance and set appropriate conditions.
一段目の処理水に重金属類が残留している場合、次に重金属捕集剤を添加する。重金属捕集剤は廃液中の重金属イオンと不溶性の錯体を形成することで重金属類を廃液から分離しやすい形態にする。重金属類は重金属捕集剤と不溶性の錯体を形成し、析出物となる。ここに第二の凝集剤を添加し、析出物を凝集沈殿させ、処理水を得る。
実際の装置では重金属捕集剤の最適な添加量は使用する重金属捕集剤や処理対象となる重金属の種類によって異なるため、例えばあらかじめ小スケールでの試験を実施し、要求される処理水水質に応じて添加量を決めておくことが望ましい。
当該廃液の処理に当たり、ｐＨ調整する前にカルシウム化合物を添加することで凝集状態を改善できる。例えば、水酸化カルシウムを添加することで凝集状態を改善する効果が期待できる。
If heavy metals remain in the first stage treated water, then add a heavy metal scavenger. The heavy metal scavenger forms an insoluble complex with heavy metal ions in the waste liquid to make it easy to separate heavy metals from the waste liquid. Heavy metals form insoluble complexes with heavy metal scavengers and become precipitates. A second flocculant is added here, and the precipitate is agglomerated to obtain treated water.
In actual equipment, the optimum amount of heavy metal scavenger added varies depending on the heavy metal scavenger used and the type of heavy metal to be treated.For example, a small-scale test is conducted beforehand to obtain the required quality of treated water. It is desirable to determine the addition amount accordingly.
In the treatment of the waste liquid, the aggregation state can be improved by adding a calcium compound before adjusting the pH. For example, the effect of improving the aggregation state can be expected by adding calcium hydroxide.
当該廃液に析出した生成物には重金属類の水酸化物や重金属と重金属捕集剤の錯体が含まれており、これらを固液分離することで、廃液から重金属類を分離・除去することができる。分離方法としては、沈降分離、凝集沈殿、ろ過などの一般的な固液分離方法を適用することができるが、固液分離方法の選定は析出物の性状に応じて適切な方法を選択することが好ましい。 The product precipitated in the waste liquid contains heavy metal hydroxides and heavy metal and heavy metal scavenger complexes, which can be separated and removed from the waste liquid by solid-liquid separation. it can. As a separation method, general solid-liquid separation methods such as sedimentation separation, coagulation sedimentation, and filtration can be applied, but the selection of the solid-liquid separation method should be selected according to the properties of the precipitate. Is preferred.
本処理方法は重金属類を除去できるものの錯化剤はそのまま廃液中に残留するため、重金属を除去した後の廃液は、必要に応じて後処理を併用し錯化剤を除去することが望ましい。例えば、錯化剤がアミン類であれば、生物分解が期待できるので、重金属除去後の処理水を生物処理することで錯化剤を分解し、処理水中の有機物濃度を低減することが可能である。 Although this treatment method can remove heavy metals, the complexing agent remains in the waste liquid as it is. Therefore, it is desirable to remove the complexing agent from the waste liquid after removing the heavy metal by using post-treatment if necessary. For example, if the complexing agent is an amine, biodegradation can be expected, so it is possible to decompose the complexing agent by biologically treating the treated water after removal of heavy metals and reduce the concentration of organic substances in the treated water. is there.
また、本処理方法の後で重金属類がわずかに残留する場合の対策として、後段にキレート樹脂吸着設備を併設することによって廃液に残留するわずかな重金属を除去することも可能である。
また、重金属除去後の廃液中の錯化剤は、重金属類が混入すると再び重金属錯体を形成し、除去しにくい錯イオン状態で重金属類が残留することになるので、重金属類を含む廃液と混合しないような処理方式を選択すべきである。
In addition, as a countermeasure when a slight amount of heavy metals remain after this treatment method, it is possible to remove a slight amount of heavy metals remaining in the waste liquid by installing a chelate resin adsorption facility in the subsequent stage.
