JP5504602B2 - Process for producing high-purity piperazine-N-carbodithioate and use thereof - Google Patents
Process for producing high-purity piperazine-N-carbodithioate and use thereof Download PDFInfo
- Publication number
- JP5504602B2 JP5504602B2 JP2008267106A JP2008267106A JP5504602B2 JP 5504602 B2 JP5504602 B2 JP 5504602B2 JP 2008267106 A JP2008267106 A JP 2008267106A JP 2008267106 A JP2008267106 A JP 2008267106A JP 5504602 B2 JP5504602 B2 JP 5504602B2
- Authority
- JP
- Japan
- Prior art keywords
- piperazine
- carbodithioate
- heavy metal
- carbon disulfide
- treating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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の安定化方法及びその製造方法である。 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. It is the stabilization method of the suppressed heavy metal processing agent, and its manufacturing method.
ピペラジンのカルボジチオ酸塩、特にピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩は有害ガス（硫化水素、二硫化炭素）の発生がなく、重金属固定可能に優れた重金属処理剤として知られている（特許文献１）。 Piperazine carbodithioate, particularly piperazine-N, N′-biscarbodithioate, is known as a heavy metal treating agent that does not generate harmful gases (hydrogen sulfide, carbon disulfide) and is excellent in fixing heavy metals ( Patent Document 1).
一方、ピペラジン以外のアミンのカルボジチオ酸塩では有害ガス（硫化水素、二硫化炭素）が発生するという問題があり、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩は、それ自身からの有害ガスの発生がなく重金属固定可能に優れているが、他のアミンのカルボジチオ酸塩に混合しても、他のアミンのカルボジチオ酸塩からの有害ガスの発生抑止をすることまではできなかった。 On the other hand, carbodithioates of amines other than piperazine have a problem that harmful gases (hydrogen sulfide, carbon disulfide) are generated. Piperazine-N, N′-biscarbodithioate has a problem of harmful gases from itself. There is no generation and it is excellent in being able to fix heavy metals, but even when mixed with carbodithioates of other amines, it has not been possible to suppress the generation of harmful gases from carbodithioates of other amines.
アミンのカルボジチオ酸塩からの有害ガスの発生を抑止するために別途アミンを添加する方法が知られている（特許文献２、３）。しかし、添加されたアミンは重金属と反応して不溶化しないため、アミンガス自身のガス発生の問題や、重金属の処理後にアミンが流出すると環境上の問題があった。 In order to suppress the generation of harmful gas from the carbodithioate of amine, a method of adding an amine separately is known (Patent Documents 2 and 3). However, since the added amine does not react with the heavy metal to be insolubilized, there are problems of gas generation of the amine gas itself and environmental problems when the amine flows out after the heavy metal treatment.
ピペラジン−Ｎ−カルボジチオ酸塩はピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に付随する副生物としか認識されていなかった。 Piperazine-N-carbodithioate was only recognized as a byproduct associated with piperazine-N, N'-biscarbodithioate.
ピペラジン−Ｎ−カルボジチオ酸塩は、従来、ピペラジン、二硫化炭素及びアルカリ水酸化物の反応によって合成されていたが、その反応が水溶液中で行われていたため、ピペラジン−Ｎ−カルボジチオ酸塩とピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩は競争反応となり、ピペラジン−Ｎ−カルボジチオ酸塩を選択的に製造された例はなかった。 Piperazine-N-carbodithioate has been conventionally synthesized by the reaction of piperazine, carbon disulfide and alkali hydroxide, but since the reaction was performed in an aqueous solution, piperazine-N-carbodithioate and piperazine -N, N'-biscarbodithioate became a competitive reaction, and there was no example in which piperazine-N-carbodithioate was selectively produced.
