JP5272306B2 - Heavy metal treating agent and method for treating heavy metal contaminants - Google Patents

Heavy metal treating agent and method for treating heavy metal contaminants Download PDF

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JP5272306B2
JP5272306B2 JP2006351558A JP2006351558A JP5272306B2 JP 5272306 B2 JP5272306 B2 JP 5272306B2 JP 2006351558 A JP2006351558 A JP 2006351558A JP 2006351558 A JP2006351558 A JP 2006351558A JP 5272306 B2 JP5272306 B2 JP 5272306B2
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carbodithioate
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piperazine
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JP2008273995A (en
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義則 阿山
利登 長嶺
満明 吉光
紳正 鈴木
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東ソー株式会社
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本発明は、重金属を含有する固体廃棄物、例えば、ゴミ焼却場から排出される焼却灰及び飛灰、重金属に汚染された土壌、排水処理後に生じる汚泥等に含有される鉛、水銀、クロム、カドミウム等の有害な重金属を簡便に固定化し、不溶出化することを可能にする重金属処理剤に関するものであり、特に高効率で重金属を固定化することのできる重金属処理剤及び重金属汚染物質の処理方法に関するものである。   The present invention is a solid waste containing heavy metal, for example, incineration ash and fly ash discharged from a garbage incineration plant, soil contaminated with heavy metal, lead contained in sludge generated after wastewater treatment, mercury, chromium, It relates to a heavy metal treatment agent that makes it possible to easily immobilize and elute harmful heavy metals such as cadmium, and in particular, to treat heavy metal treatment agents and heavy metal contaminants that can immobilize heavy metals with high efficiency. It is about the method.
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。   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.
キレート系薬剤としてはアミン誘導体のカルボジチオ酸塩が主に用いられている。特にピペラジンカルボジチオ酸塩では他のアミン誘導体と比較して、硫化水素及び二硫化炭素等の有害ガス発生が少ないため広く重金属処理剤として広く用いられている。(例えば特許文献1参照)
しかし、従来のアミン誘導体のカルボジチオ酸塩では有害な重金属の不溶化において、金属種に対する選択性が低く、鉛、水銀、クロム、カドミウム等の有害な重金属を不溶化する際に例えば銅等が共存する場合、銅等も不溶化され、結果的に多量に薬剤を使用する必要があった。特に銅の含有量が相対的に多い場合、有害でない金属の不溶化が進み、有害金属の不溶化が不十分になる場合があった。
As chelating agents, carbodithioates of amine derivatives are mainly used. In particular, piperazine carbodithioate is widely used as a heavy metal treating agent because it generates less harmful gases such as hydrogen sulfide and carbon disulfide than other amine derivatives. (For example, see Patent Document 1)
However, conventional amine derivative carbodithioates have low selectivity for metal species in the insolubilization of harmful heavy metals, and in the case of insolubilization of harmful heavy metals such as lead, mercury, chromium and cadmium, coexist with copper, etc. Copper and the like were also insolubilized, and as a result, it was necessary to use a large amount of chemicals. In particular, when the content of copper is relatively high, insolubilization of non-hazardous metals progresses, and the insolubilization of harmful metals may become insufficient.
一方、これまで重金属処理剤であるアミン誘導体のカルボジチオ酸塩にアミンを添加する方法が知られている。(特許文献2、3参照)従来のアミンの添加目的は、二硫化炭素ガスの発生を抑止するものであったが、アミンの添加量が少なく、有害な重金属の不溶化における選択性の向上効果は十分でなかった。特に高温で不安定なピペラジン以外のアミンのカルボジチオ酸塩を用いた場合、二硫化炭素が発生する高温条件下の使用において、カルボジチオ酸塩の分解によって発生する二硫化炭素によってアミンが消費され、選択性の向上効果が消失、或いは不安定となった。   On the other hand, a method of adding an amine to a carbodithioate of an amine derivative that is a heavy metal treating agent has been known. (Refer to Patent Documents 2 and 3) The conventional purpose of adding amine is to suppress the generation of carbon disulfide gas, but the amount of amine added is small, and the effect of improving selectivity in insolubilizing harmful heavy metals is It was not enough. When amine carbodithioate other than piperazine, which is unstable at high temperature, is used, amine is consumed by carbon disulfide generated by decomposition of carbodithioate when used under high temperature conditions where carbon disulfide is generated. The effect of improving the properties disappeared or became unstable.