In addition, the complexing agent in the waste liquid after removal of heavy metals will form heavy metal complexes again when heavy metals are mixed in, and heavy metals will remain in a complex ion state that is difficult to remove, so mix with waste liquids containing heavy metals. You should select a processing method that does not.
本発明による別の処理方法では、最初に当該廃液に酸を添加し当該廃液のｐＨが６以上の中性付近になるように酸を添加する。上述したように重金属類の溶解度とアミン類の性質を利用し、適切なｐＨに調整することで廃液中の重金属類濃度の一部を水酸化物として析出させ、廃液中の重金属類濃度を低減することが可能になる。
実際の装置では槽内の廃液のｐＨ測定手段と酸供給設備を備え、槽内の廃液がｐＨ６以上の中性付近、すなわちｐＨが６〜７を維持するように酸の添加量を制御することが望ましい。
次に廃液中に残留した重金属類を除去するため、廃液に重金属捕集剤を添加する。重金属類と重金属捕集剤は不溶性の錯体を形成するため、ここに凝集剤を添加し、先に析出した重金属の水酸化物と共に重金属−重金属捕集剤の錯体を同時に凝集・沈殿させる。
In another treatment method according to the present invention, an acid is first added to the waste liquid, and the acid is added so that the pH of the waste liquid is around 6 or more neutral. As described above, by utilizing the solubility of heavy metals and the properties of amines, by adjusting to an appropriate pH, a portion of the heavy metal concentration in the waste liquid is precipitated as a hydroxide, thereby reducing the heavy metal concentration in the waste liquid. It becomes possible to do.
The actual apparatus is equipped with a means for measuring the pH of waste liquid in the tank and an acid supply facility, and the amount of acid added is controlled so that the waste liquid in the tank is near
Next, in order to remove heavy metals remaining in the waste liquid, a heavy metal scavenger is added to the waste liquid. Since the heavy metal and the heavy metal scavenger form an insoluble complex, an aggregating agent is added here, and the heavy metal-heavy metal scavenger complex is coagulated and precipitated simultaneously with the previously precipitated heavy metal hydroxide.
当該廃液に析出した生成物には重金属類の水酸化物や重金属と重金属捕集剤の錯体が含まれており、これらを固液分離することで、廃液から重金属類を分離・除去することができる。分離方法としては、沈降分離、凝集沈殿、ろ過などの一般的な固液分離方法を適用することができるが、固液分離方法の選定は析出物の性状に応じて適切な方法を選択することが好ましい。 The product precipitated in the waste liquid contains heavy metal hydroxides and heavy metal and heavy metal scavenger complexes, which can be separated and removed from the waste liquid by solid-liquid separation. it can. As a separation method, general solid-liquid separation methods such as sedimentation separation, coagulation sedimentation, and filtration can be applied, but the selection of the solid-liquid separation method should be selected according to the properties of the precipitate. Is preferred.
本発明の処理装置の一態様を図１に模式的に示す。本発明の処理対象となる重金属含有廃液は、重金属類を含む廃液であり、さらに重金属と錯体を形成する錯化剤が共存している廃液である。図１に示すように、本発明の処理装置は、重金属含有廃液を収容する反応槽１０と、反応槽１０に重金属含有廃液を供給する配管１と、反応槽１０内の重金属含有廃液に酸を供給する配管２を備えている。本発明の処理装置は、さらに攪拌装置１２と、ｐＨ測定手段１３と、固液分離装置１５とを備えている。
