JP2012167056A - Method of producing carbodithioate of solid amine - Google Patents
Method of producing carbodithioate of solid amine Download PDFInfo
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本発明は、重金属処理剤として有用なアミンのカルボジチオ酸塩を固体状で効率的に得る製造方法を提供するものである。 The present invention provides a production method for efficiently obtaining a carbodithioate salt of an amine useful as a heavy metal treating agent in a solid state.
アミンのカルボジチオ酸塩は飛灰、土壌、廃水等の重金属の固定化処理剤として用いられている。重金属処理剤としてのアミンのカルボジチオ酸塩は通常は２０〜６０重量％程度の水溶液が用いられているが、昨今、固体（粉末状）の重金属処理剤の要求が高まっている。 Amine carbodithioate is used as an immobilizing agent for heavy metals such as fly ash, soil and wastewater. As the carbodithioate of amine as a heavy metal treating agent, an aqueous solution of about 20 to 60% by weight is usually used, but recently, the demand for a solid (powdered) heavy metal treating agent is increasing.
これまで、アミンのカルボジチオ酸塩を含む固体状の重金属処理剤としては例えば、カルボジチオ酸塩３〜３０重量部に対してアルカリ水酸化物やアルカリ土類水酸化物を１００重量部用いる重金属処理剤（例えば特許文献１参照）、ケイ酸カルシウムを担体とした重金属処理剤（例えば特許文献２参照）、不溶性である遷移金属のカルボジチオ酸塩（例えば特許文献３参照）、カルボジチオ酸塩溶液を高温で噴霧乾燥したもの（例えば特許文献４参照）、デンプンにキレート剤を含ませて粉末状にしたもの（例えば特許文献５参照）等が報告されている。 So far, as a solid heavy metal treating agent containing an amine carbodithioate, for example, a heavy metal treating agent using 100 parts by weight of alkali hydroxide or alkaline earth hydroxide with respect to 3 to 30 parts by weight of carbodithioate (For example, refer to Patent Document 1), heavy metal treating agent using calcium silicate as a carrier (for example, refer to Patent Document 2), insoluble transition metal carbodithioate (for example, refer to Patent Document 3), carbodithioate solution at high temperature A spray-dried product (see, for example, Patent Document 4), a starch powder containing a chelating agent (see, for example, Patent Document 5), and the like have been reported.
しかし、従来の濃縮や噴霧乾燥によって固体状の重金属処理剤を得る方法では、水溶液の蒸発に多大なエネルギーが必要であり、経済的でなかった。 However, in the conventional method of obtaining a solid heavy metal treating agent by concentration or spray drying, a large amount of energy is required for evaporation of the aqueous solution, which is not economical.
これに対して、固体状のピペラジンのカルボジチオ酸塩（例えば特許文献６，７参照）、固体状のジエチルアミンのカルボジチオ酸塩（例えば特許文献８参照）をアミンのカルボジチオ酸塩の飽和水溶液を循環することにより効率的に得る方法が提案されている。しかしながら、これらの方法ではピペラジンのカルボジチオ酸ナトリウム塩やジエチルアミンのカルボジチオ酸ナトリウム塩のような水への溶解度が約２０重量％と比較的低いアミンのカルボジチオ酸塩では従来の方法に比べて効率的ではあったが、アミンのカルボジチオ酸カリウム塩のような水への溶解度が３０重量％を超えるカルボジチオ酸塩の場合、収率が低くなり必ずしも効率的とはいえなかった。 On the other hand, solid piperazine carbodithioate (see, for example, Patent Documents 6 and 7) and solid diethylamine carbodithioate (for example, see Patent Document 8) are circulated in a saturated aqueous solution of amine carbodithioate. There has been proposed a method for efficiently obtaining this. However, in these methods, amine carbodithioate having a relatively low solubility in water, such as piperazine sodium carbodithioate and diethylamine sodium carbodithioate, is less efficient than the conventional method. However, in the case of carbodithioate having a solubility in water of more than 30% by weight, such as amine carbodithioate potassium salt, the yield was low and it was not necessarily efficient.