特許第3391173号Japanese Patent No. 3391173 特開平9−1110号JP-A-9-1110 特開平9−234450号JP 9-234450 A
本発明は、有害な重金属を選択的に不溶化することが出来、より少量で有害な重金属処理を可能とする重金属処理剤およびそれを用いた処理方法を提供することにある。   An object of the present invention is to provide a heavy metal treating agent capable of selectively insolubilizing harmful heavy metals and capable of treating harmful heavy metals in a smaller amount, and a treatment method using the same.
本発明は上記の課題を解決すべく鋭意検討を重ねた結果、分子内にアミノ基を三つ以上有する直鎖状及び/または分岐状のポリアミンからなる群より選ばれる1種または2種以上と、アミンのカルボジチオ酸塩を含んでなる重金属処理剤では、有害な重金属の不溶化選択性が高く、少量で重金属処理が可能であることを見出し、特にアミンのカルボジチオ酸塩がピペラジンカルボジチオ酸塩の場合に金属に対する選択性の信頼性が高く、ピペラジンカルボジチオ酸塩以外を用いた場合にもポリアミンをカルボジチオ酸塩に対して100モル超用いることにより選択性が維持されることを見出し、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present invention has one or more selected from the group consisting of linear and / or branched polyamines having three or more amino groups in the molecule. It has been found that a heavy metal treating agent comprising an amine carbodithioate has a high insolubilization selectivity for harmful heavy metals and can be treated with a small amount of heavy metal. Particularly, an amine carbodithioate can be used as a piperazine carbodithioate. In this case, the selectivity to the metal is highly reliable, and even when a piperazine carbodithioate other than piperazine is used, it has been found that the selectivity is maintained by using polyamine more than 100 moles relative to the carbodithioate It came to complete.
以下、本発明に係わる重金属処理剤および重金属汚染物質の処理方法についてその詳細を説明する。   Hereinafter, the heavy metal treating agent and the method for treating heavy metal contaminants according to the present invention will be described in detail.
本発明の重金属処理剤は、分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンからなる群から選ばれる1種または2種以上、及びアミンのカルボジチオ酸塩を含んでなるものである。本発明の重金属処理剤はこれら2つの成分を含んでいれば他に特に制限はないが、取扱いの観点から水溶液で用いることが好ましい。   The heavy metal treating agent of the present invention contains one or more selected from the group consisting of linear and / or branched polyamines having three or more amino groups in the molecule, and carbodithioates of amines. It is what. The heavy metal treating agent of the present invention is not particularly limited as long as it contains these two components, but it is preferably used in an aqueous solution from the viewpoint of handling.
分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンは他のアミンと比較して、有害な重金属に対するアミンのカルボジチオ酸塩の処理選択性を向上するため、用いるアミンのカルボジチオ酸塩の量を低減することができる。選択性向上の理由は必ずしも定かではないが、有害性の低い銅等に対してポリアミンがマスキング能力を有することが考えられる。   A linear and / or branched polyamine having three or more amino groups in the molecule improves the processing selectivity of the amine carbodithioate against harmful heavy metals compared to other amines. The amount of carbodithioate can be reduced. The reason for the improvement in selectivity is not necessarily clear, but it is conceivable that the polyamine has a masking ability with respect to copper or the like having low toxicity.