One embodiment of the processing apparatus of the present invention is schematically shown in FIG. The heavy metal-containing waste liquid to be treated according to the present invention is a waste liquid containing heavy metals, and is a waste liquid in which a complexing agent that forms a complex with heavy metals coexists. As shown in FIG. 1, the treatment apparatus of the present invention includes a
図１に示す本発明の処理装置では、反応槽１０に配管１を通して重金属含有廃液が移送され、反応槽１０内の重金属含有廃液に配管２を通して塩酸等の酸が添加され、廃液のｐＨが調整され、配管１８を通して凝集剤が添加される。廃液は反応槽１０内で貯留・攪拌される。次に反応槽１０内で処理された廃液は固液分離装置１５に移送され、固液分離装置１５において固液分離され、処理水３と重金属を含むスラリー４とに分離される。
In the treatment apparatus of the present invention shown in FIG. 1, the heavy metal-containing waste liquid is transferred to the
本発明の処理装置の別の一態様を図２に模式的に示す。図２に示す態様においては、第一の反応槽１１に配管１を通して重金属含有廃液が移送され、第一の反応槽１１内の重金属含有廃液に配管２を通して酸を添加することにより廃液のｐＨが６以上の中性付近、すなわちｐＨが６〜７になるように調整され、配管１８を通して第一の凝集剤が添加される。廃液は第一の反応槽１１内で貯留・攪拌される。第一の反応槽１１内で処理された廃液は第一固液分離装置１６に移送されて、第一の固液分離装置１６において固液分離され、スラリー４が分離除去される。その後、廃液は第二の反応槽１４に移送される。第二の反応槽１４内の重金属含有廃液に配管７を通して重金属捕集剤が添加され、配管１９を通して第二の凝集剤が添加される。第二の反応槽１４内で処理された廃液は第二固液分離装置１７に移送されて、第二固液分離装置１７において固液分離され、処理水６と重金属を含むスラリー８とに分離される。
Another embodiment of the processing apparatus of the present invention is schematically shown in FIG. In the embodiment shown in FIG. 2, the heavy metal-containing waste liquid is transferred to the
本発明の処理装置の別の一態様を図３に模式的に示す。図３に示す態様においては、反応槽１０に配管１を通して重金属含有廃液が移送され、反応槽１０内の重金属含有廃液に配管２を通して酸を添加することにより廃液のｐＨが６以上の中性付近、すなわちｐＨ６〜７になるように調整され、廃液は反応槽１０内で貯留・攪拌される。次に反応槽１０内の廃液に配管７を通して重金属捕集剤が添加され、配管１８を通して凝集剤が添加される。反応槽１０内で処理された廃液は固液分離装置１５に移送されて、固液分離装置１５において固液分離され、処理水３と重金属を含むスラリー４とに分離される。
Another embodiment of the processing apparatus of the present invention is schematically shown in FIG. In the embodiment shown in FIG. 3, the heavy metal-containing waste liquid is transferred to the
次に実施例を挙げ、本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
実施例１
実施例１では重金属として銅、錯化剤としてモノエタノールアミンを含む廃液を処理した。廃液の性状は、ｐＨが１３．１、銅濃度が９５８ｍｇ／Ｌ、ＣＯＤＣｒ（二クロム酸カリウムによる化学的酸素要求量）が７４，９００ｍｇ／Ｌであった。
当該廃液の処理操作は、当該廃液に塩酸を添加しｐＨを６に調整した。その後凝集剤としてアニオン性高分子凝集剤を添加し、析出物を凝集沈殿させ、上澄を処理水として回収した。アニオン性高分子凝集剤にはエバグロースＡ−１５１（商品名）（水ｉｎｇ社製）を用いた。処理水を水質分析した所、銅濃度は３２０ｍｇ／Ｌであり、廃液中の銅の約３分の２が除去できた。
EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.
Example 1
In Example 1, a waste liquid containing copper as a heavy metal and monoethanolamine as a complexing agent was treated. As for the properties of the waste liquid, the pH was 13.1, the copper concentration was 958 mg / L, and CODCr (chemical oxygen demand by potassium dichromate) was 74,900 mg / L.
In the treatment of the waste liquid, hydrochloric acid was added to the waste liquid and the pH was adjusted to 6. Thereafter, an anionic polymer flocculant was added as a flocculant to precipitate the precipitate, and the supernatant was recovered as treated water. Ebagulose A-151 (trade name) (manufactured by Mizuing) was used as the anionic polymer flocculant. When water quality analysis was performed on the treated water, the copper concentration was 320 mg / L, and about two-thirds of the copper in the waste liquid could be removed.