最近になって、ピペラジン−Ｎ−カルボジチオ酸塩の価値が見直され、その含有量が高い重金属処理剤が提案されている（特許文献４参照）。しかしピペラジン−Ｎ−カルボジチオ酸塩の合成が水溶液中で実施されていたため、未反応のピペラジンを大量に含有するものしか得られていなかった。例えば特許文献の合成例１では、ピペラジン−Ｎ、Ｎ'−ビスカルボジチオ酸塩が２０％でピペラジン−Ｎ−カルボジチオ酸塩の比率が８０％の合成物が得られている。しかしピペラジン（１００部、１．１６モル相当）と二硫化炭素（８９部、１．１７モル相当）を１：１で反応させて、ピペラジンに二硫化炭素が２分子結合したピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩が２０重量％生成しているため、ピペラジンが全て反応するには二硫化炭素が不足し、ピペラジン−Ｎ−カルボジチオ酸塩に対して未反応のピペラジンが６重量％以上（モル％では１３モル％以上）含有したものであった。 Recently, the value of piperazine-N-carbodithioate has been reviewed, and a heavy metal treating agent having a high content has been proposed (see Patent Document 4). However, since synthesis of piperazine-N-carbodithioate was carried out in an aqueous solution, only those containing a large amount of unreacted piperazine were obtained. For example, in Synthesis Example 1 in the patent document, a synthesized product is obtained in which piperazine-N, N′-biscarbodithioate is 20% and the ratio of piperazine-N-carbodithioate is 80%. However, piperazine (100 parts, equivalent to 1.16 moles) and carbon disulfide (89 parts, equivalent to 1.17 moles) are reacted at a ratio of 1: 1, and piperazine-N, N in which two molecules of carbon disulfide are bonded to piperazine. Since 20% by weight of '-biscarbodithioate is formed, carbon disulfide is insufficient for all reaction of piperazine, and unreacted piperazine is not less than 6% by weight with respect to piperazine-N-carbodithioate. (In mol%, 13 mol% or more).
この様に、従来の水溶液中での反応では、ピペラジン−Ｎ−カルボジチオ酸とピペラジン−Ｎ，Ｎ'−ビスカルボジチオ酸の生成が必ず競争反応となる方法で製造されていたため、得られるピペラジン−Ｎ−カルボジチオ酸には必ず未反応ピペラジンの残存が避けられず、高純度のピペラジン−Ｎ−カルボジチオ酸塩、即ち未反応ピペラジンを含有しないピペラジン−Ｎ−カルボジチオ酸塩が有効に利用できていなかった。 As described above, in the conventional reaction in an aqueous solution, the production of piperazine-N-carbodithioic acid and piperazine-N, N′-biscarbodithioic acid is always produced by a competitive reaction. In N-carbodithioic acid, unreacted piperazine remains inevitably, and high-purity piperazine-N-carbodithioate, that is, piperazine-N-carbodithioate containing no unreacted piperazine, was not effectively used. .
本発明の目的は、高純度でピペラジンを含有しないピペラジン−Ｎ−カルボジチオ酸を重金属処理剤の有効成分として利用することにより、重金属処理剤の保管時、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、なおかつ重金属処理後もアミンの流出の問題がない重金属処理剤を提供することにある。 The object of the present invention is to use piperazine-N-carbodithioic acid which is high in purity and does not contain piperazine as an active ingredient of a heavy metal treating agent, so that the heavy metal treating agent can be stored, transported, used, particularly at high temperatures. An object of the present invention is to provide a heavy metal treating agent that suppresses the generation of harmful carbon disulfide and the like and is free from the problem of amine spillage even after heavy metal treatment.
本発明者等は、未反応ピペラジンを含まないピペラジン−Ｎ−カルボジチオ酸塩を用いれば、少なくともピペラジン以外の一種以上のアミンのカルボジチオ酸塩と混合して重金属処理剤として用いることにより、ピペラジン−Ｎ−カルボジチオ酸塩が他のアミンのカルボジチオ酸塩の分解に由来する有害ガスの発生を低減でき、なおかつ未反応ピペラジンを含まないために重金属処理剤からピペラジンのガス発生や流出の問題がないことを見出し、その様な未反応ピペラジンを含まないピペラジン−Ｎ−カルボジチオ酸塩は、有機溶媒中で選択的に合成できることを見出し、本発明を完成させるに到ったものである。 If the present inventors use piperazine-N-carbodithioate that does not contain unreacted piperazine, it is mixed with at least one carbodithioate of an amine other than piperazine and used as a heavy metal treating agent. -Carbodithioate can reduce the generation of harmful gases resulting from the decomposition of carbodithioate of other amines, and since it does not contain unreacted piperazine, there is no problem of gas generation or outflow of piperazine from heavy metal treatment agents. The present inventors have found that piperazine-N-carbodithioate containing no unreacted piperazine can be selectively synthesized in an organic solvent, and have completed the present invention.
