JP2012214429A - Aqueous piperazine-n, n '-biscarbodithioate solution, and method of producing the same - Google Patents

Aqueous piperazine-n, n '-biscarbodithioate solution, and method of producing the same Download PDF

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JP2012214429A
JP2012214429A JP2011180509A JP2011180509A JP2012214429A JP 2012214429 A JP2012214429 A JP 2012214429A JP 2011180509 A JP2011180509 A JP 2011180509A JP 2011180509 A JP2011180509 A JP 2011180509A JP 2012214429 A JP2012214429 A JP 2012214429A
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piperazine
biscarbodithioate
carbon disulfide
aqueous solution
carbodithioate
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JP5831036B2 (en
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Yoshinori Ayama
義則 阿山
Yasuyuki Nagai
康行 長井
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Tosoh Corp
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    • C07—ORGANIC CHEMISTRY
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof

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Abstract

PROBLEM TO BE SOLVED: To solve a problem wherein distill-away treatment or the like by an inert gas is required to enhance the ratio of a piperazine-N, N '-biscarbodithioate of high heavy metal treatment ability, when producing the piperazine carbodithioate useful as a heavy metal treating agent, and wherein an industrial production method therefor is required.SOLUTION: The piperazine-N, N '-biscarbodithioate is produced with addition of a hydrophobic solvent in a method of reacting piperazine, carbon disulfide of reaction equivalent or more with respect to the piperazine, and an alkali metal hydroxide, in an aqueous solution. The method can produce the piperazine-N, N '-biscarbodithioate not containing piperazine-N-biscarbodithioate, without requiring the distill-away treatment or the like by the inert gas.

Description

本発明は重金属処理剤として有用なピペラジンカルボジチオ酸塩水溶液及びその製造方法に関し、さらに詳しくはピペラジン−Ｎ−カルボジチオ酸塩を含まないピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の水溶液及びその製造方法を提供するものである。   The present invention relates to an aqueous piperazine carbodithioate aqueous solution useful as a heavy metal treating agent and a method for producing the same, and more specifically, an aqueous solution of piperazine-N, N′-biscarbodithioate not containing piperazine-N-carbodithioate and the method thereof A manufacturing method is provided.

環境問題、特に廃棄物処理にまつわる環境汚染の問題は、わが国のみならず世界共通の課題である。わが国では、廃棄物焼却によって発生する飛灰をキレート薬剤によって重金属の不溶化をした後に管理型の最終処分場で処理しており、廃棄物焼却灰による土壌、地下水中の重金属の汚染を防止する技術が確立されている。   Environmental problems, particularly environmental pollution problems associated with waste disposal, are common issues not only in Japan but also in the world. In Japan, fly ash generated by incineration of waste is insolubilized with heavy metals using a chelating agent and then processed at a managed final disposal site to prevent contamination of heavy metals in soil and groundwater by waste incineration ash Is established.

飛灰中の重金属を不溶化できるキレート剤としては、各種アミンのカルボジチオ酸塩が用いられるが、特にピペラジンのカルボジチオ酸塩では重金属固定化能だけでなく、使用に際して有害ガスの発生がなく、安定性及び安全性に優れた薬剤として広く用いられている（例えば特許文献１参照）。   As chelating agents that can insolubilize heavy metals in fly ash, carbodithioates of various amines are used, but piperazine carbodithioates not only have the ability to immobilize heavy metals but also generate no harmful gases when used, and are stable. And it is widely used as a drug excellent in safety (see, for example, Patent Document 1).

一方、最近になって、わが国周辺のアジア諸国においても、廃棄物焼却後の飛灰をキレート剤で処理し安全に処理することが検討され始めている。それに伴い飛灰処理用のキレート剤に対する世界的な需要も増大しつつある。   On the other hand, recently, in Asian countries around Japan, it has begun to consider the treatment of fly ash after waste incineration with a chelating agent for safe treatment. Accordingly, worldwide demand for chelating agents for fly ash treatment is increasing.

重金属処理剤として優れた性能を有するピペラジンのカルボジチオ酸塩には、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩と、ピペラジン−Ｎ−カルボジチオ酸塩の２つの化学構造が存在し得るが、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の方が高い重金属処理能を有している。   There are two chemical structures of piperazine-N, N′-biscarbodithioate and piperazine-N-carbodithioate in piperazine carbodithioate having excellent performance as a heavy metal treating agent. -N, N'-biscarbodithioate has a higher ability to treat heavy metals.

ピペラジンのカルボジチオ酸塩は、ピペラジン、二硫化炭素及びアルカリ金属水酸化物を水溶液中で混合し、二硫化炭素の沸点以下の低温（約４０℃前後）で反応した後、熟成処理することが必要である。従来の熟成は、カルボジチオ酸塩の分解を抑止するためにアルカリ過剰の条件下で行われていた。   Piperazine carbodithioate must be aged after mixing piperazine, carbon disulfide and alkali metal hydroxide in an aqueous solution and reacting at a low temperature (about 40 ° C) below the boiling point of carbon disulfide. It is. Conventional aging has been carried out under alkali-excess conditions in order to inhibit the decomposition of the carbodithioate.

