JP5066920B2 - 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 PDFInfo
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- JP5066920B2 JP5066920B2 JP2007003689A JP2007003689A JP5066920B2 JP 5066920 B2 JP5066920 B2 JP 5066920B2 JP 2007003689 A JP2007003689 A JP 2007003689A JP 2007003689 A JP2007003689 A JP 2007003689A JP 5066920 B2 JP5066920 B2 JP 5066920B2
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Description
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する鉛、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、保存時、輸送時、使用時、特に高温での使用時においても有害ガスの発生が抑制された重金属処理剤及び重金属汚染物質の処理方法である。 The present invention relates to solid waste containing heavy metals, such as incineration ash and fly ash discharged from garbage incineration plants, soil contaminated with heavy metals, sludge generated after wastewater treatment, mercury, chromium, cadmium It is related to a heavy metal treatment agent that makes it possible to easily fix and remove non-eluting harmful heavy metals such as harmful gases even when stored, transported, used, especially at high temperatures. A suppressed heavy metal treating agent and a method for treating heavy metal contaminants.
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知られている。 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 for insolubilizing heavy metals by adding a heavy metal treatment agent such as a chelate-based drug is known.
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。ピペラジンカルボジチオ酸塩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）また、ジエチレントリアミン等の直鎖状アミンを原料とするカルボジチオ酸塩を使用する方法が知られている（例えば特許文献２参照）。 As chelating agents, carbodithioates of amine derivatives are mainly used. Piperazine carbodithioate is widely used as a heavy metal treating agent because it produces less harmful gases such as hydrogen sulfide and carbon disulfide than other amine derivatives. (For example, refer patent document 1) Moreover, the method of using the carbodithioic acid salt which uses linear amines, such as diethylenetriamine, as a raw material is known (for example, refer patent document 2).
しかし、ピペラジンカルボジチオ酸塩を除くアミン誘導体のカルボジチオ酸塩を用いた場合、保管時、輸送時、使用時、特に高温での使用時において有害な二硫化炭素等を発生する等の問題があった。 However, when amine derivative carbodithioates other than piperazine carbodithioate are used, there are problems such as generation of harmful carbon disulfide during storage, transportation, use, especially when used at high temperatures. It was.
一方、重金属処理剤のキレート系薬剤にアミンやアルコールを添加する方法が知られている。（例えば特許文献３、４参照）これらのアミンやアルコールの添加は、二硫化炭素やアンモニアガスの発生を抑制するためであるが、アミンを用いる場合にはアミン臭がする場合があり、又アルコールを用いた場合にはアルコールが酸として機能するために、アンモニア臭は抑制されるが二硫化炭素が発生するという問題点があった。 On the other hand, a method of adding an amine or alcohol to a chelate agent of a heavy metal treating agent is known. (For example, refer to Patent Documents 3 and 4) The addition of these amines and alcohols is to suppress the generation of carbon disulfide and ammonia gas. When alcohol is used, since the alcohol functions as an acid, ammonia odor is suppressed but carbon disulfide is generated.
本発明の目的は、保管時、輸送時、使用時、特に高温での使用時において有害な二硫化炭素等の発生を抑制し、なおかつアミン臭等の問題がない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 use a heavy metal treatment agent that suppresses the generation of harmful carbon disulfide and the like during storage, transportation, use, particularly when used at high temperatures, and has no problems such as amine odor, and the like. It is to provide a processing method.
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、アルコキシド及び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、有害な二硫化炭素等の発生が抑制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 found that a heavy metal treating agent comprising an alkoxide and an amine carbodithioate suppresses the generation of harmful carbon disulfide and the like. The invention has been completed.
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アルコキシド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制限はないが、取り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 comprises an alkoxide and an amine carbodithioate. The heavy metal treating agent of the present invention is not limited as long as it contains these two components, but it is preferably used in an aqueous solution from the viewpoint of handling.
アルコキシドはアミンのカルボジチオ酸塩が分解する際に発生する二硫化炭素と反応しキサントゲン酸塩を形成するため、有害な二硫化炭素の発生を抑制することができると考えられる。 Since alkoxide reacts with carbon disulfide generated when amine carbodithioate is decomposed to form xanthate, it is considered that generation of harmful carbon disulfide can be suppressed.
アルコールも二硫化炭素と反応してキサントゲン酸塩を生成するが、アルコールは酸として機能し、アミンのカルボジチオ酸塩の安定性を低下させる。 Alcohol also reacts with carbon disulfide to form xanthates, but the alcohol functions as an acid, reducing the stability of the amine carbodithioate.
アミンのカルボジチオ酸塩にアルコールを添加した場合、カルボジチオ酸塩とアルコールが反応して一部アルコキシドを形成する場合があるが、アルコールがカルボジチオ酸塩を分解するため、二硫化炭素が抑制されない。 When an alcohol is added to the amine carbodithioate, the carbodithioate and the alcohol may react to form a part of the alkoxide. However, since the alcohol decomposes the carbodithioate, carbon disulfide is not suppressed.