実施例２
実施例２では実施例１と同じ廃液を処理した。最初に当該廃液に塩酸を添加しｐＨを６に調整した。その後第一凝集剤としてアニオン性高分子凝集剤を添加し、析出物を凝集沈殿させ、上澄を一段目処理水として回収した。アニオン性高分子凝集剤にはエバグロースＡ−１５１（商品名）を用いた。
次に、一段目処理水に重金属捕集剤を原水１Ｌあたりに換算して３ｍＬ添加し、良く攪拌した。重金属捕集剤としてはＬ−６００Ｍ(商品名)（水ｉｎｇ社製）を用いた。その後、第二凝集剤として両性高分子凝集剤を添加し析出物を凝集沈殿し、上澄を処理水として回収した。両性高分子凝集剤にはエバグロースＢ−１３４（商品名）（水ｉｎｇ社製）を用いた。処理水を水質分析した所、銅濃度は０．１ｍｇ／Ｌ未満まで低下しており、実施例１と比較して、銅濃度をさらに低減でき、良好な処理を達成することができた。
Example 2
In Example 2, the same waste liquid as in Example 1 was treated. First, hydrochloric acid was added to the waste liquid to adjust the pH to 6. Thereafter, an anionic polymer flocculant was added as a first flocculant to precipitate the precipitate, and the supernatant was recovered as first-stage treated water. Ebagulose A-151 (trade name) was used as the anionic polymer flocculant.
Next, 3 mL of a heavy metal scavenger was added to the first-stage treated water in terms of 1 L of raw water and stirred well. L-600M (trade name) (manufactured by Mizuing Inc.) was used as a heavy metal scavenger. Thereafter, an amphoteric polymer flocculant was added as a second flocculant to precipitate the precipitate, and the supernatant was recovered as treated water. As the amphoteric polymer flocculant, Ebagulose B-134 (trade name) (manufactured by Mizuing Inc.) was used. As a result of water quality analysis of the treated water, the copper concentration was reduced to less than 0.1 mg / L. Compared with Example 1, the copper concentration could be further reduced and good treatment could be achieved.
実施例３
実施例３では実施例１及び２と成分が同じであるが濃度が異なる廃液を処理した。すなわち、重金属として銅、錯化剤としてモノエタノールアミンを含む廃液を処理した。廃液の性状は、ｐＨが１３．１、銅濃度が２，３５０ｍｇ／Ｌ、ＣＯＤＣｒが１０２，０００ｍｇ／Ｌであった。実施例３では当該廃液を純水で８倍に希釈してから処理試験操作を行った。
最初に希釈した当該廃液に塩酸を添加しｐＨを６に調整した。その後両性高分子凝集剤を添加し、析出物を凝集沈殿させ、上澄を一段目処理水として回収した。両性高分子凝集剤にはエバグロースＢ−１３４(商品名)を用いた。次に、一段目処理水に実施例２とは異なる重金属捕集剤を原水１Ｌあたりに換算して１６ｍＬ添加し、良く攪拌した。重金属捕集剤にはＭｅｔａｌＣａｔｃｈｅｒ(商品名)（ＡＣＣＯＴ ＴＥＣＨＮＯＬＯＧＩＥＳ社製）を用いた。その後、両性高分子凝集剤を添加し析出物を凝集沈殿し、上澄を処理水として回収した。両性高分子凝集剤にはエバグロースＢ−１３４(商品名)を用いた。処理水を水質分析した所、銅濃度は０．５ｍｇ／Ｌ未満まで低下しており、実施例１や２よりも銅濃度の高い廃液であっても廃液を希釈することで処理が成り立つことを確認できた。
Example 3
In Example 3, waste liquids having the same components but different concentrations as in Examples 1 and 2 were treated. That is, a waste liquid containing copper as a heavy metal and monoethanolamine as a complexing agent was treated. As for the properties of the waste liquid, the pH was 13.1, the copper concentration was 2,350 mg / L, and the CODCr was 102,000 mg / L. In Example 3, a treatment test operation was performed after the waste liquid was diluted 8 times with pure water.