本発明の重金属処理剤における分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンとしては、例えば、ヘキサエチレンペンタミン、テトラエチレンペンタミン、トリエチレンテトラミン、ジエチレンテトラミン、3−アミノエチルテトラエチレンペンタミン、2−アミノエチルトリエチレンテトラミン等を挙げることができ、いずれのものであってもよいが、特に分子内に四つ以上のアミノ基を有するポリアミンでは有害な重金属への選択性向上効果が特に高く、好ましい。   Examples of the linear and / or branched polyamine having three or more amino groups in the molecule in the heavy metal treating agent of the present invention include, for example, hexaethylenepentamine, tetraethylenepentamine, triethylenetetramine, diethylenetetramine, 3-aminoethyltetraethylenepentamine, 2-aminoethyltriethylenetetramine and the like can be mentioned, and any of them may be used, but heavy metals that are harmful particularly in polyamines having four or more amino groups in the molecule The effect of improving the selectivity to is particularly high and preferable.
本発明の重金属処理剤における、アミンのカルボジチオ酸塩は、熱安定性の非常に高いピペラジンカルボジチオ酸塩が特に好ましい。熱的に不安定なアミンのカルボジチオ酸塩では、分解に伴い二硫化炭素が発生し、二硫化炭素とポリアミンが反応してカルボジチオ酸塩となり、実質的にポリアミンとして存在するものが減少し、有害な重金属への選択性が低下する、または選択性がなくなる。ピペラジンカルボジチオ酸塩は、熱的に安定なため、上述のメカニズムによる選択性の低下がない。   The amine carbodithioate in the heavy metal treating agent of the present invention is particularly preferably a piperazine carbodithioate having very high thermal stability. Thermally unstable amine carbodithioate generates carbon disulfide with decomposition, and carbon disulfide and polyamine react to form carbodithioate, reducing what is substantially present as polyamine, which is harmful. The selectivity to heavy metals is reduced or lost. Since piperazine carbodithioate is thermally stable, there is no reduction in selectivity due to the mechanism described above.
ピペラジンカルボジチオ酸塩としては、ピペラジン−N−カルボジチオ酸塩、ピペラジン−N,N’−ビスカルボジチオ酸塩、又はそれらの混合物が例示できる。特にピペラジン−N,N’−ビスカルボジチオ酸塩、又はその比率の高いものが好ましい。これらの塩としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩が用いられるが、熱的安定性、溶解性の点からナトリウム塩、カリウム塩が好ましい。   Examples of the piperazine carbodithioate include piperazine-N-carbodithioate, piperazine-N, N′-biscarbodithioate, or a mixture thereof. In particular, piperazine-N, N′-biscarbodithioate or a compound having a high ratio thereof is preferable. As these salts, alkali metal salts, alkaline earth metal salts, and ammonium salts are used, and sodium salts and potassium salts are preferable from the viewpoint of thermal stability and solubility.
本発明の重金属処理剤を水溶液で用いる場合、アミンのカルボジチオ酸塩の濃度は高い方が好ましく、20〜60重量%、特に35〜45重量%の範囲が好ましい。   When the heavy metal treating agent of the present invention is used in an aqueous solution, the amine carbodithioate concentration is preferably higher, and is preferably in the range of 20 to 60% by weight, particularly 35 to 45% by weight.
分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンの量は重金属汚染物質の状態、重金属の含有量や重金属の形態にもよるが、アミンのカルボジチオ酸塩に対して0.01〜100000モル%、特に100モル%を超え2500モル量%までの範囲が好ましい。分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンの量が必要以上に多いと、処理物がアミン臭を発する原因等となり、一方少なすぎると本発明の選択性効果が十分に発揮されない。   The amount of linear and / or branched polyamines having three or more amino groups in the molecule depends on the state of heavy metal contaminants, the content of heavy metals and the form of heavy metals, but the amount of amine carbodithioate A range of 0.01 to 100,000 mol%, particularly more than 100 mol% and up to 2500 mol% is preferable. If the amount of the linear and / or branched polyamine having three or more amino groups in the molecule is more than necessary, the treated product may give off an amine odor, and if the amount is too small, the selectivity of the present invention. The effect is not fully demonstrated.