従来、重金属処理能の高いピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩比率の高いピペラジンのカルボジチオ酸塩を製造する方法としては、反応時に過剰の二硫化炭素を用い、最終的に未反応の二硫化炭素を不活性ガスで留去（除去）する方法が知られている（例えば特許文献１参照）。また反応時に原料を分割混合する方法や、ピペラジンカルボジチオ酸の存在下で反応する方法（例えば特許文献２、３参照）が知られている。   Conventionally, as a method for producing a piperazine carbodithioate having a high ratio of heavy metal treating piperazine-N, N′-biscarbodithioate, an excess of carbon disulfide is used in the reaction, and finally unreacted A method of distilling off (removing) carbon disulfide with an inert gas is known (see, for example, Patent Document 1). Also known are a method of dividing and mixing the raw materials during the reaction, and a method of reacting in the presence of piperazine carbodithioic acid (see, for example, Patent Documents 2 and 3).

しかし、従来の方法で過剰の二硫化炭素を用いてピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩比率を向上させる方法では事後に大量の窒素ガスでの留去処理が必要となり、工業的でなかった。また、ピペラジンの水溶液に二硫化炭素とアルカリ金属水酸化物を分割混合する方法ではピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩比率を向上させることができるものの、分割回数を多数に増やす必要があり操作が煩雑になる問題があった。ピペラジンカルボジチオ酸の存在下で反応する方法でも同様に、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩比率を向上させることができるものの、ピペラジンカルボジチオ酸が不溶性の固体であるために均一な反応が困難となる場合や、ピペラジンカルボジチオ酸が反応槽（特に攪拌翼）に析出すると反応制御が困難となる場合があり、改善が求められていた。   However, the conventional method using an excess of carbon disulfide to improve the ratio of piperazine-N, N′-biscarbodithioate requires an after-treatment with a large amount of nitrogen gas, which is industrial. There wasn't. In addition, the method of dividing and mixing carbon disulfide and alkali metal hydroxide in an aqueous solution of piperazine can improve the ratio of piperazine-N, N′-biscarbodithioate, but it is necessary to increase the number of divisions to a large number. There was a problem that the operation was complicated. Similarly, the method of reacting in the presence of piperazine carbodithioic acid can improve the ratio of piperazine-N, N′-biscarbodithioate, but it is uniform because piperazine carbodithioic acid is an insoluble solid. When the reaction becomes difficult or when piperazinecarbodithioic acid is deposited in the reaction vessel (especially a stirring blade), the reaction control may become difficult, and improvement has been demanded.

特許第３３９１１７３号公報Japanese Patent No. 3391173 特開２００３−２２１３８９号公報JP 2003-221389 A 特開２００８−１４３８１０号公報JP 2008-143810 A

ピペラジン−Ｎ−カルボジチオ酸塩を含まないピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩からなる重金属処理剤を製造するためには、不活性ガスで留去処理や固体のピペラジンカルボジチオ酸が析出する中での反応制御が必要であった。   In order to produce a heavy metal treating agent comprising piperazine-N, N′-biscarbodithioate that does not contain piperazine-N-carbodithioate, distillation treatment with an inert gas or solid piperazinecarbodithioic acid is precipitated. It was necessary to control the reaction.

本発明者等は、ピペラジン、ピペラジンに対して反応当量以上の二硫化炭素、アルカリ金属水酸化物を水溶液中で反応する方法において、反応時に疎水性溶媒を添加することで、事後の不活性ガスの留去処理やピペラジンカルボジチオ酸析出下での反応制御をすることなく、ピペラジン−Ｎ−カルボジチオ酸塩を含まないピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液が製造できることを見出し、本発明を完成するに至ったものである。   In the method of reacting piperazine, carbon disulfide having a reaction equivalent or more with respect to piperazine in an aqueous solution, alkali metal hydroxide in an aqueous solution, a hydrophobic solvent is added at the time of the reaction, so that the subsequent inert gas It was found that a piperazine-N, N′-biscarbodithioate aqueous solution containing no piperazine-N-carbodithioate can be produced without controlling the reaction under the distillation treatment of piperazine and precipitation of piperazine carbodithioic acid. The invention has been completed.

以下、本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail.

本発明は、ピペラジン−Ｎ−カルボジチオ酸塩を含まないピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液に関するものである。ピペラジン−Ｎ−カルボジチオ酸塩が含まれない場合、重金属処理能力が高く、安定的な重金属処理効果を得ることができ、さらに、長期的な保存における処理能力の低下を抑制することができる。   The present invention relates to an aqueous piperazine-N, N′-biscarbodithioate aqueous solution that does not contain piperazine-N-carbodithioate. When piperazine-N-carbodithioate is not included, the heavy metal treatment ability is high, a stable heavy metal treatment effect can be obtained, and further, the reduction of the treatment ability in long-term storage can be suppressed.

本発明のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液におけるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩としては、例えばカリウム塩、ナトリウム塩等が挙げられ、その中でも特にカリウム塩が好ましい。   Examples of the piperazine-N, N′-biscarbodithioate in the piperazine-N, N′-biscarbodithioate aqueous solution of the present invention include, for example, potassium salt, sodium salt, etc. Among them, potassium salt is particularly preferable. .