本発明の重金属処理剤は、当初からアルコキシドを添加することにより、重金属処理剤中にアルコールが存在しないため、アミンのカルボジチオ酸塩の分解を促進する様なことがない。 In the heavy metal treating agent of the present invention, by adding an alkoxide from the beginning, no alcohol is present in the heavy metal treating agent, so that the decomposition of the amine carbodithioate is not accelerated.
本発明の用いるアルコキシドとしては、特に限定されるものではないが、例えばメトキシド、エトキシド、プロポキシド、ブトキシド等が例示され、特に重金属処理剤と不溶性錯体を生成しないアルカリ金属アルコキシド又はアルカリ土類金属アルコキシドが好ましい。また溶解度が高く、安価なナトリウムアルコキシド又はカリウムアルコキシドが好ましい。 The alkoxide used in the present invention is not particularly limited, and examples thereof include methoxide, ethoxide, propoxide, butoxide and the like, and in particular, alkali metal alkoxide or alkaline earth metal alkoxide that does not form an insoluble complex with a heavy metal treating agent. Is preferred. In addition, an inexpensive sodium alkoxide or potassium alkoxide having high solubility is preferable.
本発明におけるアミンのカルボジチオ酸塩は特に限定されるものではないが、例えば、脂肪族または芳香族アミン化合物から誘導されるカルボジチオ酸塩が挙げられ、脂肪族アミン化合物として、ジエチルアミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が例示される。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、熱的安定性及び安価なことからナトリウム塩又はカリウム塩が好ましい。 The amine carbodithioate in the present invention is not particularly limited, and examples thereof include carbodithioate derived from an aliphatic or aromatic amine compound. Examples of the aliphatic amine compound include diethylamine, ethylenediamine, diethylenetriamine, Examples include triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. As these salts, alkali metal salts, alkaline earth metal salts, and ammonium salts are used, but sodium salts or potassium salts are preferred because of their thermal stability and low cost.
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ほうが好ましく、２０〜６０重量％、特に３５〜５０重量％の範囲が望ましい。 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 50% by weight.
本発明の重金属処理剤のアルコキシドの量は、アミンのカルボジチオ酸塩の濃度、安定性にもよるが、０．０１〜２０重量％、特に０．５〜１０重量％の範囲が好ましい。アルコキシド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等の原因となり、少なすぎると本発明の有害ガス発生抑制効果が発揮されない。 The amount of the alkoxide of the heavy metal treating agent of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.5 to 10% by weight, although it depends on the concentration and stability of the carbodithioate of amine. If the amount of alkoxide is excessively large, it causes a decrease in the solubility of amine carbodithioate, and if it is too small, the harmful gas generation suppressing effect of the present invention is not exhibited.
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、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 inorganic heavy metal treating agents, organic solvents, and alkali hydroxides.
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と重金属汚染物質を混合すればよい。 The heavy metal processing method using the heavy metal processing agent of the present invention is not particularly limited, and the heavy metal processing agent of the present invention and heavy metal contaminants may be mixed.
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０．０１〜３０重量％の範囲で使用される。また処理を容易にするために、重金属汚染物質に対して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 heavy metal contaminant at the time of kneading | mixing.
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は、保管時、輸送時、使用時、特に高温での使用時において有害ガスの発生が抑制され、安全性が高められた重金属処理剤である。 The heavy metal treating agent of the present invention is a heavy metal treating agent that has improved safety by suppressing generation of harmful gases during storage, transportation, use, and particularly at high temperatures.
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。
（二硫化炭素発生試験）
実施例１
テトラエチレンペンタミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４，Ｎ５−ペンタカルボジチオ酸ナトリウム４５％水溶液１００重量部に対してナトリウムメトキシド５重量部を添加混合して重金属処理剤とした。得られた重金属処理剤８０．０ｇを１Ｌのフラスコ中に採取し、フラスコ内で６５℃に加温した。１時間後、フラスコ内の温度が一定になった後にフラスコ内に８００ｍｌの水を注入し、フラスコ内の気相部を排出し、該排出ガス中の二硫化炭素を二硫化炭素検知管（ＧＡＳＴＥＣ社製Ｎｏ １３）で測定したところ、検出限界（２．５ｐｐｍ）以下であり、許容濃度の１０ｐｐｍを下回った。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
(Carbon disulfide generation test)
Example 1
A heavy metal treating agent was prepared by adding and mixing 5 parts by weight of sodium methoxide to 100 parts by weight of 45% aqueous solution of tetraethylenepentamine-N1, N2, N3, N4, N5-pentacarbodithioate. 80.0 g of the obtained heavy metal treating agent was collected in a 1 L flask and heated to 65 ° C. in the flask. After 1 hour, after the temperature in the flask became constant, 800 ml of water was injected into the flask, the gas phase in the flask was discharged, and carbon disulfide in the discharged gas was detected with a carbon disulfide detector tube (GASTEC). It was below the detection limit (2.5 ppm) when measured by No. 13) manufactured by the company, and was below the allowable concentration of 10 ppm.