本発明の重金属処理剤において分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンとアミンのカルボジチオ酸塩を予め混合して使用する場合、用いるアミンのカルボジチオ酸塩の濃度はアミンの種類にもよるが、0.1〜60重量%、特に5〜45重量%、さらに20〜40重量%が好ましい。濃度が高くなりすぎると溶解度や粘性等の問題が生じ、小さすぎると処理能力が十分に発揮されない。   In the heavy metal treating agent of the present invention, when a linear and / or branched polyamine having three or more amino groups in the molecule and an amine carbodithioate are mixed in advance, the amine carbodithioate used The concentration depends on the type of amine, but is preferably 0.1 to 60% by weight, particularly 5 to 45% by weight, and more preferably 20 to 40% by weight. If the concentration is too high, problems such as solubility and viscosity will occur, and if it is too low, the treatment capacity will not be sufficiently exhibited.
本発明の重金属処理剤において分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンとアミンのカルボジチオ酸塩を予め混合して使用する場合、用いるポリアミンの量はアミンのカルボジチオ酸塩の種類及び用いるポリアミンの種類にもよるが、0.1〜90重量%が好ましく、特に3〜70重量%が好ましく、さらに20〜40重量%が好ましい。ポリアミンの量が必要以上に多いとアミンのカルボジチオ酸塩の溶解度低下の原因となり、少なすぎると本発明の選択性向上効果が十分に発揮されない。   In the heavy metal treating agent of the present invention, when a linear and / or branched polyamine having three or more amino groups in the molecule and an amine carbodithioate are mixed in advance, the amount of polyamine used is Although depending on the type of carbodithioate and the type of polyamine used, it is preferably 0.1 to 90% by weight, particularly preferably 3 to 70% by weight, and more preferably 20 to 40% by weight. If the amount of polyamine is larger than necessary, the solubility of amine carbodithioate will be reduced, and if it is too small, the effect of improving the selectivity of the present invention will not be sufficiently exhibited.
更にポリアミンはアミンのカルボジチオ酸塩に対して100モル%を超える範囲であることが望ましい。100モル%未満では、アミンのカルボジチオ酸塩の分解による二硫化炭素の発生がある場合に、選択性が低下或いは不安定化しやすい。   Further, the polyamine is desirably in a range exceeding 100 mol% with respect to the carbodithioate of the amine. If it is less than 100 mol%, the selectivity tends to be lowered or unstable when carbon disulfide is generated due to decomposition of the amine carbodithioate.
本発明の重金属処理剤には、本発明の効果を妨げない範囲で、他の成分を含んでもよい。他の成分としては、例えば、本発明の範囲外のアミン、カルボジチオ酸塩、無機系重金属処理剤、有機溶媒、アルカリ水酸化物等が例示できる。   The heavy metal treating agent of the present invention may contain other components as long as the effects of the present invention are not hindered. Examples of other components include amines, carbodithioates, inorganic heavy metal treating agents, organic solvents, and alkali hydroxides that are outside the scope of the present invention.
本発明の重金属処理剤を用いた重金属処理方法は、特に限定されるものではなく、本発明の重金属処理剤(又はその各成分を別々に添加する場合を含む)と被処理物を混合すればよい。   The heavy metal treatment method using the heavy metal treatment agent of the present invention is not particularly limited, and the heavy metal treatment agent of the present invention (or including the case where each of its components is added separately) and the object to be treated are mixed. Good.