本発明の目的は、重金属処理剤として有用なアミンのカルボジチオ酸塩、特に水への溶解度が３０重量％を超えるアミンのカルボジチオ酸塩を固体状で効率的に得る製造方法を提供することにある。 An object of the present invention is to provide a production method for efficiently obtaining a carbodithioate of an amine useful as a heavy metal treating agent, particularly an amine carbodithioate having a solubility in water of more than 30% by weight in a solid state. .
本発明者等は、重金属処理剤として有用なアミンのカルボジチオ酸塩、特に溶解度が３０重量％を超えるアミンのカルボジチオ酸塩を固体状で効率的に得る製造方法について鋭意検討を重ねた結果、水溶液中でアミン、二硫化炭素、金属水酸化物を混合して反応するアミンのカルボジチオ酸塩水溶液の製造方法において、水溶性の有機溶媒を共存させることにより、効率的に固体状のアミンのカルボジチオ酸塩を得ることが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。 As a result of intensive studies on a production method for efficiently obtaining a carbodithioate of an amine useful as a heavy metal treating agent, particularly an amine carbodithioate having a solubility of more than 30% by weight as a solid, In a method for producing an aqueous solution of an amine carbodithioate that reacts by mixing an amine, carbon disulfide, and a metal hydroxide, a solid amine carbodithioic acid can be efficiently produced by coexisting a water-soluble organic solvent. The present inventors have found that a salt can be obtained and have completed the present invention.
以下に本発明の固体状のアミンのカルボジチオ酸塩の製造方法について説明する。 The method for producing a solid amine carbodithioate according to the present invention will be described below.
本発明の固体状のアミンのカルボジチオ酸塩の製造方法は、水溶液中でアミン、二硫化炭素、金属水酸化物を混合して反応するアミンのカルボジチオ酸塩水溶液の製造方法において水溶性の有機溶媒を共存させることにより、固体状のアミンのカルボジチオ酸塩を効率的に析出させ、分離することで固体状のアミンのカルボジチオ酸塩を得ることができる。 The method for producing a solid amine carbodithioate according to the present invention is a method for producing an amine carbodithioate aqueous solution in which an amine, carbon disulfide, and a metal hydroxide are mixed and reacted in an aqueous solution. By coexisting, a solid amine carbodithioate can be efficiently precipitated and separated to obtain a solid amine carbodithioate.
本発明の製造方法で使用するアミンとしては特に限定はなく、例えばエチレンジアミン、ジエチレントリアミン等のポリエチレンポリアミン；ジメチルアミン、ジエチルアミン、ジブチルアミン等のジアルキルアミン；モノメチルアミン、モノエチルアミン等のモノアルキルアミン；エタノールアミン等のアルカノールアミン等；ピペラジン、Ｎ−アミノエチルピペラジン、ピロリジン等の環状アミン等を挙げることができる。これらの中でもアミンのカルボジチオ酸塩の結晶性が高く、分離が容易であることからジメチルアミン、ジエチルアミン、ピペラジン、Ｎ−アミノエチルピペラジン、ピロリジン等が好ましく、さらに重金属処理剤として実用的なジエチルアミン、ピペラジン、Ｎ−アミノエチルピペラジン等が好ましく、安定性が高いピペラジンが特に好ましい。 The amine used in the production method of the present invention is not particularly limited. For example, polyethylene polyamines such as ethylenediamine and diethylenetriamine; dialkylamines such as dimethylamine, diethylamine and dibutylamine; monoalkylamines such as monomethylamine and monoethylamine; ethanolamine Examples thereof include cyclic amines such as piperazine, N-aminoethylpiperazine, and pyrrolidine. Among these, dimethylamine, diethylamine, piperazine, N-aminoethylpiperazine, pyrrolidine and the like are preferable because of high crystallinity of amine carbodithioate and easy separation. Diethylamine and piperazine practical as heavy metal treating agents are also preferred. N-aminoethylpiperazine and the like are preferable, and piperazine having high stability is particularly preferable.