本発明のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液の製造方法は、水溶液中でピペラジン、ピペラジンに対して反応当量以上の二硫化炭素、アルカリ金属水酸化物を混合して反応するピペラジンカルボジチオ酸塩の製造方法において、反応時に疎水性溶媒を添加することを特徴とするピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液の製造方法である。   The method for producing an aqueous piperazine-N, N′-biscarbodithioate salt solution of the present invention comprises piperazine which reacts by mixing piperazine and piperazine with carbon disulfide and alkali metal hydroxide at a reaction equivalent or higher in the aqueous solution. In the method for producing a carbodithioate, a hydrophobic solvent is added during the reaction, which is a method for producing an aqueous piperazine-N, N′-biscarbodithioate.

本発明では反応時に疎水性溶媒を用いることにより、従来、反応後に留去が必要であった過剰の二硫化炭素（ここで、過剰の二硫化炭素とは、反応当量以上の二硫化炭素から反応当量の二硫化炭素を差し引いた二硫化炭素を表す。）を疎水性溶媒中に補足可能にし、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を主成分とするピペラジンカルボジチオ酸塩水溶液と二相分離させることで、必要な水溶液相のみを取り出すことが容易となる。また、過剰な二硫化炭素による不要な副反応を抑制することができる。さらに、過剰の二硫化炭素を補足した疎水性溶媒は再利用することができる。疎水性溶媒を再利用する場合、溶媒中にはすでに過剰の二硫化炭素が補足されているため、次の反応において過剰の二硫化炭素の使用を減らすことができる。   In the present invention, by using a hydrophobic solvent during the reaction, conventionally, an excess of carbon disulfide that had to be distilled off after the reaction (where excess carbon disulfide is reacted from carbon disulfide having a reaction equivalent or more). (Representing carbon disulfide minus an equivalent amount of carbon disulfide)) in a hydrophobic solvent, and an aqueous piperazine carbodithioate aqueous solution containing piperazine-N, N′-biscarbodithioate as a main component. By separating the phases, it becomes easy to take out only the necessary aqueous solution phase. In addition, unnecessary side reactions due to excess carbon disulfide can be suppressed. Furthermore, hydrophobic solvents supplemented with excess carbon disulfide can be reused. When the hydrophobic solvent is reused, the excess carbon disulfide can be reduced in the next reaction because the solvent is already supplemented with excess carbon disulfide.

本発明の製造方法で得られるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を主成分とするピペラジンカルボジチオ酸塩水溶液中にはピペラジン−Ｎ−カルボジチオ酸塩が含まれないため、１３Ｃ−ＮＭＲで測定した時には４７ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークが観測されず、１Ｈ−ＮＭＲで測定した時には２．８ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークが観測されない。 Since piperazine-carbodithioate aqueous solution mainly containing piperazine-N, N′-biscarbodithioate obtained by the production method of the present invention does not contain piperazine-N-carbodithioate, 13 C— When measured by NMR, no peak derived from piperazine-N-carbodithioate was observed around 47 ppm, and when measured by 1 H-NMR, a peak derived from piperazine-N-carbodithioate was observed near 2.8 ppm. Not.

本発明の製造方法では、反応時における二硫化炭素の使用量として、ピペラジンに対する二硫化炭素のモル比が２．００倍当量以上、３．００倍当量以下の範囲であることが好ましく、さらに２．０１倍当量以上、２．５倍当量以下、特に２．０５倍当量以上、２．５倍当量以下が好ましい。この範囲とすることによりピペラジン−Ｎ−カルボジチオ酸塩が生成することなく、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の生成率を低下させることなく、また過剰の二硫化炭素が多量となることなく、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の生産効率を低下させることがない。   In the production method of the present invention, the amount of carbon disulfide used in the reaction is preferably such that the molar ratio of carbon disulfide to piperazine is in the range of 2.00 times equivalent or more and 3.00 times equivalent or less. It is preferably 0.01 times equivalent or more and 2.5 times equivalent or less, particularly preferably 2.05 times equivalent or more and 2.5 times equivalent or less. By setting the amount within this range, piperazine-N-carbodithioate is not produced, the production rate of piperazine-N, N′-biscarbodithioate is not lowered, and excess carbon disulfide becomes large. In addition, the production efficiency of piperazine-N, N′-biscarbodithioate is not lowered.

本発明の製造方法では反応時におけるアルカリ金属水酸化物の使用量として、ピペラジンに対するアルカリ金属水酸化物のモル比が１．９５倍当量以上、２．０５倍当量以下が好ましく、特に１．９７倍当量以上、２．０２倍当量以下が好ましい。   In the production method of the present invention, the amount of the alkali metal hydroxide used during the reaction is preferably such that the molar ratio of the alkali metal hydroxide to piperazine is 1.95 times equivalent or more and 2.05 times equivalent or less, particularly 1.97. It is preferably a double equivalent or more and a 2.02 equivalent or less.

本発明の製造方法では、さらに反応終了後、疎水性溶媒を分離し得たピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液にアルカリ金属水酸化物を０．１〜３．０重量％、特に０．３〜１．５重量％添加することが好ましい。アルカリ金属水酸化物を過剰に添加することによって、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液をさらに安定化することが可能となる。   In the production method of the present invention, after completion of the reaction, 0.1 to 3.0% by weight of an alkali metal hydroxide is added to the piperazine-N, N′-biscarbodithioate aqueous solution obtained by separating the hydrophobic solvent. It is particularly preferable to add 0.3 to 1.5% by weight. By adding an excessive amount of alkali metal hydroxide, it is possible to further stabilize the piperazine-N, N′-biscarbodithioate aqueous solution.