重金属処理剤の使用量は重金属汚染物質の状態、重金属の含有量や重金属の形態により異なるが、通常、例えば飛灰に対しては0.01重量%〜30重量%の範囲で使用される。また処理を容易にするために、処理物に対して5〜50重量%の加湿水を混練時に添加してもよい。   The amount of heavy metal treating agent used varies depending on the state of heavy metal contaminants, the content of heavy metals and the form of heavy metals, but is usually used in the range of 0.01% to 30% by weight, for example, for fly ash. Moreover, in order to make a process easy, you may add 5-50 weight% humidified water with respect to a processed material at the time of kneading | mixing.
また、本発明の重金属処理法として特に限定されるものではないが、重金属汚染物質の状態、重金属の含有量や重金属の形態により、分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンからなる群から選ばれる1種または2種以上と、アミンのカルボジチオ酸塩を添加し、混合することで処理することができる。   Further, the heavy metal treatment method of the present invention is not particularly limited. However, depending on the state of heavy metal contaminants, the content of heavy metals and the form of heavy metals, a straight chain having three or more amino groups in the molecule and / or Alternatively, one or two or more selected from the group consisting of branched polyamines and amine carbodithioate may be added and mixed.
銅の含有量が高い重金属汚染物質の場合、アミンの重金属選択性(マスキング効果)を十分に発揮させるため、分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンからなる群から選ばれる1種または2種以上と、アミンのカルボジチオ酸塩を別々に添加する、特にポリアミンからなる群から選ばれる1種または2種以上を先に汚染物質に添加することが好ましい。   In the case of heavy metal pollutants with a high copper content, in order to fully exhibit the heavy metal selectivity (masking effect) of the amine, from linear and / or branched polyamines having three or more amino groups in the molecule It is preferable to add one or more selected from the group consisting of the above and the carbodithioate of the amine separately, and in particular, add one or more selected from the group consisting of the polyamine to the pollutant first.
本発明の重金属処理剤は、重金属汚染物質として飛灰、土壌、スラッジ等の処理に用いることができる。   The heavy metal treating agent of the present invention can be used for treating fly ash, soil, sludge and the like as heavy metal contaminants.
これらの重金属汚染物質中の有害な重金属としては鉛、カドミウム、クロム、水銀のいずれかを含有する物質が例示できる。   Examples of harmful heavy metals in these heavy metal contaminants include substances containing any of lead, cadmium, chromium, and mercury.
本発明の重金属処理剤、又は本発明の重金属処理法では、重金属汚染物質中の有害重金属に対する選択性が高いため、少量の薬剤で処理でき、非有害重金属の共存の影響によって有害な重金属の不溶化がおろそかになるという問題がなく、重金属処理の信頼性が高い。特にアミンのカルボジチオ酸塩成分として、ピペラジンカルボジチオ酸塩を用いた場合、当該塩の熱分解等に起因するポリアミンの消耗がなく、優れた性能が発揮される。   The heavy metal treatment agent of the present invention or the heavy metal treatment method of the present invention has high selectivity for harmful heavy metals in heavy metal pollutants, so it can be treated with a small amount of chemicals, and insoluble heavy metals are insolubilized due to the coexistence of non-hazardous heavy metals. There is no problem of neglecting, and the reliability of heavy metal processing is high. In particular, when piperazine carbodithioate is used as the carbodithioate component of the amine, the polyamine is not consumed due to thermal decomposition of the salt, and excellent performance is exhibited.
以下発明を実施例で説明するが、本発明はこれらの実施例に限定されるものではない。
(鉛選択性確認試験)
ピペラジン−N,N’−ビスカルボジチオ酸カリウムを35重量%含有する水溶液に対して、純水、ペンタエチレンヘキサミン(東ソー製)、テトラエチレンペンタミン(東ソー製)、トリエチレンテトラミン(東ソー製)、ジエチレントリアミン(東ソー製)、エチレンジアミン(東ソー製)、トリエチレンジアミン(東ソー製)、N−アミノエチルピペラジン(東ソー製)をそれぞれ添加した。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
(Lead selectivity confirmation test)
Pure water, pentaethylenehexamine (manufactured by Tosoh), tetraethylenepentamine (manufactured by Tosoh), triethylenetetramine (manufactured by Tosoh) with respect to an aqueous solution containing 35% by weight of potassium piperazine-N, N′-biscarbodithioate Diethylenetriamine (manufactured by Tosoh), ethylenediamine (manufactured by Tosoh), triethylenediamine (manufactured by Tosoh), and N-aminoethylpiperazine (manufactured by Tosoh) were added.