以下、本発明に係わる重金属処理剤についてその詳細を説明する。 Hereinafter, the details of the heavy metal treating agent according to the present invention will be described.
本発明の重金属処理剤はピペラジン−Ｎ−カルボジチオ酸塩及び、少なくともピペラジン以外の一種以上のアミンのカルボジチオ酸塩を含んでなるものである。 The heavy metal treating agent of the present invention comprises piperazine-N-carbodithioate and at least one carbodithioate of an amine other than piperazine.
ピペラジン−Ｎ−カルボジチオ酸塩は、それ自身が耐熱性、耐酸性が高く分解によって有害ガス（硫化水素、二硫化炭素等）の発生がなく、ピペラジン以外のアミンのカルボジチオ酸塩が分解する際に発生する有害ガスの発生を抑制することができる。 Piperazine-N-carbodithioate itself has high heat resistance and acid resistance, and there is no generation of harmful gases (hydrogen sulfide, carbon disulfide, etc.) due to decomposition, and when carbodithioate of amines other than piperazine decomposes. Generation | occurrence | production of the harmful gas to generate | occur | produce can be suppressed.
本発明の重金属処理剤は未反応ピペラジンを含有しないものが好ましく、未反応ピペラジンがピペラジン−Ｎ−カルボジチオ酸塩に対して少なくとも１０モル％以下、さらに５モル％以下、特に１モル％以下で、全く含有しないことが好ましい。未反応ピペラジンを含有すると、重金属処理剤からピペラジンガスの発生、或いは重金属処理後にピペラジンが流出するという問題がある。 The heavy metal treating agent of the present invention preferably contains no unreacted piperazine, and the unreacted piperazine is at least 10 mol% or less, further 5 mol% or less, particularly 1 mol% or less with respect to piperazine-N-carbodithioate, It is preferable not to contain at all. When unreacted piperazine is contained, there is a problem that piperazine gas is generated from the heavy metal treating agent or piperazine flows out after the heavy metal treatment.
本発明におけるピペラジン以外の一種以上の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の主にピペラジン以外のアミンが例示される。 The carbodithioate of one or more amines other than piperazine in the present invention is not particularly limited, and examples thereof include carbodithioate derived from an aliphatic or aromatic amine compound, and as an aliphatic amine compound, Examples are mainly amines other than piperazine such as diethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like.
本発明におけるピペラジン−Ｎ−カルボジチオ酸塩及び、少なくともピペラジン以外の一種以上のアミンのカルボジチオ酸塩は、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。 In the present invention, piperazine-N-carbodithioate and at least one kind of amine carbodithioate other than piperazine are alkali metal salts, alkaline earth metal salts, and ammonium salts, but they are thermally stable and inexpensive. Therefore, sodium salt or potassium salt is preferable.
本発明では、ピペラジン以外の一種以上のアミンのカルボジチオ酸塩の他に、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を含んでも良いが、少なくともピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩よりもピペラジン−Ｎ−カルボジチオ酸塩の比率が多いことが好ましい。ピペラジン−Ｎ−カルボジチオ酸塩中に含まれるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩は少なくとも５０モル％以下、さらに１０モル％以下、特に５モル％以下で、全く含まないものが好ましい。ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の比率が多くなると、ピペラジン以外の一種以上のアミンのカルボジチオ酸塩と混合して用いた場合に、ピペラジン以外の一種以上のアミンのカルボジチオ酸塩から発生する有害ガスの抑止力が小さくなるからである。 In the present invention, piperazine-N, N′-biscarbodithioate may be included in addition to carbodithioate of one or more amines other than piperazine, but at least piperazine-N, N′-biscarbodithioate is included. It is preferable that the ratio of piperazine-N-carbodithioate is larger than that. The piperazine-N, N′-biscarbodithioate contained in the piperazine-N-carbodithioate is preferably at least 50 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less, and not contained at all. When the ratio of piperazine-N, N′-biscarbodithioate is increased, when mixed with a carbodithioate of one or more amines other than piperazine, the carbodithioate of one or more amines other than piperazine is used. This is because the deterring power of generated harmful gas is reduced.
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 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.
本発明の重金属処理剤を水溶液で用いる場合、ピペラジン−Ｎ−カルボジチオ酸塩と少なくともピペラジン以外の一種以上のアミンのカルボジチオ酸塩の総計濃度は高い方が好ましく、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 total concentration of piperazine-N-carbodithioate and at least one carbodithioate of one or more amines other than piperazine is preferably higher, and is preferably 20 to 60% by weight, particularly 35 to 35% by weight. A range of 50% by weight is desirable.