本発明の製造方法で使用する疎水性溶媒としては、特に限定はなく、例えば、ペンタン、ヘキサン、ヘプタン等の炭化水素やベンゼン、トルエン、クロロベンゼン、ジクロロベンゼン、クロロホルム、ジエチルエーテル、酢酸エチル、塩化メチレン等を例示することができ、これらの溶媒の中でも特に水に対する溶解度が高い場合、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を主成分とするピペラジンカルボジチオ酸塩水溶液中に混入する疎水性溶媒の量が増加してしまうことから、水に対する溶解度が１重量％以下であるペンタン、ヘキサン、ヘプタン等の炭化水素、ベンゼン、トルエン、クロロベンゼン、ジクロロベンゼン、クロロホルム等が好ましく、特に０．１重量％以下であるペンタン、ヘキサン、ヘプタン等の炭化水素、トルエン、クロロベンゼン、ジクロロベンゼン等が好ましく、中でも比重が軽くピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液との比重差が大きいヘキサン、ヘプタン等の炭化水素が好ましい。また、これらの化合物の二種以上を混合して使用してもよい。   The hydrophobic solvent used in the production method of the present invention is not particularly limited, for example, hydrocarbons such as pentane, hexane, heptane, benzene, toluene, chlorobenzene, dichlorobenzene, chloroform, diethyl ether, ethyl acetate, methylene chloride. The hydrophobicity mixed in the piperazine carbodithioate aqueous solution mainly composed of piperazine-N, N′-biscarbodithioate when the solubility in water is particularly high among these solvents. Since the amount of the solvent increases, hydrocarbons such as pentane, hexane and heptane having a solubility in water of 1% by weight or less, benzene, toluene, chlorobenzene, dichlorobenzene, chloroform and the like are preferable, particularly 0.1% by weight. % Of hydrocarbons such as pentane, hexane, heptane, etc. Ene, chlorobenzene, dichlorobenzene and the like are preferable, among them the specific gravity is lighter piperazine -N, N'-bis carbonitrile specific gravity difference between the dithio acid salt aqueous solution is large hexane, hydrocarbons such as heptane preferred. Moreover, you may use it, mixing 2 or more types of these compounds.

本発明で用いる疎水性溶媒の使用量としては、過剰の二硫化炭素に対して１００〜１００００重量％が好ましく、特に２００〜２０００重量％が好ましい。この範囲とすることにより、二硫化炭素の補足効果が低下することがないため、二硫化炭素を留去する必要がなく又は不要な副反応を生じる可能性がなく；二硫化炭素を補足しすぎることがないため、ピペラジン−Ｎ−カルボジチオ酸塩が残存する可能性がなく、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩を主成分とするピペラジンカルボジチオ酸塩水溶液の生産効率が低下することもない。   As the usage-amount of the hydrophobic solvent used by this invention, 100-10000 weight% is preferable with respect to excess carbon disulfide, and 200-2000 weight% is especially preferable. By setting the amount within this range, the carbon disulfide capture effect does not decrease, so there is no need to distill off carbon disulfide or cause unnecessary side reactions; too much carbon disulfide is captured. Therefore, there is no possibility that piperazine-N-carbodithioate remains, and the production efficiency of the piperazine carbodithioate aqueous solution mainly composed of piperazine-N, N′-biscarbodithioate is reduced. Nor.

本発明で用いる疎水性溶媒の添加方法としては、特に限定はなく、最初から全量原料と共に添加する方法、反応の途中で添加する方法、予め二硫化炭素と混合し添加する方法等が例示できる。   The method for adding the hydrophobic solvent used in the present invention is not particularly limited, and examples thereof include a method of adding the whole amount together with the raw materials, a method of adding in the middle of the reaction, a method of mixing with carbon disulfide in advance and the like.

本発明の製造方法で用いるアルカリ金属水酸化物としては、水酸化カリウム及び／又は水酸化ナトリウムを用いることが好ましい。   As the alkali metal hydroxide used in the production method of the present invention, potassium hydroxide and / or sodium hydroxide is preferably used.

本発明の製造方法では、ピペラジンカルボジチオ酸塩水溶液中にピペラジン−Ｎ−カルボジチオ酸塩が含まれないものを製造することができる。ピペラジン−Ｎ−カルボジチオ酸塩がないことにより、特に重金属固定可能がより高くなり、かつより安定な性能が期待できる。   In the production method of the present invention, a piperazine-carbodithioate aqueous solution containing no piperazine-N-carbodithioate can be produced. Due to the absence of piperazine-N-carbodithioate, it is possible to fix a heavy metal in particular, and a more stable performance can be expected.