鉛100mg/L、銅2mg/L水溶液に対して上記調製液を0.045重量%添加し、1時間攪拌後ろ過し、ろ液中の鉛と銅の残存量をICPで分析した。結果を表1に示す。   0.045% by weight of the above prepared solution was added to 100 mg / L of lead and 2 mg / L of copper aqueous solution, stirred for 1 hour and filtered, and the residual amounts of lead and copper in the filtrate were analyzed by ICP. The results are shown in Table 1.
ペンタエチレンヘキサミン、テトラエチレンペンタミン、トリエチレンテトラミン、ジエチレントリアミンを添加したものでは鉛の残存量が低下する一方、水溶液中に銅が残存し、有害な鉛に対する不溶化選択性が高かった。一方、アミノ基が2つ以下のポリアミンおよび環状のポリアミンでは、銅に対するマスキング能が認められなかった。   In the case of addition of pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine, the residual amount of lead decreased, while copper remained in the aqueous solution, and the insolubilization selectivity to harmful lead was high. On the other hand, in the case of polyamines having 2 or less amino groups and cyclic polyamines, no masking ability for copper was observed.
(重金属処理能力試験)
実施例1
飛灰(Ca=13.7%、Na=2.7%、K=3.0%、Pb=1800ppm、Zn=7400ppm、Cu=7300ppmを含む)50重量部に対し、水10重量部(飛灰に対して20重量部)と、テトラエチレンペンタミン(東ソー製)2.5重量部(飛灰に対して5重量部)とピペラジン−N,N’−ビスカルボジチオ酸カリウム(35重量%含有する水溶液)を0.5重量部(飛灰に対して1重量部)を加え、混練した。(ピペラジン−N,N’−ビスカルボジチオ酸カリウムに対してポリアミンが2371モル%相当。)
処理後、昭和48年環境庁告示13号試験に従い溶出試験を行った。鉛の溶出結果を表2に示す。鉛の溶出は基準値以下であり、不溶化された。
(Heavy metal processing ability test)
Example 1
For 50 parts by weight of fly ash (including Ca = 13.7%, Na = 2.7%, K = 3.0%, Pb = 1800 ppm, Zn = 7400 ppm, Cu = 7300 ppm), 10 parts by weight of water (flying) 20 parts by weight of ash), 2.5 parts by weight of tetraethylenepentamine (manufactured by Tosoh Corp.) (5 parts by weight of fly ash) and potassium piperazine-N, N′-biscarbodithioate (35% by weight) 0.5 parts by weight (aqueous solution containing 1 part by weight with respect to fly ash) was added and kneaded. (Polyamine is equivalent to 2371 mol% with respect to potassium piperazine-N, N'-biscarbodithioate.)
After the treatment, a dissolution test was conducted according to the Environmental Agency Notification No. 13 test in 1973. The lead elution results are shown in Table 2. Lead elution was below the standard value and was insolubilized.