本発明の重金属処理剤中のピペラジン−Ｎ−カルボジチオ酸塩の量は、混合する他のアミンのカルボジチオ酸塩の濃度、安定性にもよるが、１〜２０重量％、特に３〜１５重量％の範囲が好ましい。ピペラジン−Ｎ−カルボジチオ酸塩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 piperazine-N-carbodithioate in the heavy metal treating agent of the present invention depends on the concentration and stability of the carbodithioate of other amines to be mixed, but it is 1 to 20% by weight, particularly 3 to 15% by weight. The range of is preferable. If the amount of piperazine-N-carbodithioate is larger than necessary, the solubility of amine carbodithioate will be reduced, and if it is too small, the harmful gas generation suppressing effect of the present invention will not be 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、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 and alkali hydroxides.
次に本発明の重金属処理剤の製造法について説明する。 Next, the manufacturing method of the heavy metal processing agent of this invention is demonstrated.
本発明の重金属処理剤中のピペラジン−Ｎ−カルボジチオ酸塩は、ピペラジンと二硫化炭素を有機溶媒中で反応させ、生成したピペラジン−Ｎ−カルボジチオ酸をアルカリ水酸化物水溶液と反応させることによって製造することができる。 Piperazine-N-carbodithioate in the heavy metal treating agent of the present invention is produced by reacting piperazine and carbon disulfide in an organic solvent, and reacting the resulting piperazine-N-carbodithioic acid with an aqueous alkali hydroxide solution. can do.
アルカリ水酸化物としては、水酸化ナトリウム、水酸化カリウムが特に好ましい。 As the alkali hydroxide, sodium hydroxide and potassium hydroxide are particularly preferable.
ピペラジン、二硫化炭素とアルカリ水酸化物を水溶液中で反応させる従来の方法では、ピペラジン−Ｎ−カルボジチオ酸塩の比率の高いものを得ようとすると必ずピペラジン及びピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩が副生し、一方、ピペラジンを完全に反応させて全てをカルボジチオ酸塩とすると、ピペラジン−Ｎ−カルボジチオ酸塩の比率が小さいものしか得られなかった。 In the conventional method in which piperazine, carbon disulfide and alkali hydroxide are reacted in an aqueous solution, piperazine and piperazine-N, N′-biscarbohydrate are always obtained in order to obtain a high ratio of piperazine-N-carbodithioate. On the other hand, dithioate was produced as a by-product, while when piperazine was completely reacted to convert all to carbodithioate, only a small ratio of piperazine-N-carbodithioate was obtained.
ピペラジン−Ｎ−カルボジチオ酸塩を選択的に製造するためには、ピペラジンと二硫化炭素の反応を有機溶媒中、特にピペラジンと二硫化炭素を溶解する有機溶媒中で行うことが好ましい。ピペラジン−Ｎ−カルボジチオ酸は有機溶媒には不溶であるため、ピペラジンと二硫化炭素が反応してピペラジン−Ｎ−カルボジチオ酸が生成すると直ちに析出し、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸へ転化する前に高純度なピペラジン−Ｎ−カルボジチオ酸として分離できる。その様にして得られたピペラジン−Ｎ−カルボジチオ酸にアルカリ水酸化物を反応させると、未反応ピペラジン及びピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を含有しない高純度のピペラジン−Ｎ−カルボジチオ酸塩を選択的に製造することができる。 In order to selectively produce piperazine-N-carbodithioate, it is preferable to carry out the reaction of piperazine and carbon disulfide in an organic solvent, particularly in an organic solvent in which piperazine and carbon disulfide are dissolved. Since piperazine-N-carbodithioic acid is insoluble in organic solvents, when piperazine reacts with carbon disulfide to form piperazine-N-carbodithioic acid, it immediately precipitates and becomes piperazine-N, N′-biscarbodithioic acid. It can be separated as high purity piperazine-N-carbodithioic acid before conversion. When piperazine-N-carbodithioic acid thus obtained is reacted with an alkali hydroxide, high-purity piperazine-N-carbodithio containing no unreacted piperazine and piperazine-N, N′-biscarbodithioate is obtained. Acid salts can be selectively produced.