Hydrochloric acid was added to the waste liquid diluted first to adjust the pH to 6. Thereafter, an amphoteric polymer flocculant was added to precipitate the precipitate, and the supernatant was recovered as first-stage treated water. Ebagulose B-134 (trade name) was used as the amphoteric polymer flocculant. Next, 16 mL of a heavy metal scavenger different from that in Example 2 was added to the first-stage treated water in terms of 1 L of raw water and stirred well. MetalCatcher (trade name) (manufactured by ACCOT TECHNOLOGIES) was used as the heavy metal scavenger. Thereafter, an amphoteric polymer flocculant was added to precipitate the precipitate, and the supernatant was recovered as treated water. Ebagulose B-134 (trade name) was used as the amphoteric polymer flocculant. When the water quality of the treated water was analyzed, the copper concentration was reduced to less than 0.5 mg / L, and even if the waste liquid has a copper concentration higher than that of Examples 1 and 2, it can be treated by diluting the waste liquid. It could be confirmed.
実施例４
実施例４では実施例３と同じ廃液を処理した。最初に当該廃液を純水で約８倍に希釈した後、塩酸を添加し、ｐＨを６に調整した。次に実施例３と同じ重金属捕集剤を原水１Ｌあたりに換算して１２ｍＬ添加し、良く攪拌した。その後、アニオン性高分子凝集剤と凝集助剤として塩化鉄（ＩＩＩ）を添加し析出物を凝集沈殿し、上澄を処理水として回収した。アニオン性高分子凝集剤にはエバグロースＡ−１５１(商品名)を用いた。処理水の銅濃度は０．５ｍｇ／Ｌ未満まで低下した。実施例３は処理に二つの反応槽が必要であったが、実施例４では一つの反応槽でも処理が成り立つことを確認できた。
Example 4
In Example 4, the same waste liquid as in Example 3 was treated. First, the waste liquid was diluted about 8 times with pure water, and hydrochloric acid was added to adjust the pH to 6. Next, 12 mL of the same heavy metal scavenger as in Example 3 was added per 1 L of raw water, and stirred well. Thereafter, iron chloride (III) was added as an anionic polymer flocculant and a flocculant auxiliary agent to precipitate the precipitate, and the supernatant was recovered as treated water. Ebagulose A-151 (trade name) was used as the anionic polymer flocculant. The copper concentration of treated water decreased to less than 0.5 mg / L. In Example 3, two reaction vessels were necessary for the treatment, but in Example 4, it was confirmed that the treatment was possible even in one reaction vessel.
実施例５
実施例５では実施例３及び４と同じ廃液を処理したが、実施例３及び４と異なり、廃液を希釈することなく処理操作を実施した。最初に当該廃液に塩酸を添加し、ｐＨを６に調整した。次に実施例３と同じ重金属捕集剤を原水１Ｌあたりに換算して２５ｍＬ添加し、良く攪拌した。その後、析出物を凝集させるため塩化鉄（ＩＩＩ）と両性高分子凝集剤を添加し析出物を凝集沈殿し、上澄を処理水として回収した。両性高分子凝集剤にはエバグロースＢ−１３４(商品名)を用いた。処理水の銅濃度は０．５ｍｇ／Ｌ未満までに低下しており、廃液を希釈しなくても処理が成り立つことを確認した。実施例５の方式は実施例３及び４と比較して、希釈操作を省いたため処理水発生量の低減には有効であったが、重金属捕集剤の必要量が増えたため、これらの特徴を考慮して廃液希釈の有無を選択することが好ましい。
Example 5
In Example 5, the same waste liquid as in Examples 3 and 4 was treated. However, unlike Examples 3 and 4, the treatment operation was performed without diluting the waste liquid. First, hydrochloric acid was added to the waste liquid to adjust the pH to 6. Next, 25 mL of the same heavy metal scavenger as in Example 3 was added per 1 L of raw water and stirred well. Thereafter, iron (III) chloride and an amphoteric polymer flocculant were added to agglomerate the precipitate, and the precipitate was agglomerated and the supernatant was recovered as treated water. Ebagulose B-134 (trade name) was used as the amphoteric polymer flocculant. The copper concentration of the treated water was lowered to less than 0.5 mg / L, and it was confirmed that the treatment was achieved without diluting the waste liquid. Compared with Examples 3 and 4, the method of Example 5 was effective in reducing the amount of treated water generated because the dilution operation was omitted, but these features were increased because the necessary amount of heavy metal scavenger increased. It is preferable to select the presence or absence of dilution of the waste liquid in consideration of the above.