実施例2
テトラエチレンペンタミン(東ソー製)を1.0重量部(飛灰に対して2重量部)とする以外は実施例1と同様の操作を行った。結果を表2に示す。(ピペラジン−N,N’−ビスカルボジチオ酸カリウムに対してポリアミンが948モル%相当。)
実施例3
テトラエチレンペンタミン(東ソー製)0.5重量部(飛灰に対して5重量部)とピペラジン−N,N’−ビスカルボジチオ酸カリウム(35重量%含有する水溶液)0.5重量部(飛灰に対して1重量部)を予め混合した薬剤を、実施例1と同様の灰に添加し、混練した。(ピペラジン−N,N’−ビスカルボジチオ酸カリウムに対してポリアミンが474モル%相当。)
処理後、昭和48年環境庁告示13号試験に従い溶出試験を行った。鉛の溶出結果を表2に示す。鉛の溶出は基準値以下であり、不溶化された。結果を表2に示す。
Example 2
The same operation as in Example 1 was performed except that tetraethylenepentamine (manufactured by Tosoh) was changed to 1.0 part by weight (2 parts by weight with respect to fly ash). The results are shown in Table 2. (The polyamine is equivalent to 948 mol% with respect to potassium piperazine-N, N′-biscarbodithioate.)
Example 3
0.5 parts by weight of tetraethylenepentamine (manufactured by Tosoh) (5 parts by weight with respect to fly ash) and 0.5 parts by weight of piperazine-N, N′-biscarbodithioate (35% by weight aqueous solution) ( A drug in which 1 part by weight of fly ash) was mixed in advance was added to the same ash as in Example 1 and kneaded. (Polyamine is equivalent to 474 mol% with respect to potassium piperazine-N, N'-biscarbodithioate.)
After the treatment, a dissolution test was conducted according to the Environmental Agency Notification No. 13 test in 1973. The lead elution results are shown in Table 2. Lead elution was below the standard value and was insolubilized. The results are shown in Table 2.
実施例4
テトラエチレンペンタミン(東ソー製)を0.25重量部(飛灰に対して0.5重量部)とする以外は実施例3と同様の操作を行った。結果を表2に示す。(ピペラジン−N,N’−ビスカルボジチオ酸カリウムに対してポリアミンが237モル%相当。)
実施例5
テトラエチレンペンタミン(東ソー製)の代わりにトリエチレンテトラミン(東ソー製)を0.5重量部(飛灰に対して1.0重量部)とする以外は実施例1と同様の操作を行った。結果を表2に合わせて示す。(ピペラジン−N,N’−ビスカルボジチオ酸カリウムに対してポリアミンが614モル%相当。)
ポリアミン添加量が低減すると、鉛以外の金属に対するマスキング効果が低減し、基準値は満足しているものの、鉛の溶出量が増大した。
Example 4
The same operation as in Example 3 was performed except that tetraethylenepentamine (manufactured by Tosoh) was changed to 0.25 parts by weight (0.5 parts by weight with respect to fly ash). The results are shown in Table 2. (Polyamine is equivalent to 237 mol% with respect to potassium piperazine-N, N'-biscarbodithioate.)
Example 5
The same operation as in Example 1 was performed except that triethylenetetramine (manufactured by Tosoh) was changed to 0.5 parts by weight (1.0 parts by weight with respect to fly ash) instead of tetraethylenepentamine (manufactured by Tosoh). . The results are shown in Table 2. (Polyamine is equivalent to 614 mol% with respect to potassium piperazine-N, N′-biscarbodithioate.)
When the amount of polyamine added was reduced, the masking effect on metals other than lead was reduced, and although the reference value was satisfied, the amount of lead elution increased.
比較例1
テトラエチレンペンタミンを添加しないこと以外は実施例1と同様の操作を行った。結果を表2に合わせて示す。ピペラジン−N,N’−ビスカルボジチオ酸カリウムが銅の不溶化に消費され、鉛の不溶化が不十分になったと考えられた。
Comparative Example 1
The same operation as in Example 1 was performed except that tetraethylenepentamine was not added. The results are shown in Table 2. It was considered that potassium piperazine-N, N′-biscarbodithioate was consumed for insolubilization of copper and lead insolubilization was insufficient.