上記の反応を進めるにあたり、ピペラジンと一時に反応させる二硫化炭素はピペラジンのモル当量より小さくすることが好ましく、具体的にはピペラジンの当量未満の二硫化炭素の反応を少なくとも２回以上、さらに複数回に分けて、連続的又は間歇的に反応を繰り返すことが好ましい。反応系おけるピペラジンに対する二硫化炭素の存在比率を小さくする（即ち反応する二硫化炭素に対するピペラジンの比率を増大する）ことによって、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸の副生を抑制し、ピペラジン−Ｎ−カルボジチオ酸の純度を高めることができる。 In proceeding with the above reaction, the carbon disulfide to be reacted with piperazine at a time is preferably smaller than the molar equivalent of piperazine. Specifically, the reaction of carbon disulfide with less than the equivalent of piperazine is performed at least twice or more. The reaction is preferably repeated continuously or intermittently. By reducing the abundance ratio of carbon disulfide to piperazine in the reaction system (ie, increasing the ratio of piperazine to reacting carbon disulfide), by-product piperazine-N, N′-biscarbodithioic acid is suppressed, The purity of piperazine-N-carbodithioic acid can be increased.
有機溶媒中でのピペラジンと二硫化炭素の反応と、生成したピペラジン−Ｎ−カルボジチオ酸と水酸化アルカリの反応は別々に行っても良いが、有機溶媒と水溶液の二層で連続的に反応させても良い。 The reaction of piperazine and carbon disulfide in an organic solvent and the reaction of the generated piperazine-N-carbodithioic acid and alkali hydroxide may be carried out separately, but they are continuously reacted in two layers of an organic solvent and an aqueous solution. May be.
特にピペラジン−Ｎ−カルボジチオ酸塩中のピペラジンの含有量を低減させるには、有機溶媒中で生成し析出したピペラジン−Ｎ−カルボジチオ酸を一旦単離し、有機溶媒で洗浄して未反応ピペラジンを除去した後、別途水溶液中で水酸化アルカリと反応させればよい。 In particular, in order to reduce the content of piperazine in piperazine-N-carbodithioate, piperazine-N-carbodithioic acid formed and precipitated in an organic solvent is once isolated and washed with an organic solvent to remove unreacted piperazine. Then, it may be separately reacted with an alkali hydroxide in an aqueous solution.
本発明で用いる有機溶媒は、ピペラジン、二硫化炭素を溶解し、ピペラジン−Ｎ−カルボジチオ酸塩を溶解せず、なおかつ水に不溶な有機溶媒であることが好ましく、例えばハロゲン化炭化水素やエーテルが例示できる。 The organic solvent used in the present invention is preferably an organic solvent that dissolves piperazine and carbon disulfide, does not dissolve piperazine-N-carbodithioate, and is insoluble in water. It can be illustrated.
本発明の重金属処理剤は、上記の方法で得られたペラジン−Ｎ−カルボジチオ酸塩をピペラジン以外のアミンのカルボジチオ酸塩（又はその水溶液）と混合して製造することができる。 The heavy metal treating agent of the present invention can be produced by mixing the perazine-N-carbodithioate obtained by the above method with a carbodithioate of an amine other than piperazine (or an aqueous solution thereof).
ピペラジン以外のアミンのカルボジチオ酸塩の製造方法は特に限定されないが、水溶液中でアミンと二硫化炭素及び水酸化アルカリを反応させればよい。 Although the manufacturing method of the carbodithioate of amines other than piperazine is not specifically limited, What is necessary is just to make an amine, carbon disulfide, and an alkali hydroxide react in aqueous solution.
ピペラジン以外の一種以上のアミン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の主にピペラジン以外のアミンが例示される。 The one or more amines other than piperazine are not particularly limited, and examples thereof include carbodithioates derived from aliphatic or aromatic amine compounds. Examples of aliphatic amine compounds include diethylamine, ethylenediamine, diethylenetriamine, and triamine. Examples include amines other than piperazine such as ethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
上記のアミンを水溶液中で二硫化炭素と水酸化アルカリと反応させ、最終的に未反応の二硫化炭素を除去すれば、アミンのカルボジチオ酸塩水溶液が得られる。 When the above amine is reacted with carbon disulfide and alkali hydroxide in an aqueous solution and finally unreacted carbon disulfide is removed, an aqueous solution of amine carbodithioate can be obtained.