本発明の製造方法で使用する金属水酸化物としては特に限定はなく、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；マグネシウム、カルシウム等のアルカリ土類金属水酸化物等が挙げられる。中でもコスト面で安価な水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム等が好ましく、特に水酸化ナトリウム、水酸化カリウムが好ましい。 The metal hydroxide used in the production method of the present invention is not particularly limited. For example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium and calcium Thing etc. are mentioned. Of these, inexpensive sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like are preferable, and sodium hydroxide and potassium hydroxide are particularly preferable.
本発明の製造方法で使用する水溶性の有機溶媒としては、例えば、酸素含有化合物、窒素含有化合物、硫黄含有化合物等が挙げられ、特に酸素含有化合物が好ましく、該酸素含有化合物としては、例えばメタノール、エタノール、プロパノール等のアルコール類；エチレングリコール、プロピレングリコール、トリメチレングリコール、ブタンジオール、ペンタンジオール、ヘキシレングリコール、シクロヘキサンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、グリセリン等の多価アルコール類；ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、ジアセトンアルコール、メチルエチルケトン等のケトン類；アセトアルデヒド等のアルデヒド類等が挙げられ、コストの面でメタノール、エタノール、アセトン等が好ましい。 Examples of the water-soluble organic solvent used in the production method of the present invention include an oxygen-containing compound, a nitrogen-containing compound, a sulfur-containing compound, and the like. Particularly, an oxygen-containing compound is preferable, and the oxygen-containing compound is, for example, methanol. Alcohols such as ethanol and propanol; polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylene glycol, butanediol, pentanediol, hexylene glycol, cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, and glycerin; Ethers such as dioxane and tetrahydrofuran; ketones such as acetone, diacetone alcohol and methyl ethyl ketone; aldehydes such as acetaldehyde, etc., and methanol in terms of cost, Ethanol, acetone, etc. are preferable.
本発明の製造方法で使用する水溶性の有機溶媒の量としては、得られる固体状のアミンのカルボジチオ酸塩の量及び反応過程でのハンドリングの観点から、使用する水に対して重量比で１：０．５〜１：１０であることが好ましく、特に１：１〜１：３であることが好ましい。水溶性の有機溶媒を使用することにより、アミンのカルボジチオ酸塩の析出が促進され、効率的に固体状のアミンのカルボジチオ酸塩を得ることができる。 The amount of the water-soluble organic solvent used in the production method of the present invention is 1 by weight with respect to the water to be used from the viewpoint of the amount of carbodithioate of solid amine obtained and handling in the reaction process. : 0.5 to 1:10 is preferable, and 1: 1 to 1: 3 is particularly preferable. By using a water-soluble organic solvent, precipitation of amine carbodithioate is promoted, and a solid amine carbodithioate can be efficiently obtained.
本発明の製造方法における水溶性の有機溶媒の添加方法としては特に限定はなく、最初にアミンと水と水溶性の有機溶媒を溶解させる方法；アミンと水を溶解させた後、二硫化炭素、金属水酸化物を添加し反応終了後に水溶性の有機溶媒を添加する方法；二硫化炭素、金属水酸化物、水溶性の有機溶媒をと同時に添加する方法等が例示でき、特に最初にアミンと水と水溶性の有機溶媒を溶解させる方法が反応時のハンドリングが良好であることから好ましい。 The method for adding a water-soluble organic solvent in the production method of the present invention is not particularly limited. First, a method in which an amine, water, and a water-soluble organic solvent are dissolved; after the amine and water are dissolved, carbon disulfide; Examples include a method of adding a metal hydroxide and adding a water-soluble organic solvent after completion of the reaction; a method of simultaneously adding carbon disulfide, a metal hydroxide, a water-soluble organic solvent, etc. A method of dissolving water and a water-soluble organic solvent is preferable because of good handling during the reaction.