実施例２
テトラエチレンペンタミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４，Ｎ５−ペンタカルボジチオ酸ナトリウム４５％水溶液をジエチレントリアミン−Ｎ１，Ｎ２，Ｎ３−トリスカルボジチオ酸ナトリウム４０％水溶液とした以外は実施例１と同様の操作を行った。二硫化炭素の検知濃度は５ｐｐｍであり、許容濃度の１０ｐｐｍを下回った。
Example 2
Example 1 except that a 45% aqueous solution of tetraethylenepentamine-N1, N2, N3, N4, N5-pentacarbodithioate was changed to a 40% aqueous solution of diethylenetriamine-N1, N2, N3-triscarbodithioate. The operation was performed. The detected concentration of carbon disulfide was 5 ppm, which was below the allowable concentration of 10 ppm.
実施例３
テトラエチレンペンタミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４，Ｎ５−ペンタカルボジチオ酸ナトリウム４５％水溶液をエチレンジアミン−Ｎ，Ｎ’−ビスカルボジチオ酸ナトリウム１５％水溶液とした以外は実施例１と同様の操作を行った。二硫化炭素の検知濃度は４ｐｐｍであり、許容濃度の１０ｐｐｍを下回った。
Example 3
The same operation as in Example 1 except that the 45% aqueous solution of sodium tetraethylenepentamine-N1, N2, N3, N4, N5-pentacarbodithioate was changed to a 15% aqueous solution of ethylenediamine-N, N′-biscarbodithioate. Went. The detected concentration of carbon disulfide was 4 ppm, which was below the allowable concentration of 10 ppm.
比較例１
ナトリウムメトキシドを添加混合しない以外は実施例１と同様の操作を行った。二硫化炭素の検知濃度は１３ｐｐｍであり、許容濃度の１０ｐｐｍを上回っていた。
Comparative Example 1
The same operation as in Example 1 was performed except that sodium methoxide was not added and mixed. The detected concentration of carbon disulfide was 13 ppm, which exceeded the allowable concentration of 10 ppm.
比較例２
ナトリウムメトキシドを添加混合しない以外は実施例２と同様の操作を行った。二硫化炭素の検知濃度は２０ｐｐｍであり、許容濃度の１０ｐｐｍを上回っていた。
Comparative Example 2
The same operation as in Example 2 was performed except that sodium methoxide was not added and mixed. The detected concentration of carbon disulfide was 20 ppm, which exceeded the allowable concentration of 10 ppm.
比較例３
ナトリウムメトキシドを添加混合しない以外は実施例３と同様の操作を行った。二硫化炭素の検知濃度は３５ｐｐｍであり、許容濃度の１０ｐｐｍを上回っていた。
Comparative Example 3
The same operation as in Example 3 was performed except that sodium methoxide was not added and mixed. The detected concentration of carbon disulfide was 35 ppm, which exceeded the allowable concentration of 10 ppm.
比較例４
ナトリウムメトキシドをメタノールとした以外は実施例１と同様の操作を行った。二硫化炭素の検知濃度は１０ｐｐｍであった。メタノールが酸として機能し、テトラエチレンペンタミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４，Ｎ５，−ペンタカルボジチオ酸ナトリウムの分解を促進したため、ナトリウムメトキシドほどの二硫化炭素抑制効果を示さなかったと考えられた。
Comparative Example 4
The same operation as in Example 1 was carried out except that sodium methoxide was changed to methanol. The detected concentration of carbon disulfide was 10 ppm. Since methanol functioned as an acid and promoted the decomposition of sodium tetraethylenepentamine-N1, N2, N3, N4, N5, -pentacarbodithioate, it was considered that the carbon disulfide inhibitory effect was not as good as sodium methoxide. It was.
（重金属処理能力試験）
実施例４
飛灰（Ｃａ＝２３．８％、Ｎａ＝１．６％、Ｋ＝４．４％、Ｐｂ＝３７００ｐｐｍ、Ｚｎ＝１６４００ｐｐｍ、Ｃｕ＝６００ｐｐｍを含む）５０重量部に対し、水１５重量部（飛灰に対して３０重量部）と実施例１の重金属処理剤１．５重量部（飛灰に対して３重量部）を加え、混練した。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。鉛の溶出量は０．０５ｍｇ／Ｌ以下であり、十分に不溶化された。
(Heavy metal processing ability test)
Example 4
Flying ash (Ca = 23.8%, Na = 1.6%, K = 4.4%, Pb = 3700ppm, Zn = 16400ppm, Cu = 600ppm included) 50 parts by weight of water 15 parts by weight (flying 30 parts by weight with respect to ash) and 1.5 parts by weight of the heavy metal treating agent of Example 1 (3 parts by weight with respect to fly ash) were added and kneaded. After the treatment, a dissolution test was conducted according to the Environmental Agency Notification No. 13 test in 1973. The elution amount of lead was 0.05 mg / L or less and was sufficiently insolubilized.
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