比較例2
ピペラジン−N,N’−ビスカルボジチオ酸カリウムを35重量%含有する水溶液を1.5重量部(飛灰に対して3重量部)とする以外は比較例1と同様の操作を行った。結果を表2に示す。鉛の溶出は低減したが、まだ不十分であった。
Comparative Example 2
The same operation as in Comparative Example 1 was performed except that the aqueous solution containing 35% by weight of piperazine-N, N′-biscarbodithioate was changed to 1.5 parts by weight (3 parts by weight with respect to fly ash). The results are shown in Table 2. Lead elution was reduced but still inadequate.
比較例3
ピペラジン−N,N’−ビスカルボジチオ酸カリウムを35重量%含有する水溶液を2重量部(飛灰に対して4重量部)とする以外は比較例1と同様の操作を行った。結果を表2に示す。
Comparative Example 3
The same operation as in Comparative Example 1 was performed except that the aqueous solution containing 35% by weight of piperazine-N, N′-biscarbodithioate was changed to 2 parts by weight (4 parts by weight with respect to fly ash). The results are shown in Table 2.
実施例6
各種アミンのカルボジチオ酸塩に対して添加ポリアミンを5重量%加えた水溶液を65℃に加熱し、二硫化炭素の発生及び有害な重金属に対する不溶化選択性の有無を測定した。結果を表3に示す。
Example 6
An aqueous solution in which 5% by weight of an added polyamine was added to carbodithioate of various amines was heated to 65 ° C., and the presence or absence of carbon disulfide generation and insolubilization selectivity against harmful heavy metals was measured. The results are shown in Table 3.
ピペラジンビスカルボジチオ酸塩では二硫化炭素の発生はないが、直鎖状及び/または分岐状のポリアミンを添加しない場合と環状アミンであるN−アミノエチルピペラジンを添加した場合において選択性は観測されなかった。   Piperazine biscarbodithioate does not generate carbon disulfide, but selectivity is observed when linear and / or branched polyamines are not added and when cyclic amine N-aminoethylpiperazine is added. There wasn't.
ピペラジンビスカルボジチオ酸塩以外のアミン塩では加熱によって二硫化炭素の発生し、ポリアミンを添加した場合にも二硫化炭素の発生によってポリアミンがカルボジチオ酸塩に転化し、選択性が低下した。   In amine salts other than piperazine biscarbodithioate, carbon disulfide was generated by heating, and even when polyamine was added, polyamine was converted to carbodithioate due to the generation of carbon disulfide, and the selectivity decreased.

Claims (5)

  1. ピペラジンカルボジチオ酸塩、分子内に三つ以上のアミノ基を有する直鎖状及び/または分岐状のポリアミンからなる群より選ばれる1種または2種以上をピペラジンカルボジチオ酸塩に対して100mol%を超える量含んでなる重金属処理剤。 Piperazine carbodithioate , 100 mol% of one or more selected from the group consisting of linear and / or branched polyamines having three or more amino groups in the molecule with respect to piperazine carbodithioate A heavy metal treating agent comprising an amount exceeding 1 .
  2. ポリアミンの含有量が0.1〜90重量%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。The heavy metal treating agent according to claim 1, wherein the polyamine content is 0.1 to 90% by weight.
  3. 請求項1または2に記載の重金属処理剤と重金属汚染物質とを混合する重金属汚染物質の処理方法。The processing method of the heavy metal contaminant which mixes the heavy metal processing agent of Claim 1 or 2, and a heavy metal contaminant.
  4. 重金属汚染物質が飛灰、土壌、スラッジであることを特徴とする請求項3に記載の重金属汚染物質の処理方法。The heavy metal contaminant treatment method according to claim 3, wherein the heavy metal contaminant is fly ash, soil, or sludge.
  5. 重金属汚染物質が鉛、カドミウム、クロム、水銀のいずれかを含有する物質であることを特徴とする請求項3または4に記載の重金属汚染物質の処理方法。5. The method for treating a heavy metal pollutant according to claim 3, wherein the heavy metal pollutant is a substance containing any one of lead, cadmium, chromium and mercury.
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