本発明の製造方法における水溶性の有機溶媒以外の原料の添加方法としては、特に限定はなく、分割添加、連続添加する方法等が例示でき、水にアミンを溶解させた後、二硫化炭素、金属水酸化物の順で交互に分割添加する方法又は時間差をつけて同時に添加する方法が好ましく、特に２分割以上に分割して交互に添加する方法が好ましい。 The addition method of the raw materials other than the water-soluble organic solvent in the production method of the present invention is not particularly limited, and examples thereof include divided addition, a continuous addition method, and the like. After dissolving the amine in water, carbon disulfide, A method in which the metal hydroxides are alternately added in the order of the metal hydroxide or a method in which they are added simultaneously with a time difference is preferable, and a method in which the metal hydroxides are added in two or more divided portions is particularly preferable.
本発明の製造方法における水溶性の有機溶媒以外の原料の量としては、特に限定はなく、二硫化炭素はアミンの二硫化炭素と反応するアミノ基に対して０．９〜１．２倍当量が好ましく、特に０．９５〜１．１倍当量が好ましく、金属水酸化物はアミンの二硫化炭素と反応するアミノ基に対して０．９５〜１．２倍当量が好ましく、特に０．９７〜１．１倍当量が好ましい。 The amount of the raw material other than the water-soluble organic solvent in the production method of the present invention is not particularly limited, and carbon disulfide is 0.9 to 1.2 times equivalent to the amino group that reacts with carbon disulfide of the amine. In particular, 0.95-1.1 times equivalent is preferred, and the metal hydroxide is preferably 0.95-1.2 times equivalent to the amino group reacting with carbon disulfide of the amine, especially 0.97. -1.1 times equivalent is preferable.
本発明の製造方法では反応により生成するアミンのカルボジチオ酸塩の濃度は特に限定はなく、得られる固体状のアミンのカルボジチオ酸カリウム塩の量及びハンドリングの観点から、１０〜６０重量％とすることが好ましく、特に３０〜５０重量％とすることが好ましい。 In the production method of the present invention, the concentration of the amine carbodithioate formed by the reaction is not particularly limited, and is 10 to 60% by weight from the viewpoint of the amount and handling of the solid amine carbodithioate potassium salt. Is preferable, and it is particularly preferably 30 to 50% by weight.
本発明の製造方法において得られる固体状のアミンのカルボジチオ酸塩の分離方法には固体と液体を分離できれば特に限定はなく、例えば、遠心分離、フィルタープレス、重力ろ過、真空ろ過、減圧ろ過等を例示することができる。また、得られた固体状のアミンのカルボジチオ酸塩については、必要に応じ付着している水や水溶性の有機溶媒を除去する乾燥を行い、その乾燥方法としては特に限定はなく、例えば、真空乾燥、熱乾燥、流動乾燥等を例示することができる。 The solid amine carbodithioate separation method obtained in the production method of the present invention is not particularly limited as long as the solid and the liquid can be separated. For example, centrifugation, filter press, gravity filtration, vacuum filtration, vacuum filtration, etc. It can be illustrated. In addition, the obtained solid amine carbodithioate is subjected to drying to remove the adhering water and water-soluble organic solvent as necessary, and the drying method is not particularly limited, for example, vacuum Examples thereof include drying, heat drying, and fluid drying.
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はなく、２０〜４５℃が好ましく、特に２５〜４０℃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, preferably 20 to 45 ° C, particularly preferably 25 to 40 ° C.
本発明の製造方法はアミンのカルボジチオ酸塩であれば、特に限定なく、従来の方法に比べて効率的に固体状のアミンのカルボジチオ酸塩を得ることができ、特にアミンのカルボジチオ酸塩の水への溶解度が３０重量％以上、さらに４０重量％以上の場合、特にその効果が顕著である。 The production method of the present invention is not particularly limited as long as it is an amine carbodithioate, and a solid amine carbodithioate can be obtained more efficiently than conventional methods. The effect is particularly remarkable when the solubility in water is 30% by weight or more, and further 40% by weight or more.