本発明の製造方法において、反応時における原料混合方法は特に限定はなく、本発明の原料組成比を維持しながら、連続添加、或いは分割添加する方法が例示でき、特にピペラジン、疎水性溶媒を含む溶液に、二硫化炭素、アルカリ金属水酸化物を交互に２分割以上に分割し添加する方法；二硫化炭素、疎水性溶媒を含む溶液に、ピペラジン、アルカリ金属水酸化物を交互に２分割以上に分割し添加する方法等が好ましく、ピペラジン、疎水性溶媒を含む溶液に、二硫化炭素、アルカリ金属水酸化物の順で交互に２分割以上に分割し添加する方法；二硫化炭素、疎水性溶媒を含む溶液に、ピペラジン、アルカリ金属水酸化物の順で交互に２分割以上に分割し添加する方法等がさらに好ましい。   In the production method of the present invention, the raw material mixing method at the time of reaction is not particularly limited, and examples thereof include a method of continuous addition or divided addition while maintaining the raw material composition ratio of the present invention, particularly including piperazine and a hydrophobic solvent. A method in which carbon disulfide and alkali metal hydroxide are alternately divided into two or more portions and added to the solution; piperazine and alkali metal hydroxide are alternately divided into two or more portions in a solution containing carbon disulfide and a hydrophobic solvent. The method is preferably divided and added to a solution containing piperazine and a hydrophobic solvent, in which carbon disulfide and alkali metal hydroxide are alternately divided into two or more in this order; carbon disulfide and hydrophobic. A method of adding a solution containing a solvent in two or more portions alternately in the order of piperazine and alkali metal hydroxide is more preferable.

本発明の製造方法において、反応時、及び熟成時の温度は特に限定されるものではなく、室温（２０℃）〜４５℃が好ましく、特に３０℃〜４５℃で行うことが好ましい。   In the production method of the present invention, the temperature at the time of reaction and aging is not particularly limited, and is preferably room temperature (20 ° C.) to 45 ° C., particularly preferably 30 ° C. to 45 ° C.

本発明におけるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩の濃度は特に限定はなく、重金属処理剤として適宜使用可能な濃度とすることができ、２０〜５０重量％が好ましく、特に３０〜４５重量％が好ましい。   The concentration of piperazine-N, N′-biscarbodithioate in the present invention is not particularly limited, and may be a concentration that can be appropriately used as a heavy metal treating agent, preferably 20 to 50% by weight, particularly 30 to 45%. % By weight is preferred.

本発明では、さらにピペラジンを添加することにより、より長期的な保存に対する処理能力の低下を防止することができる。ピペラジンの添加量としては、特に限定はなく、ピペラジンのカルボジチオ酸塩が安定であることから、０．１〜２重量％が好ましく、特に０．２〜１重量％が好ましい。   In the present invention, by further adding piperazine, it is possible to prevent a decrease in processing capacity for longer-term storage. The amount of piperazine added is not particularly limited, and is preferably 0.1 to 2% by weight, particularly preferably 0.2 to 1% by weight because the carbodithioate salt of piperazine is stable.

本発明の製造方法では、不活性ガスによる過剰な二硫化炭素の留去処理や固形のピペラジンカルボジチオ酸の析出中での反応制御をすることなくピペラジン−Ｎ−カルボジチオ酸塩を含まないピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩からなる重金属処理剤を製造することができる。   In the production method of the present invention, piperazine containing no piperazine-N-carbodithioate without controlling the reaction during the distillation of excess carbon disulfide with an inert gas or the precipitation of solid piperazine carbodithioic acid. A heavy metal treating agent comprising N, N′-biscarbodithioate can be produced.

実施例６で得られた水溶液の１３Ｃ−ＮＭＲスペクトルである。It is a 13 C-NMR spectrum of the aqueous solution obtained in Example 6. 実施例６で得られた水溶液の１Ｈ−ＮＭＲスペクトルである。2 is a 1 H-NMR spectrum of an aqueous solution obtained in Example 6. 比較例１で得られた水溶液の１３Ｃ−ＮＭＲスペクトルである。3 is a 13 C-NMR spectrum of an aqueous solution obtained in Comparative Example 1. 比較例１で得られた水溶液の１Ｈ−ＮＭＲスペクトルである。2 is a 1 H-NMR spectrum of an aqueous solution obtained in Comparative Example 1.

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。 なお、実施例におけるＮＭＲ測定は、ＶＡＲＩＡＮ製のＧｅｍｉｎｉ−２００を使用し、溶媒として重水、標準物質として３−トリメチルシリルプロピオン酸ナトリウム−２，２，３，３−ｄ４を用い行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Incidentally, NMR measurement in the examples, using a Gemini-200 manufactured by VARIAN, was carried out heavy water, the 3-tri sodium propionate-2,2,3,3-d 4 as a standard substance used as the solvent.