次に本発明の重金属処理剤を用いた重金属処理について説明する。 Next, heavy metal treatment using the heavy metal treating agent of the present invention will be described.
本発明の重金属処理剤は、重金属を含有した土壌、排水、廃棄物、焼却灰等と混合することにより、重金属の溶出を防止することができる。本発明の重金属処理剤の重金属固定化における使用方法は、通常の他の重金属処理剤と同様の方法が適用でき、重金属処理剤に必要に応じて水、アルカリ水酸化物や塩化鉄等のｐＨ調整剤と適宜混合して用いればよい。 The heavy metal treating agent of the present invention can prevent elution of heavy metals by mixing with soil, drainage, waste, incinerated ash, etc. containing heavy metals. The method of use of the heavy metal treatment agent of the present invention in immobilizing heavy metals can be applied in the same manner as other normal heavy metal treatment agents, and pH of water, alkali hydroxide, iron chloride, etc. as necessary for the heavy metal treatment agent. What is necessary is just to mix and use suitably with a regulator.
本発明の重金属処理剤は、重金属固定化能に優れ、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（硫化水素、二硫化炭素等）の発生が抑制される。 The heavy metal treating agent of the present invention has excellent heavy metal immobilization ability and suppresses the generation of harmful gases (hydrogen sulfide, carbon disulfide, etc.) 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。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
合成例１ ピペラジン−Ｎ−カルボジチオ酸カリウムの合成
攪拌装置、温度計、コンデンサー、滴下ロートを備えた３００ｍＬの４口フラスコに、窒素気流下で、クロロホルム４０ｍｌにピペラジン１０ｇを溶解させた後、クロロホルム６６ｍｌに二硫化炭素９．７ｇを溶解させた溶液の２／３の量を１６分間かけて滴下した。次に４８％ＫＯＨ水溶液を１５．３ｇと純水２０．０ｇを混合した水溶液を添加した。次に、残りの二硫化炭素／クロロホルム溶液を１０分間かけて滴下した。攪拌を停止すると、黄緑色の水層及び白濁半透明の二層に分離した。黄緑色の相を１３Ｃ−ＮＭＲで測定したところ、ピペラジン−Ｎ−カルボジチオ酸カリウム９８ｍｏｌ％、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム２ｍｏｌ％、ピペラジン０ｍｏｌ％であった。
Synthesis Example 1 Synthesis of potassium piperazine-N-carbodithioate In a 300 mL four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 10 g of piperazine was dissolved in 40 ml of chloroform under a nitrogen stream, and then 66 ml of chloroform. 2/3 of a solution in which 9.7 g of carbon disulfide was dissolved was added dropwise over 16 minutes. Next, an aqueous solution in which 15.3 g of 48% KOH aqueous solution and 20.0 g of pure water were mixed was added. Next, the remaining carbon disulfide / chloroform solution was added dropwise over 10 minutes. When the stirring was stopped, the mixture was separated into a yellow-green aqueous layer and a cloudy translucent two-layer. When the yellowish green phase was measured by 13 C-NMR, it was found to be 98 mol% piperazine-N-carbodithioate, 2 mol% piperazine-N, N′-biscarbodithioate, and 0 mol% piperazine.
合成例２ ピペラジン−Ｎ−カルボジチオ酸ナトリウムの合成
攪拌装置、温度計、コンデンサー、滴下ロートを備えた３００ｍＬの４口フラスコに、窒素気流下で、ジクロロメタン１００ｍｌにピペラジン５ｇを溶解させた後、ジクロロメタン６６ｍｌに二硫化炭素４．９ｇを溶解させた溶液の２／３の量を１６分間かけて滴下した。次に４８％ＫＯＨ水溶液を５．５ｇと純水３０．０ｇを混合した水溶液を添加した。次に、残りの二硫化炭素／クロロホルム溶液を１０分間かけて滴下した。攪拌を停止すると、黄緑色の水層及び白濁半透明の二層に分離した。黄緑色の相を１３Ｃ−ＮＭＲで測定したところ、ピペラジン−Ｎ−カルボジチオ酸ナトリウム９７ｍｏｌ％、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム３ｍｏｌ％、ピペラジン０ｍｏｌ％であった。
Synthesis Example 2 Synthesis of Piperazine-sodium N-carbodithioate In a 300 mL four-necked flask equipped with a stirrer, thermometer, condenser and dropping funnel, 5 g of piperazine was dissolved in 100 ml of dichloromethane under a nitrogen stream, and then 66 ml of dichloromethane. 2/3 of the solution in which 4.9 g of carbon disulfide was dissolved was added dropwise over 16 minutes. Next, an aqueous solution in which 5.5 g of 48% KOH aqueous solution and 30.0 g of pure water were mixed was added. Next, the remaining carbon disulfide / chloroform solution was added dropwise over 10 minutes. When the stirring was stopped, the mixture was separated into a yellow-green aqueous layer and a cloudy translucent two-layer. When the yellowish green phase was measured by 13 C-NMR, it was 97 mol% of piperazine-N-carbodithioate sodium, 3 mol% of piperazine-N, N′-biscarbodithioate, and 0 mol% of piperazine.