本発明の製造方法では重金属処理剤として有用なアミンのカルボジチオ酸塩を効率的に固体状で得ることができ、特にアミンのカルボジチオ酸塩の水への溶解度が３０重量％以上の場合、特に効果的である。 In the production method of the present invention, a carbodithioate salt of an amine useful as a heavy metal treating agent can be efficiently obtained in a solid state, particularly when the solubility of the amine carbodithioate salt in water is 30% by weight or more. Is.
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.
実施例１
ピペラジン４３．８ｇ、純水３４．３ｇ、二硫化炭素７６．７ｇ（ピペラジンの二硫化炭素と反応するアミノ基に対して０．９９倍当量）、４８．５％水酸化カリウム１２１．８ｇ（ピペラジンの二硫化炭素と反応するアミノ基に対して１．０４倍当量）、エタノール１２３．４ｇ（水：エタノール＝１：１．３（重量比））とし、ピペラジンを純水及びエタノールに４０℃で溶解させた後、攪拌しながら４０℃にて二硫化炭素と４８．５％水酸化カリウムをそれぞれ交互に４分割して滴下した。滴下終了後、３０分熟成し、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムが析出したスラリー溶液が得られた。（反応により生成するピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムの濃度は３９．６重量％）
析出したピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムを減圧ろ過にてろ別し、固体状のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム１９１．８ｇを得た。
Example 1
Piperazine 43.8 g, pure water 34.3 g, carbon disulfide 76.7 g (0.99 equivalents to the amino group reacting with piperazine carbon disulfide), 48.5% potassium hydroxide 121.8 g (piperazine ) And ethanol (123.4 g (water: ethanol = 1: 1.3 (weight ratio))), and piperazine in pure water and ethanol at 40 ° C. After dissolution, carbon disulfide and 48.5% potassium hydroxide were alternately added dropwise at 40 ° C. with stirring in four portions. After completion of the dropwise addition, the mixture was aged for 30 minutes to obtain a slurry solution in which potassium piperazine-N, N′-biscarbodithioate was precipitated. (The concentration of piperazine-N, N′-biscarbodithioate potassium produced by the reaction is 39.6% by weight)
The precipitated potassium piperazine-N, N′-biscarbodithioate was filtered off under reduced pressure to obtain 191.8 g of solid potassium piperazine-N, N′-biscarbodithioate.
水への溶解度が３０重量％を超える３９．６重量％であるアミンのカルボジチオ酸塩を固体状で効率的に得ることができた。 An amine carbodithioate having a water solubility of more than 30% by weight and 39.6% by weight could be efficiently obtained as a solid.
実施例２
ピペラジン４３．８ｇ、純水２８．６ｇ、二硫化炭素７６．７ｇ（ピペラジンの二硫化炭素と反応するアミノ基に対して０．９９倍当量）、４８．５％水酸化カリウム１２１．８ｇ（ピペラジンの二硫化炭素と反応するアミノ基に対して１．０４倍当量）、アセトン１２９．１ｇ（水：アセトン＝１：１．４（重量比））とし、ピペラジンを純水及びアセトンに４０℃で溶解させた後、攪拌しながら４０℃にて二硫化炭素と４８．５％水酸化カリウムをそれぞれ交互に４分割して滴下した。滴下終了後、３０分熟成し、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムが析出したスラリー溶液が得られた。（反応により生成するピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムの濃度は３９．６重量％）
析出したピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムを減圧ろ過にてろ別し、固体状のピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム１６５．６ｇを得た。
Example 2
Piperazine 43.8 g, pure water 28.6 g, carbon disulfide 76.7 g (0.99 equivalents to the amino group reacting with carbon disulfide of piperazine), 48.5% potassium hydroxide 121.8 g (piperazine 1.04 times equivalent to the amino group reacting with carbon disulfide), 129.1 g of acetone (water: acetone = 1: 1.4 (weight ratio)), and piperazine in pure water and acetone at 40 ° C. After dissolution, carbon disulfide and 48.5% potassium hydroxide were alternately added dropwise at 40 ° C. with stirring in four portions. After completion of the dropwise addition, the mixture was aged for 30 minutes to obtain a slurry solution in which potassium piperazine-N, N′-biscarbodithioate was precipitated. (The concentration of piperazine-N, N′-biscarbodithioate potassium produced by the reaction is 39.6% by weight)
The precipitated potassium piperazine-N, N′-biscarbodithioate was filtered off under reduced pressure to obtain 165.6 g of solid potassium piperazine-N, N′-biscarbodithioate.