実施例１
攪拌装置、温度計、コンデンサー、滴下ロートを備えた１Ｌ４口フラスコに水１８９．４ｇ、無水ピペラジン５６．０ｇ（０．６５ｍｏｌ）、ヘキサン７５．０ｇを一括で仕込
み、３５℃にてピペラジンを溶解させた。４０℃、攪拌下で、二硫化炭素１２３．８ｇ（１．６３ｍｏｌ）、４８．５％水酸化カリウム水溶液１５０．４ｇ（１．３０ｍｏｌ）を４分割し、６時間かけて滴下（反応）し（ピペラジンに対し、アルカリ金属水酸化物のモル比２．００倍当量・二硫化炭素のモル比２．５０倍当量。疎水性溶媒：過剰の二硫化炭素に対し３０２重量％。水溶液中のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩濃度は４０．９重量％）１５分熟成後、ヘキサン相と分離した黄色透明の液体を得た。得られた黄色液体を分液漏斗にて分離、採取し、１５分間攪拌した後、４８．５％水酸化カリウム水溶液を５．２ｇ添加し、ろ過を行った。 Example 1
A 1L 4-neck flask equipped with a stirrer, thermometer, condenser, and dropping funnel was charged with 189.4 g of water, 56.0 g (0.65 mol) of anhydrous piperazine, and 75.0 g of hexane all at once, and the piperazine was dissolved at 35 ° C. It was. Under stirring at 40 ° C., 123.8 g (1.63 mol) of carbon disulfide and 150.4 g (1.30 mol) of 48.5% aqueous potassium hydroxide solution were divided into four portions and dropped (reacted) over 6 hours ( Molar ratio of alkali metal hydroxide to 2.00 times equivalent and carbon disulfide to 2.50 times equivalent to piperazine Hydrophobic solvent: 302 wt% with respect to excess carbon disulfide. N, N′-biscarbodithioate concentration was 40.9 wt%) After aging for 15 minutes, a yellow transparent liquid separated from the hexane phase was obtained. The obtained yellow liquid was separated and collected with a separatory funnel and stirred for 15 minutes, and then 5.2 g of 48.5% potassium hydroxide aqueous solution was added, followed by filtration.

得られた水溶液を１３Ｃ−ＮＭＲで測定した結果、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。 As a result of measuring the obtained aqueous solution by 13 C-NMR, only peaks derived from the main component piperazine-N, N′-biscarbodithioate were observed at around 53 ppm and around 210 ppm, and around 47 ppm and around 55 ppm. No peak derived from piperazine-N-carbodithioate was observed.

実施例２
ヘキサン７５．０ｇをｐ−ジクロロベンゼン７５．０ｇとした以外は実施例１と同様の操作を行った。得られた液体は黄色透明であり、１３Ｃ−ＮＭＲで測定した結果、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。 Example 2
The same operation as in Example 1 was performed except that 75.0 g of hexane was changed to 75.0 g of p-dichlorobenzene. The obtained liquid is yellow and transparent, and as a result of measurement by 13 C-NMR, only peaks derived from piperazine-N, N′-biscarbodithioate as a main component are observed around 53 ppm and 210 ppm, Peaks derived from piperazine-N-carbodithioate were not observed at around 47 ppm and around 55 ppm.

実施例３
ヘキサン７５．０ｇをヘプタン７５．０ｇとし、二硫化炭素を１０６．６ｇ（１．４０ｍｏｌ）とした以外は実施例１と同様の操作を行った（ピペラジンに対し、アルカリ金属水酸化物のモル比２．００倍当量・二硫化炭素のモル比２．１５倍当量。疎水性溶媒：過剰の二硫化炭素に対し９８７重量％。水溶液中のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩濃度は４０．９重量％）。得られた液体は黄色透明であり、１３Ｃ−ＮＭＲで測定した結果、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。さらに１Ｈ−ＮＭＲで測定した結果、２．８ｐｐｍ付近にピペラジン−Ｎ−ビスカルボジチオ酸塩に由来するピークは観測されなかった。 Example 3
The same operation as in Example 1 was performed except that 75.0 g of hexane was changed to 75.0 g of heptane and 106.6 g (1.40 mol) of carbon disulfide (molar ratio of alkali metal hydroxide to piperazine). 2.00 times equivalent / molar ratio of carbon disulfide 2.15 times equivalent Hydrophobic solvent: 987 wt% with respect to excess carbon disulfide The concentration of piperazine-N, N′-biscarbodithioate in aqueous solution is 40.9% by weight). The obtained liquid is yellow and transparent, and as a result of measurement by 13 C-NMR, only peaks derived from piperazine-N, N′-biscarbodithioate as a main component are observed around 53 ppm and 210 ppm, Peaks derived from piperazine-N-carbodithioate were not observed at around 47 ppm and around 55 ppm. Furthermore, as a result of measurement by 1 H-NMR, no peak derived from piperazine-N-biscarbodithioate was observed in the vicinity of 2.8 ppm.

実施例４
実施例１で分離したヘキサンを用い、二硫化炭素の添加量を１０４．０ｇ（１．３７ｍｏｌ）とした以外は実施例１と同様の操作を行った。得られた液体は黄色透明であり、１３Ｃ−ＮＭＲで測定した結果、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。 Example 4
The same operation as in Example 1 was performed except that the hexane separated in Example 1 was used and the amount of carbon disulfide added was changed to 104.0 g (1.37 mol). The obtained liquid is yellow and transparent, and as a result of measurement by 13 C-NMR, only peaks derived from piperazine-N, N′-biscarbodithioate as a main component are observed around 53 ppm and 210 ppm, Peaks derived from piperazine-N-carbodithioate were not observed at around 47 ppm and around 55 ppm.

実施例５
攪拌装置、コンデンサー、滴下ロートを二つ備えた５００ｍＬ４口フラスコに水５８．８ｇ、二硫化炭素１０１．５ｇ（１．３３ｍｏｌ）、ヘプタン２５．０ｇを一括で仕込み、３０％ピペラジン水溶液１８６．６ｇ（０．６５ｍｏｌ）、４８．５％水酸化カリウム水溶液１５０．４ｇ（１．３０ｍｏｌ）を３分割し、３０％ピペラジン水溶液、４８．５％水酸化カリウム水溶液の順で交互に滴下する以外は実施例１と同様の操作を行った（ピペラジンに対し、アルカリ金属水酸化物のモル比２．００倍当量・二硫化炭素のモル比２．０５倍当量。疎水性溶媒：過剰の二硫化炭素に対し１０００重量％。水溶液中のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩濃度は４０．９重量％）。得られた液体は黄色透明であり、１３Ｃ−ＮＭＲで測定した結果、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。さらに１Ｈ−ＮＭＲで測定した結果、２．８ｐｐｍ付近にピペラジン−Ｎ−ビスカルボジチオ酸塩に由来するピークは観測されなかった。 Example 5
A 500 mL four-necked flask equipped with a stirrer, a condenser, and two dropping funnels was charged with 58.8 g of water, 101.5 g (1.33 mol) of carbon disulfide, and 25.0 g of heptane all at once, and 186.6 g of 30% piperazine aqueous solution ( 0.65 mol), 48.5% potassium hydroxide aqueous solution 150.4 g (1.30 mol) was divided into three parts, and 30% piperazine aqueous solution and 48.5% potassium hydroxide aqueous solution were dropped alternately in this order. (Mole ratio of alkali metal hydroxide to 2.00 times equivalent and carbon disulfide to 2.05 times equivalent to piperazine, and 2.05 times equivalent of carbon disulfide. Hydrophobic solvent: to excess carbon disulfide 1000% by weight, piperazine-N, N′-biscarbodithioate concentration in aqueous solution is 40.9% by weight). The obtained liquid is yellow and transparent, and as a result of measurement by 13 C-NMR, only peaks derived from piperazine-N, N′-biscarbodithioate as a main component are observed around 53 ppm and 210 ppm, Peaks derived from piperazine-N-carbodithioate were not observed at around 47 ppm and around 55 ppm. Furthermore, as a result of measurement by 1 H-NMR, no peak derived from piperazine-N-biscarbodithioate was observed in the vicinity of 2.8 ppm.

実施例６
攪拌装置、温度計、コンデンサー、滴下ロートを備えた５００ｍＬ４口フラスコに水１８９．４ｇ、無水ピペラジン５６．０ｇ（０．６５ｍｏｌ）、ヘプタン５．０ｇを一括で仕込み、３５℃にてピペラジンを溶解させた。４０℃、攪拌下で、二硫化炭素９９．５ｇ（１．３１ｍｏｌ）、４８．５％水酸化カリウム水溶液１４８．９ｇ（１．２９ｍｏｌ）を４分割し、６時間かけて滴下（反応）し（ピペラジンに対し、アルカリ金属水酸化物のモル比１．９８倍当量・二硫化炭素のモル比２．０１倍当量。疎水性溶媒：過剰の二硫化炭素に対し１０１０重量％。水溶液中のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩濃度は４０．９重量％）１５分熟成後、ヘプタン相と分離した黄色透明の液体を得た。得られた黄色液体を分液漏斗にて分離、採取し、１５分間攪拌した後、４８．５％水酸化カリウム水溶液を６．７ｇ添加し、ろ過を行った。 Example 6
A 500 mL four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel was charged with 189.4 g of water, 56.0 g (0.65 mol) of anhydrous piperazine and 5.0 g of heptane all at once, and piperazine was dissolved at 35 ° C. It was. Under stirring at 40 ° C., 99.5 g (1.31 mol) of carbon disulfide and 148.9 g (1.29 mol) of 48.5% aqueous potassium hydroxide solution were divided into 4 portions and dropped (reacted) over 6 hours ( The molar ratio of alkali metal hydroxide to piperazine is 1.98 times equivalent and the molar ratio of carbon disulfide is 2.01 times equivalent.Hydrophobic solvent: 1010% by weight with respect to excess carbon disulfide. N, N′-biscarbodithioate concentration was 40.9 wt%) After aging for 15 minutes, a yellow transparent liquid separated from the heptane phase was obtained. The obtained yellow liquid was separated and collected with a separatory funnel, stirred for 15 minutes, and then added with 6.7 g of 48.5% aqueous potassium hydroxide solution and filtered.

得られた水溶液を１３Ｃ−ＮＭＲで測定した結果を図１に示す。５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピークのみが観測され、４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークは観測されなかった。さらに１Ｈ−ＮＭＲで測定した結果を図２に示す。２．８ｐｐｍ付近にピペラジン−Ｎ−ビスカルボジチオ酸塩に由来するピークは観測されなかった。 The result of having measured the obtained aqueous solution by 13 C-NMR is shown in FIG. Only peaks derived from the main component piperazine-N, N′-biscarbodithioate are observed around 53 ppm and 210 ppm, and peaks derived from piperazine-N-carbodithioate are observed around 47 ppm and 55 ppm. Was not. Furthermore, the result measured by 1 H-NMR is shown in FIG. No peak derived from piperazine-N-biscarbodithioate was observed around 2.8 ppm.

比較例１
二硫化炭素の添加量を９８．０ｇ（１．２９ｍｏｌ）（ピペラジンに対し、二硫化炭素のモル比１．９８倍当量）とした以外は実施例１と同様の操作を行った。得られた液体は黄色透明であり、１３Ｃ−ＮＭＲで測定した結果（図３）、５３ｐｐｍ付近及び２１０ｐｐｍ付近に主成分であるピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩に由来するピーク以外に４７ｐｐｍ付近及び５５ｐｐｍ付近にピペラジン−Ｎ−カルボジチオ酸塩に由来するピークが観測された。さらに１Ｈ−ＮＭＲで測定した結果（図４）、２．８ｐｐｍ付近にピペラジン−Ｎ−ビスカルボジチオ酸塩に由来するピークが観測された。 Comparative Example 1
The same operation as in Example 1 was carried out except that the amount of carbon disulfide added was 98.0 g (1.29 mol) (molar ratio of carbon disulfide to piperazine was 1.98 times equivalent). The obtained liquid is yellow and transparent, and the result of measurement by 13 C-NMR (FIG. 3), other than the peak derived from piperazine-N, N′-biscarbodithioate as a main component at around 53 ppm and around 210 ppm In addition, peaks derived from piperazine-N-carbodithioate were observed at around 47 ppm and around 55 ppm. Furthermore, as a result of measurement by 1 H-NMR (FIG. 4), a peak derived from piperazine-N-biscarbodithioate was observed in the vicinity of 2.8 ppm.

反応当量以上（ピペラジンに対し、二硫化炭素のモル比２．００倍当量）の二硫化炭素を用いなかったことから、ピペラジン−Ｎ−カルボジチオ酸塩を含むものであった。   Since carbon disulfide having a reaction equivalent or more (molar ratio of carbon disulfide to 2.00 times the molar ratio of piperazine) was not used, piperazine-N-carbodithioate was included.

比較例２
ヘキサンを使用しない以外は実施例１と同様の操作を行った。疎水性溶媒を用いなかったことから、熟成終了後、未反応の二硫化炭素が目視確認され、不活性ガスによる留去が必要であった。 Comparative Example 2
The same operation as in Example 1 was performed except that hexane was not used. Since a hydrophobic solvent was not used, unreacted carbon disulfide was visually confirmed after completion of ripening, and distillation with an inert gas was necessary.

本発明の製造法で得られたピペラジンのカルボジチオ酸塩の水溶液は、土壌、廃水、焼却灰、飛灰等の重金属含有物中の重金属処理に用いられる。   The aqueous solution of piperazine carbodithioate obtained by the production method of the present invention is used for heavy metal treatment in heavy metal-containing materials such as soil, wastewater, incineration ash, and fly ash.

Claims (9)

水溶液中でピペラジン、ピペラジンに対して反応当量以上の二硫化炭素、アルカリ金属水酸化物を混合して反応するピペラジンカルボジチオ酸塩の製造方法において、反応時に疎水性溶媒を添加することを特徴とするピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液の製造方法。   In a method for producing piperazine carbodithioate that reacts by mixing piperazine, piperazine with a reaction equivalent of carbon disulfide or alkali metal hydroxide in an aqueous solution, a hydrophobic solvent is added during the reaction. A method for producing a piperazine-N, N′-biscarbodithioate aqueous solution. ピペラジンに対する二硫化炭素のモル比が２．００倍当量以上、３．００倍当量以下であることを特徴とする請求項１に記載の製造方法。   The manufacturing method according to claim 1, wherein the molar ratio of carbon disulfide to piperazine is 2.00 times equivalent or more and 3.00 times equivalent or less. ピペラジンに対するアルカリ金属水酸化物のモル比が１．９５倍当量以上、２．０５倍当量以下であることを特徴とする請求項１又は２に記載の製造方法。   The manufacturing method according to claim 1 or 2, wherein the molar ratio of the alkali metal hydroxide to piperazine is 1.95 times equivalent or more and 2.05 times equivalent or less. 疎水性溶媒の水に対する溶解度が１重量％以下であることを特徴とする請求項１〜３のいずれかに記載の製造方法。   The manufacturing method according to any one of claims 1 to 3, wherein the solubility of the hydrophobic solvent in water is 1% by weight or less. 疎水性溶媒の添加量が過剰の二硫化炭素に対して１００〜１００００重量％であることを特徴とする請求項１〜４のいずれかに記載の製造方法。   The production method according to any one of claims 1 to 4, wherein the addition amount of the hydrophobic solvent is 100 to 10,000% by weight with respect to excess carbon disulfide. アルカリ金属水酸化物が水酸化カリウム及び／又は水酸化ナトリウムであることを特徴とする請求項１〜５のいずれかに記載の製造方法。 The production method according to claim 1, wherein the alkali metal hydroxide is potassium hydroxide and / or sodium hydroxide. 反応終了後、疎水性溶媒を分離したピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩からなるピペラジンカルボジチオ酸塩水溶液にさらにアルカリ金属水酸化物を混合することを特徴とする請求項１〜６のいずれかに記載の製造方法。   7. An alkali metal hydroxide is further mixed with a piperazine carbodithioate aqueous solution composed of piperazine-N, N′-biscarbodithioate from which a hydrophobic solvent has been separated after completion of the reaction. The manufacturing method in any one of. ピペラジン−Ｎ−カルボジチオ酸塩を含まないことを特徴とするピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液。   Piperazine-N, N'-biscarbodithioate aqueous solution characterized by not containing piperazine-N-carbodithioate. ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩がカリウム塩であることを特徴とする請求項８に記載のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸塩水溶液。   The piperazine-N, N'-biscarbodithioate aqueous solution according to claim 8, wherein the piperazine-N, N'-biscarbodithioate is a potassium salt.
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