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４０ｗｔ％とピペラジン−Ｎ−カルボジチオ酸カリウム１０ｗｔ％となるよう重金属処理剤の調整を行った。次に１Ｌのテドラーバッグに飛灰（Ｃａ＝２８．８%、Ｎａ＝２．１％、Ｋ＝２．３％、Ｐｂ＝１６００ｐｐｍ、Ｚｎ＝８５００ｐｐｍ、Ｃｕ＝５００ｐｐｍを含む）５gを採取し、重金属処理剤を飛灰に０．５ｇ、水を５ｇ添加し、空気を１Ｌ充填した後、混練を行った。３０分間静置後、テドラーバッグ内の二硫化炭素の測定を行った。その結果、二硫化炭素は５ｐｐｍ検出され、許容濃度の１０ｐｐｍを下回った。
Example 1
The heavy metal treating agent was adjusted to 40% by weight of sodium tetraethylenepentamine-N1, N2, N3, N4, N5-pentacarbodithioate and 10% by weight of potassium piperazine-N-carbodithioate. Next, 5 g of fly ash (Ca = 28.8%, Na = 2.1%, K = 2.3%, Pb = 1600ppm, Zn = 8500ppm, Cu = 500ppm) is collected in a 1L Tedlar bag, and heavy metals are collected. The treatment agent was added to the fly ash in an amount of 0.5 g and water in an amount of 5 g, and 1 L of air was added, followed by kneading. After standing for 30 minutes, carbon disulfide in the Tedlar bag was measured. As a result, 5 ppm of carbon disulfide was detected, which was below the allowable concentration of 10 ppm.
処理後の飛灰からの鉛の溶出濃度は、０．０５ｍｇ／Ｌ未満であり、基準値の０．３ｍｇ／Ｌを下回った。 The elution concentration of lead from the fly ash after the treatment was less than 0.05 mg / L, which was lower than the standard value of 0.3 mg / L.
実施例２
ピペラジン−Ｎ−カルボジチオ酸カリウムをピペラジン−Ｎ−カルボジチオ酸ナトリウムとする以外は実施例１と同様の操作を行った。その結果、二硫化炭素は４ｐｐｍ検出され、許容濃度の１０ｐｐｍを下回った。
Example 2
The same operation as in Example 1 was carried out except that piperazine-N-carbodithioic acid potassium was changed to piperazine-N-carbodithioic acid sodium. As a result, 4 ppm of carbon disulfide was detected, which was below the allowable concentration of 10 ppm.