１，２，７，１８，１９ 配管
３ 処理水
４，８ スラリー
１０ 反応槽
１１ 第一の反応槽
１２ 攪拌装置
１３ ｐＨ測定手段
１４ 第二の反応槽
１５ 固液分離装置
１６ 第一固液分離装置
１７ 第二固液分離装置
1, 2, 7, 18, 19
Claims (13)
当該廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に第一の凝集剤を添加して析出物を沈殿・分離することを特徴とする重金属含有廃液の処理方法。 A method for treating a waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals,
A method for treating a heavy metal-containing waste liquid, wherein an acid is added to the waste liquid to adjust the pH to around neutrality of 6 or more, and then a first flocculant is added to precipitate and separate the precipitate.
当該廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に重金属捕集剤を添加し、次に凝集剤を添加して重金属類を含む固形物を沈殿することを特徴とする重金属含有廃液の処理方法。 A method for treating a waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals,
A heavy metal characterized by adding an acid to the waste liquid to adjust the pH to around neutrality of 6 or higher, then adding a heavy metal scavenger, and then adding a flocculant to precipitate a solid containing heavy metals. Treatment method for waste liquid.
当該廃液に酸を供給する手段と、当該廃液に第一の凝集剤を供給する手段と、当該廃液のｐＨ測定手段と、当該廃液を貯留・攪拌する反応槽を備え、
前記反応槽において廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に第一の凝集剤を添加して析出物を沈殿・分離することを特徴とする重金属含有廃液の処理装置。 An apparatus for treating waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals,
Means for supplying acid to the waste liquid, means for supplying the first flocculant to the waste liquid, pH measuring means for the waste liquid, and a reaction tank for storing and stirring the waste liquid,
An apparatus for treating a heavy metal-containing waste liquid, wherein an acid is added to the waste liquid in the reaction vessel to adjust the pH to around neutrality of 6 or more, and then a first flocculant is added to precipitate and separate the precipitate.
当該廃液に酸を供給する手段と、当該廃液に凝集剤を供給する手段と、当該廃液のｐＨ測定手段と、当該廃液に重金属捕集剤を供給する手段とを有する反応槽を備え、
前記反応槽において廃液に酸を添加しｐＨ６以上の中性付近に調整し、次に重金属捕集剤を添加し、さらに凝集剤を添加して重金属類を分離・除去することを特徴とする重金属含有廃液の処理装置。 An apparatus for treating waste liquid containing heavy metals and a complexing agent that forms a complex with heavy metals,
A reaction tank having a means for supplying an acid to the waste liquid, a means for supplying a flocculant to the waste liquid, a pH measuring means for the waste liquid, and a means for supplying a heavy metal scavenger to the waste liquid,
In the reaction vessel, an acid is added to the waste liquid to adjust the pH to around neutrality of 6 or more, then a heavy metal scavenger is added, and a flocculant is further added to separate and remove heavy metals. Waste liquid treatment equipment.
前記重金属含有廃液の処理装置の後段に設置され、処理水を生物処理する手段を有する生物処理装置とを備えることを特徴とする廃液の処理装置。 The heavy metal-containing waste liquid treatment apparatus according to any one of claims 9 to 12,
A wastewater treatment apparatus, comprising a biological treatment apparatus installed at a subsequent stage of the heavy metal-containing wastewater treatment apparatus and having means for biologically treating treated water.
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| JP2019111478A (en) * | 2017-12-22 | 2019-07-11 | 水ｉｎｇ株式会社 | Method and device of removing heavy metals |
| CN115246685A (en) * | 2021-12-17 | 2022-10-28 | 浙江海洋大学 | A water purification device for aquaculture seedlings |
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