水への溶解度が３０重量％を超える３９．６重量％であるアミンのカルボジチオ酸塩を固体状で効率的に得ることができた。 An amine carbodithioate having a water solubility of more than 30% by weight and 39.6% by weight could be efficiently obtained as a solid.
実施例３
Ｎ−アミノエチルピペラジン５５．６ｇ、純水４７．２ｇ、二硫化炭素６４．９ｇ（Ｎ−アミノエチルピペラジンの二硫化炭素と反応するアミノ基に対して０．９９倍当量）、４８．５％水酸化ナトリウム７５．１ｇ（Ｎ−アミノエチルピペラジンの二硫化炭素と反応するアミノ基に対して１．０６倍当量）、エタノール１５７．２ｇ（水：エタノール＝１：１．５（重量比））とし、Ｎ−アミノエチルピペラジンを純水及びエタノールに４０℃で溶解させた後、攪拌しながら４０℃にて二硫化炭素と４８．５％水酸化ナトリウムをそれぞれ交互に４分割して滴下した。滴下終了後、３０分熟成し、Ｎ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウムが析出したスラリー溶液が得られた。（反応により生成するＮ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウムの濃度は３４．７重量％）
析出したＮ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウムを減圧ろ過にてろ別し、固体状のＮ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウム１２２．０ｇを得た。
Example 3
55.6 g of N-aminoethylpiperazine, 47.2 g of pure water, 64.9 g of carbon disulfide (0.99 times equivalent to the amino group reacting with carbon disulfide of N-aminoethylpiperazine), 48.5% Sodium hydroxide 75.1 g (1.06 times equivalent to amino group reacting with carbon disulfide of N-aminoethylpiperazine), ethanol 157.2 g (water: ethanol = 1: 1.5 (weight ratio)) Then, N-aminoethylpiperazine was dissolved in pure water and ethanol at 40 ° C., and carbon disulfide and 48.5% sodium hydroxide were alternately added dropwise at 40 ° C. while stirring at 4 ° C. After completion of the dropwise addition, the mixture was aged for 30 minutes to obtain a slurry solution in which sodium N-aminoethylpiperazine-N ′, N ″ -biscarbodithioate was precipitated. (N-aminoethylpiperazine-N ′, produced by reaction) (The concentration of sodium N ″ -biscarbodithioate is 34.7% by weight)
Precipitated sodium N-aminoethylpiperazine-N ′, N ″ -biscarbodithioate was filtered off under reduced pressure and solid sodium N-aminoethylpiperazine-N ′, N ″ -biscarbodithioate 122.0 g. Got.
水への溶解度が３０重量％を超える３４．７重量％であるアミンのカルボジチオ酸塩を固体状で効率的に得ることができた。 An amine carbodithioate having a solubility in water of more than 30% by weight and 34.7% by weight could be efficiently obtained as a solid.
比較例１
ピペラジン４３．８ｇ、純水１５７．７ｇ、二硫化炭素７６．７ｇ、４８．５％水酸化カリウム１２１．８ｇとし、ピペラジンを純水に４０℃で溶解させた後、攪拌しながら４０℃にて二硫化炭素と４８．５％水酸化カリウムをそれぞれ交互に４分割して滴下した。滴下終了後、３０分熟成したところ、ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムの析出は確認されなかった。（反応により生成するピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムの濃度は３９．６重量％）
水溶性の有機溶媒を用いなかったことから、アミンのカルボジチオ酸塩を固体状で得ることができなかった。
Comparative Example 1
Piperazine 43.8g, pure water 157.7g, carbon disulfide 76.7g, 48.5% potassium hydroxide 121.8g, and piperazine was dissolved in pure water at 40 ° C, and then stirred at 40 ° C. Carbon disulfide and 48.5% potassium hydroxide were alternately added dropwise in four portions. After completion of the dropwise addition, the mixture was aged for 30 minutes, and no precipitation of piperazine-N, N′-biscarbodithioate potassium was confirmed. (The concentration of piperazine-N, N′-biscarbodithioate potassium produced by the reaction is 39.6% by weight)
Since no water-soluble organic solvent was used, the carbodithioate of amine could not be obtained in solid form.
比較例２
Ｎ−アミノエチルピペラジン５５．６ｇ、純水２０４．４ｇ、二硫化炭素６４．９ｇ、４８．５％水酸化ナトリウム７５．１ｇとし、Ｎ−アミノエチルピペラジンを純水に４０℃で溶解させた後、攪拌しながら４０℃にて二硫化炭素と４８．５％水酸化ナトリウムをそれぞれ交互に４分割して滴下した。滴下終了後、３０分熟成したところ、Ｎ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウムの析出は確認されなかった。（反応により生成するＮ−アミノエチルピペラジン−Ｎ’，Ｎ”−ビスカルボジチオ酸ナトリウムの濃度は３４．７重量％）
水溶性の有機溶媒を用いなかったことから、アミンのカルボジチオ酸塩を固体状で得ることができなかった。
Comparative Example 2
After 55.6 g of N-aminoethylpiperazine, 204.4 g of pure water, 64.9 g of carbon disulfide, and 75.1 g of 48.5% sodium hydroxide, N-aminoethylpiperazine was dissolved in pure water at 40 ° C. While stirring, carbon disulfide and 48.5% sodium hydroxide were alternately added dropwise in 4 portions at 40 ° C. After completion of the dropwise addition, the mixture was aged for 30 minutes, and precipitation of sodium N-aminoethylpiperazine-N ′, N ″ -biscarbodithioate was not confirmed. (N-aminoethylpiperazine-N ′, N produced by the reaction) “The concentration of sodium biscarbodithioate is 34.7% by weight)
Since no water-soluble organic solvent was used, the carbodithioate of amine could not be obtained in solid form.
本発明の製造法で得られた固体状のアミンのカルボジチオ酸塩は、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 solid amine 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, incinerated ash, and fly ash.
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| JPH11114528A (en) * | 1997-10-15 | 1999-04-27 | Nippon Soda Co Ltd | Solid heavy metal fixing agent |
| JP2006124401A (en) * | 2001-11-21 | 2006-05-18 | Nippon Soda Co Ltd | Method for producing aqueous solution containing piperazine-bis(carbodithionic acid) salt |
| JP2010095605A (en) * | 2008-10-16 | 2010-04-30 | Tosoh Corp | Method for manufacturing high-purity piperazine-n-carbodithioic acid salt and use of the same |
| JP2010150501A (en) * | 2008-11-18 | 2010-07-08 | Tosoh Corp | Solid heavy metal processing agent, method for producing the same and use of the same |
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| US2563007A (en) * | 1947-08-25 | 1951-08-07 | Phillips Petroleum Co | Production of alkali metal salts of n-substituted dithiocarbamic acids |
| JPH11114528A (en) * | 1997-10-15 | 1999-04-27 | Nippon Soda Co Ltd | Solid heavy metal fixing agent |
| JP2006124401A (en) * | 2001-11-21 | 2006-05-18 | Nippon Soda Co Ltd | Method for producing aqueous solution containing piperazine-bis(carbodithionic acid) salt |
| JP2010095605A (en) * | 2008-10-16 | 2010-04-30 | Tosoh Corp | Method for manufacturing high-purity piperazine-n-carbodithioic acid salt and use of the same |
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| CN112552262A (en) * | 2020-08-13 | 2021-03-26 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN112552262B (en) * | 2020-08-13 | 2022-03-08 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
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