比較例1
ピペラジン−Ｎ−カルボジチオ酸カリウムをＮ−アミノエチルピペラジン−Ｎ’−カルボジチオ酸ナトリウムとする以外は実施例１と同様の操作を行った。その結果、二硫化炭素は２１ｐｐｍと許容濃度の１０ｐｐｍを上回った。
Comparative Example 1
The same operation as in Example 1 was performed except that potassium piperazine-N-carbodithioate was changed to sodium N-aminoethylpiperazine-N′-carbodithioate. As a result, carbon disulfide exceeded 21 ppm and the allowable concentration of 10 ppm.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008267106A JP5504602B2 (en) | 2008-10-16 | 2008-10-16 | Process for producing high-purity piperazine-N-carbodithioate and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008267106A JP5504602B2 (en) | 2008-10-16 | 2008-10-16 | Process for producing high-purity piperazine-N-carbodithioate and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010095605A JP2010095605A (en) | 2010-04-30 |
| JP5504602B2 true JP5504602B2 (en) | 2014-05-28 |
Family
ID=42257517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008267106A Active JP5504602B2 (en) | 2008-10-16 | 2008-10-16 | Process for producing high-purity piperazine-N-carbodithioate and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5504602B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5782733B2 (en) * | 2011-02-15 | 2015-09-24 | 東ソー株式会社 | Method for producing solid amine carbodithioate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2775106B2 (en) * | 1988-01-26 | 1998-07-16 | 日本ケミファ株式会社 | Liver disease therapeutic agent and piperazine derivative |
| JP4188045B2 (en) * | 2002-09-26 | 2008-11-26 | 日本曹達株式会社 | Heavy metal fixing agent and method for stabilizing low temperature of heavy metal fixing agent |
| JP3858004B2 (en) * | 2003-05-30 | 2006-12-13 | 栗田工業株式会社 | Heavy metal immobilizing agent and method for treating heavy metal-containing material |
| JP4394915B2 (en) * | 2003-09-16 | 2010-01-06 | ミヨシ油脂株式会社 | Heavy metal immobilizing agent and method for immobilizing heavy metals in solid substances |
| JP2005089564A (en) * | 2003-09-16 | 2005-04-07 | Miyoshi Oil & Fat Co Ltd | Heavy metal-immobilizing treatment agent and method for immobilizing heavy metal in solid substance |
| JP4632346B2 (en) * | 2004-05-28 | 2011-02-16 | ミヨシ油脂株式会社 | Waste treatment method and heavy metal immobilization treatment composition |
| JP4968765B2 (en) * | 2005-08-26 | 2012-07-04 | ミヨシ油脂株式会社 | Metal fixing agent |
| JP2010090193A (en) * | 2008-10-03 | 2010-04-22 | Tosoh Corp | Suppressant for harmful gas generation and application thereof |
-
2008
- 2008-10-16 JP JP2008267106A patent/JP5504602B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010095605A (en) | 2010-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU779718B2 (en) | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control | |
| JP5272306B2 (en) | Heavy metal treating agent and method for treating heavy metal contaminants | |
| JP5504571B2 (en) | Heavy metal treating agent and method for treating heavy metal contaminants | |
| JP4867701B2 (en) | Heavy metal treating agent and method for stabilizing heavy metal contaminants using the same | |
| JP4961822B2 (en) | Heavy metal treatment agent excellent in low-temperature stability and heavy metal treatment method using the same | |
| JP5504602B2 (en) | Process for producing high-purity piperazine-N-carbodithioate and use thereof | |
| JP4822253B2 (en) | Method for producing formate from carbon dioxide and hydrogen | |
| JP4867700B2 (en) | Heavy metal treatment agent and method for treating heavy metal contaminants using the same | |
| JP3895018B2 (en) | Solid heavy metal fixative | |
| JP5439990B2 (en) | Solid heavy metal treating agent, production method and use thereof | |
| JP2013060517A (en) | Heavy metal treating agent, manufacturing method of heavy metal treating agent, and method for treatment of heavy metal-containing material using the same | |
| JP5252028B2 (en) | Heavy metal treating agent and method for stabilizing heavy metal contaminants using the same | |
| JP2010090193A (en) | Suppressant for harmful gas generation and application thereof | |
| JP5439979B2 (en) | Solid heavy metal treating agent, production method and use thereof | |
| JP4406751B2 (en) | Method for storing or transporting hydrogen peroxide-containing wastewater and processing method | |
| JP2010184835A (en) | Method for recovering iodine | |
| JP5066920B2 (en) | Heavy metal treating agent and method for treating heavy metal contaminants | |
| JP5782733B2 (en) | Method for producing solid amine carbodithioate | |
| WO2010058774A1 (en) | Solid heavy metal processing agent, method for producing same and use of same | |
| JP5182115B2 (en) | Heavy metal immobilization treatment method, treatment agent used therefor, and production method thereof | |
| JP5903866B2 (en) | Heavy metal treating agent and method for treating heavy metal-containing material using the same | |
| JP5493788B2 (en) | Heavy metal treating agent and method for treating heavy metal contaminants | |
| JP5725273B2 (en) | Method for deodorizing liquid or mud, deodorant and method for producing the same | |
| JP5747536B2 (en) | Method for producing solid amine carbodithioate and method for producing amine carbodithioate aqueous solution | |
| JPH0379286B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110921 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130730 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130930 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131119 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140120 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140218 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140303 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5504602 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |