JP5439990B2 - Solid heavy metal treating agent, production method and use thereof - Google Patents

Solid heavy metal treating agent, production method and use thereof Download PDF

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JP5439990B2
JP5439990B2 JP2009162099A JP2009162099A JP5439990B2 JP 5439990 B2 JP5439990 B2 JP 5439990B2 JP 2009162099 A JP2009162099 A JP 2009162099A JP 2009162099 A JP2009162099 A JP 2009162099A JP 5439990 B2 JP5439990 B2 JP 5439990B2
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piperazine
heavy metal
potassium
biscarbodithioate
dihydrate
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JP2010150504A (en
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義則 阿山
英樹 疋田
利登 長嶺
満明 吉光
康行 長井
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東ソー株式会社
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本発明は、輸送経済性、保存安定性(有効成分濃度の安定、固結防止)に優れ、使用時
における安全性(有害ガス非発生)及び有害な鉛に対する反応選択性に優れる固体状の重金属処理剤を提供するものである。
The present invention is a solid heavy metal that is excellent in transportation economy, storage stability (stable active ingredient concentration, anti-caking), safety in use (no harmful gas generation), and excellent reaction selectivity for harmful lead. A treatment agent is provided.
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30〜60%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 30 to 60% is usually used, but recently, the demand for a solid (powdered) heavy metal treating agent is increasing.
これまで、固体状の賦形剤に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が提案されている。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重量部用いる方法(特許文献1)、ケイ酸カルシウムを担体とする方法(特許文献2)、不溶性である遷移金属のカルボジチオ酸塩を用いる方法(特許文献3)、カルボジチオ酸塩溶液を高温で噴霧乾燥したものを用いる方法(特許文献4)、デンプンにキレート剤を含ませて粉末状にしたもの(特許文献5)、等がある。   So far, solid heavy metal treating agents containing amine carbodithioate in solid excipients have been proposed. For example, a method of using 100 parts by weight of alkali hydroxide or alkaline earth hydroxide with respect to 3 to 30 parts by weight of carbodithioate (Patent Document 1), a method using calcium silicate as a carrier (Patent Document 2), A method using a carbodithioate of an insoluble transition metal (Patent Document 3), a method using a spray-dried carbodithioate solution at a high temperature (Patent Document 4), and a starch containing a chelating agent in powder form (Patent Document 5) and the like.
しかし、従来の固形の重金属処理剤は、固体中の有効成分濃度が低いものしかなかった。さらに従来水溶液の重金属処理剤を用いているところで不溶性のカルボジチオ酸塩を水に分散してスラリーとして用いた場合、配管の詰まり等の原因となり、使い難いという問題があった。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。溶媒の除去におけるエネルギー消費を避けるため、賦形剤にカルボジチオ酸塩を含ませる方法では、重金属処理剤中の賦形成分の比率が大きいため、単位重量当りの薬剤の性能が低いという問題があった。   However, conventional solid heavy metal treating agents have only a low active ingredient concentration in the solid. Further, when an insoluble carbodithioate salt is dispersed in water and used as a slurry when a conventional heavy metal treating agent in an aqueous solution is used, there is a problem that it is difficult to use due to clogging of piping and the like. In the 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. In order to avoid energy consumption in removing the solvent, the method in which the carbodithioate is included in the excipient has a problem that the performance of the drug per unit weight is low because the ratio of the formation in the heavy metal treatment agent is large. It was.
一方、ピペラジン−N,N’−ビスカルボジチオ酸塩では重金属処理能が高く、有害ガスの発生がない優れた重金属処理剤として知られている(特許文献6参照)。従来のピペラジン−N,N’−ビスカルボジチオ酸塩を有効成分とする飛灰処理は、ピペラジン−N,N’−ビスカルボジチオ酸塩の水溶液として用いられているだけであった。   On the other hand, piperazine-N, N′-biscarbodithioate is known as an excellent heavy metal treatment agent having high heavy metal treatment ability and no generation of harmful gas (see Patent Document 6). Conventional fly ash treatment using piperazine-N, N'-biscarbodithioate as an active ingredient has only been used as an aqueous solution of piperazine-N, N'-biscarbodithioate.
固体状のピペラジン−N,N’−ビスカルボジチオ酸塩は、有機溶媒中での再結晶によって得られたピペラジン−N,N’−ビスカルボジチオ酸ナトリウム塩(固体)の無水物、4水和物(又は4.5水和物)又は6水和物が微量金属の比色分析用に用いる試薬として知られているに過ぎず、重金属処理剤としては用いられていなかった(非特許文献1〜4参照)。   Solid piperazine-N, N′-biscarbodithioate is an anhydrous form of piperazine-N, N′-biscarbodithioic acid sodium salt (solid) obtained by recrystallization in an organic solvent. Japanese hydrate (or 4.5 hydrate) or hexahydrate is only known as a reagent used for colorimetric analysis of trace metals and has not been used as a heavy metal treating agent (Non-patent Document) 1-4).
特許第3895018号Japanese Patent No. 3895018 特開2004−97927号JP 2004-97927 A 特開2003−301165号JP2003-301165A 特開2003−336035号JP 2003-336035 A 特開2003−113362号JP 2003-113362 A 特許第3391173号Japanese Patent No. 3391173
本発明の目的は、輸送経済性に優れ、保存中に有効成分濃度の変動がなく、固結せず保存安定性に優れ、保存時及び使用時に有害ガスの発生がなく、なおかつ有害な鉛に対する選択性の高い重金属処理剤を提供することにある。   The object of the present invention is excellent in transportation economical efficiency, no change in active ingredient concentration during storage, no caking, excellent storage stability, no generation of harmful gases during storage and use, and against harmful lead The object is to provide a heavy metal treating agent with high selectivity.
本発明者等は、重金属処理能及び取扱い性(経済性、保存安定性、安全性)に優れた固体状の重金属処理剤について鋭意検討を重ねた結果、ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物は、当該塩の他の形態の水和物或いは無水和物にはない高い結晶性を有し、保存中に重量の変化及び固結の問題もなく、重金属含有物に直接混合して用いた場合における二硫化炭素等の有害ガスの発生を極限まで低減でき、なおかつ特に有害な鉛に対する反応選択性が向上することを見出し、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 solid heavy metal treating agent excellent in heavy metal treating ability and handleability (economic efficiency, storage stability, safety), the present inventors have conducted piperazine-N, N′-biscarbodithio. Potassium acid dihydrate has high crystallinity not found in other forms of hydrates or hydrates of the salt, and contains heavy metals without problems of weight change and consolidation during storage. It has been found that the generation of harmful gases such as carbon disulfide can be reduced to the utmost when it is used in direct mixing, and the reaction selectivity for particularly harmful lead is improved, and the present invention has been completed. is there.
以下に本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤について説明する。   The heavy metal treating agent comprising piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention will be described below.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤は、特に以下の主要なX線回折ピークを有する高い結晶性を有するものが好ましい。   The heavy metal treating agent comprising piperazine-N, N'-biscarbodithioate potassium dihydrate of the present invention is particularly preferably one having high crystallinity having the following main X-ray diffraction peaks.
高い結晶性を有するピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物では、大気中の保存において有効成分(ピペラジン−N,N’−ビスカルボジチオ酸カリウム)の含有量に変動がなく、保存中に固結し難いという特徴を有する。 Piperazine-N, N'-biscarbodithioate potassium dihydrate, which has high crystallinity, varies in content of active ingredient (piperazine-N, N'-biscarbodithioate potassium) during storage in the atmosphere And has the feature that it is difficult to consolidate during storage.
ピペラジン−N,N’−ビスカルボジチオ酸カリウムの無水和物は大気中の水分を吸収して重金属処理剤の有効成分の重量比が変化するため、重金属処理に用いる前に有効成分の再確認が必要であるが、本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物では、大気中の水分の吸収による重量変化がないためにその様な確認の必要がない。   Piperazine-N, N'-biscarbodithioic acid anhydrate absorbs moisture in the atmosphere and changes the weight ratio of the active ingredient in the heavy metal treatment agent. However, in the piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention, there is no change in weight due to the absorption of moisture in the atmosphere, so that there is no need for such confirmation.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を有効成分とする重金属処理剤は、ピペラジン−N,N’−ビスカルボジチオ酸カリウムの含有量が85重量%以上であることが好ましい。重金属処理剤の結晶粉末が全て2水和物の場合にピペラジン−N,N’−ビスカルボジチオ酸カリウムの含有量は89.7重量%である。ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物は、従来の固体状の重金属処理剤の様にアミンのカルボジチオ酸塩を他の固体塩(担体)と混合したものでなく、純粋な結晶であるため、重金属処理剤中の有効成分の含有率が高い。なお本発明では、2水和物の結晶の内部に無水和或いは低水和物が一部に含まれても、少なくとも粒子の表面部分を2水和物で構成することにより固結防止等の効果を発揮することができる。   The heavy metal treating agent containing potassium piperazine-N, N′-biscarbodithioate dihydrate of the present invention as an active ingredient has a content of potassium piperazine-N, N′-biscarbodithioate of 85% by weight or more. It is preferable that When the crystal powder of the heavy metal treating agent is all dihydrate, the content of piperazine-N, N′-biscarbodithioate potassium is 89.7% by weight. Piperazine-N, N'-biscarbodithioate potassium dihydrate is not a mixture of amine carbodithioate with other solid salt (carrier) like conventional solid heavy metal treating agent. Since it is a pure crystal | crystallization, the content rate of the active ingredient in a heavy metal processing agent is high. In the present invention, even if anhydrous or low hydrate is partially contained in the dihydrate crystal, at least the surface portion of the particle is composed of dihydrate to prevent caking. The effect can be demonstrated.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤は、薬剤の保存時及び重金属含有物と混合して用いた際において有害ガスの発生がないものである。固体状のピペラジン−N,N’−ビスカルボジチオ酸カリウムでは、無水物では二硫化炭素が発生するが、2水和物ではその様な問題が一切ない。   The heavy metal treating agent comprising piperazine-N, N′-biscarbodithioic acid potassium dihydrate of the present invention generates noxious gases during storage of the drug and when mixed with heavy metal-containing materials. There is nothing. Solid potassium potassium piperazine-N, N'-biscarbodithioate generates carbon disulfide in the anhydride, but there is no such problem in the dihydrate.
さらに本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤は、有害な鉛への反応選択性が高く、有害な鉛を効率的に固定化処理できる。例えば重金属含有物の重金属処理におけるピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物の鉛への反応選択性(対銅比較)は総固形分(飛灰+キレート剤)に対する水分添加量が20重量%程度の場合、無水和物に比べ5倍以上高いものである。水分添加量が増大した場合にも、2水和物の鉛への反応選択性の優位性は維持される。   Furthermore, the heavy metal treating agent comprising piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention has high reaction selectivity to harmful lead and efficiently fixes harmful lead. It can be processed. For example, piperazine-N, N'-biscarbodithioate potassium dihydrate reaction selectivity to lead (compared to copper) in heavy metal treatment of heavy metal-containing materials is the water content of total solids (fly ash + chelating agent) When the addition amount is about 20% by weight, it is five times higher than the anhydrous product. Even when the amount of water added is increased, the superiority of the reaction selectivity of dihydrate to lead is maintained.
本発明の重金属処理剤を用いた重金属処理における重金属含有物及び重金属処理剤の総固形分に対する水分添加量は特に限定はないが、10重量%以上50重量%以下が好ましく、特に20重量%以上40重量%以下が好ましい。例えば重金属含有物の飛灰の処理において、水分添加量が多すぎると巨大な塊状又はスラリー状となり処理灰のハンドリングが難しくなるため、水分添加量は通常、固形分に対して20〜40重量%の範囲となるよう行われる。従って、本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤は、通常の水分添加量の飛灰処理において鉛への高い反応選択性を発揮することができる。   The amount of water added to the total solid content of the heavy metal-containing material and heavy metal treatment agent in the heavy metal treatment using the heavy metal treatment agent of the present invention is not particularly limited, but is preferably 10% by weight to 50% by weight, particularly preferably 20% by weight or more. It is preferably 40% by weight or less. For example, in the treatment of heavy metal-containing fly ash, if the amount of water added is too large, it becomes a huge lump or slurry and it becomes difficult to handle the treated ash, so the amount of water added is usually 20 to 40% by weight based on the solid content. It is performed to be in the range. Therefore, the heavy metal treating agent comprising the piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention exhibits a high reaction selectivity to lead in the fly ash treatment with a normal water addition amount. can do.
本発明の重金属処理剤は、安定性向上のためにさらにアルカリ水酸化物、アルカリ土類水酸化物を含有してもよい。これらのアルカリ成分は賦形剤として用いるものではないため、その含有量はピペラジン−N,N’−ビスカルボジチオ酸カリウムに対して0.01〜5重量%、特に0.1〜2重量%の範囲で十分である。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、アルカリ土類水酸化物としては水酸化マグネシウム、水酸化カルシウムが好ましい。   The heavy metal treating agent of the present invention may further contain an alkali hydroxide or an alkaline earth hydroxide for improving the stability. Since these alkali components are not used as excipients, their content is 0.01 to 5% by weight, particularly 0.1 to 2% by weight, based on piperazine-N, N′-biscarbodithioate potassium. A range of is sufficient. As the alkali hydroxide, sodium hydroxide and potassium hydroxide are preferable, and as the alkaline earth hydroxide, magnesium hydroxide and calcium hydroxide are preferable.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物の製造方法は特に限定されるものではないが、以下の製造方法によって効率的に製造することができる。   Although the manufacturing method of the piperazine-N, N'-biscarbodithioic acid potassium dihydrate of this invention is not specifically limited, It can manufacture efficiently with the following manufacturing methods.
ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物は、ピペラジン、二硫化炭素及び水酸化カリウムをピペラジン−N,N’−ビスカルボジチオ酸カリウムの飽和水溶液中で反応し、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩を析出し、当該塩を水溶液から分離することによって製造することができる。   Piperazine-N, N'-biscarbodithioate potassium dihydrate is prepared by reacting piperazine, carbon disulfide and potassium hydroxide in a saturated aqueous solution of piperazine-N, N'-biscarbodithioate potassium. -N, N'-biscarbodithioic acid potassium salt can be precipitated and the salt can be separated from the aqueous solution.
ピペラジンとピペラジン−N,N’−ビスカルボジチオ酸塩とでは、水に対する溶解度がピペラジンの方が高い(ピペラジンは約1.8モル/L、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩で1.3モル/L(約40重量%))ため、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩の飽和溶液に対してもピペラジンをさらに溶解することができる。また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飽和水溶液は液粘性が低いため、反応性(取扱い性)に優れる。   Piperazine and piperazine-N, N′-biscarbodithioate have higher solubility in water than piperazine (piperazine is about 1.8 mol / L, piperazine-N, N′-biscarbodithioate potassium salt Therefore, piperazine can be further dissolved in a saturated solution of piperazine-N, N′-biscarbodithioic acid potassium salt. In addition, since the saturated aqueous solution of piperazine-N, N′-biscarbodithioate produced has low liquid viscosity, it is excellent in reactivity (handleability).
ピペラジン−N,N’−ビスカルボジチオ酸塩以外のアミンのカルボジチオ酸塩、例えばテトラエチレンペンタミン、ジエチレントリアミン、ポリエチレンイミン等のカルボジチオ酸塩の過飽和溶液では固体が析出せずに粘調物となるため、安定な固体状のアミンのカルボジチオ酸塩を得ることが困難である。   A carbodithioate of an amine other than piperazine-N, N′-biscarbodithioate, for example, a supersaturated solution of a carbodithioate such as tetraethylenepentamine, diethylenetriamine, and polyethyleneimine, does not precipitate a solid and becomes viscous. Therefore, it is difficult to obtain a stable solid amine carbodithioate.
本発明の方法では、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩の飽和水溶液中にピペラジンを溶解し、二硫化炭素を先に添加し、後から水酸化カリウムを添加することが好ましい。ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩の飽和水溶液中では、水酸化カリウムが過剰の状態でピペラジンと二硫化炭素を反応させるとゲル状の副生物が生成し、連続的な反応が困難となる場合がある。   In the method of the present invention, it is preferable to dissolve piperazine in a saturated aqueous solution of piperazine-N, N′-biscarbodithioic acid potassium salt, add carbon disulfide first, and then add potassium hydroxide. In a saturated aqueous solution of piperazine-N, N′-biscarbodithioic acid potassium salt, a gel-like by-product is formed when piperazine and carbon disulfide are reacted in an excess of potassium hydroxide, and a continuous reaction occurs. It can be difficult.
本発明の方法では、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩の飽和水溶液中へのピペラジン溶解及び二硫化炭素の添加と水酸化カリウムの添加を交互に繰り返すことによって、連続的にピペラジン−N,N’−ビスカルボジチオ酸カリウムを製造することができる。   In the method of the present invention, piperazine is continuously produced by dissolving piperazine in a saturated aqueous solution of piperazine-N, N′-biscarbodithioic acid salt and alternately repeating the addition of carbon disulfide and the addition of potassium hydroxide. -N, N'-biscarbodithioic acid potassium can be produced.
特に好ましい実施形態としては、ピペラジン−N,N’−ビスカルボジチオ酸カリウムの飽和水溶液中でのピペラジン、二硫化炭素及び水酸化カリウムの反応において先にピペラジンをピペラジン−N,N’−ビスカルボジチオ酸カリウムの飽和水溶液に溶解させた後、水酸化カリウムに対して二硫化炭素が過剰な状態を維持して反応させる方法が例示できる。二硫化炭素が水酸化カリウムよりも過剰な状態で反応した場合には固体状のピペラジン−N,N’−ビスカルボジチオ酸が一旦析出するが、水酸化カリウムを先に添加した場合に比べて、粘性が低く、反応性及びハンドリングが良好となり、最終的には純粋なピペラジン−N,N’−ビスカルボジチオ酸カリウムの結晶が得られる。特に二硫化炭素及び水酸化カリウムの添加をそれぞれ2回以上に分割又は時間差をつけて同時に添加する方法が好ましい。   Particularly preferred embodiments include piperazine-N, N′-biscarbohydrate previously reacted in the reaction of piperazine, carbon disulfide and potassium hydroxide in a saturated aqueous solution of piperazine-N, N′-biscarbodithioate. An example is a method in which a carbon disulfide is reacted in an excess state with respect to potassium hydroxide after being dissolved in a saturated aqueous solution of potassium dithioate. When carbon disulfide reacts in an excess state than potassium hydroxide, solid piperazine-N, N′-biscarbodithioic acid is once precipitated, but compared with the case where potassium hydroxide is added first. , Low viscosity, good reactivity and handling, and finally pure piperazine-N, N′-biscarbodithioate crystals are obtained. In particular, a method of adding carbon disulfide and potassium hydroxide at the same time by dividing each time into two or more times or adding a time difference is preferable.
水溶液中におけるピペラジン、二硫化炭素及び水酸化カリウムの反応では、ピペラジン−N,N’−ビスカルボジチオ酸カリウムの他にピペラジン−N−カルボジチオ酸カリウム、チオ炭酸塩が副生する場合があり、また未反応のピペラジンが残留する場合ある。官能基がひとつしかなく重金属処理能が低いピペラジン−N−カルボジチオ酸カリウムはピペラジン−N,N’−ビスカルボジチオ酸カリウムに比べて溶解性が高いため、本発明の方法では、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カリウムのみを選択的に結晶として回収することができる。   In the reaction of piperazine, carbon disulfide and potassium hydroxide in an aqueous solution, piperazine-N-carbodithioic acid potassium and thiocarbonate may be by-produced in addition to piperazine-N, N′-biscarbodithioic acid potassium. In addition, unreacted piperazine may remain. Piperazine-N-carbodithioate potassium, which has only one functional group and has a low heavy metal treatment capacity, has higher solubility than piperazine-N, N′-biscarbodithioate potassium, and therefore the method of the present invention has a heavy metal treatment capacity. Only high potassium piperazine-N, N′-biscarbodithioate can be selectively recovered as crystals.
ピペラジン、チオ炭酸塩も同様に水溶性が高いために水溶液中に残存し、ピペラジン−N,N’−ビスカルボジチオ酸カリウムと分離できる。濃縮や、有機溶媒抽出による方法では、ピペラジン−N−カルボジチオ酸カリウム、ピペラジン及びチオ炭酸塩がピペラジン−N,N’−ビスカルボジチオ酸カリウムと同時に析出するという問題があるが、本発明の方法では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カリウムを選択的に結晶として得ることが可能である。   Similarly, since piperazine and thiocarbonate are highly water-soluble, they remain in the aqueous solution and can be separated from piperazine-N, N′-biscarbodithioate potassium. In the method by concentration or organic solvent extraction, there is a problem that piperazine-N-carbodithioate potassium, piperazine and thiocarbonate precipitate simultaneously with potassium piperazine-N, N′-biscarbodithioate. Then, it is possible to selectively obtain potassium piperazine-N, N′-biscarbodithioate having high heavy metal treatment ability as crystals.
本発明において、析出した結晶の乾燥方法は2水和物を得る方法であれば特に限定されるものではないが、無水和物にまで過度に脱水しない条件とすることが好ましい。析出した結晶の乾燥によって結晶性が低下しても、さらに水分を含有する雰囲気中で水和することによって再結晶化は可能であり、ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物の結晶とすることができる。乾燥後の水和による結晶化は、粉砕及び/又は強制流動中で行うことが好ましい。   In the present invention, the method for drying the precipitated crystals is not particularly limited as long as it is a method for obtaining a dihydrate, but it is preferable that the crystal is not excessively dehydrated to an anhydrous product. Even if the crystallinity decreases due to drying of the precipitated crystals, it can be recrystallized by hydration in an atmosphere containing water, and piperazine-N, N′-biscarbodithioate potassium · 2 water. Japanese crystals can be obtained. Crystallization by hydration after drying is preferably performed in pulverization and / or forced flow.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を含んでなる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処理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てもよい。   The heavy metal treating agent comprising piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention is mixed with heavy metal-containing soil, waste water, waste, incinerated ash, etc. Elution can be prevented. The method of using the heavy metal treatment agent of the present invention in the heavy metal immobilization treatment can be applied in the same manner as other normal heavy metal treatment agents, such as water, alkali hydroxide or iron chloride as required for the heavy metal treatment agent. You may mix and use suitably with a pH adjuster.
ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物は、水に溶解した後に重金属含有物と混合して用いても良いが、水と同時に直接混合することが好ましく、特に直接混合した後に水を添加して用いることが好ましい。   Piperazine-N, N′-biscarbodithioate potassium dihydrate may be used after being dissolved in water and mixed with a heavy metal-containing material, but it is preferable to mix directly with water, particularly direct mixing. It is preferable to add water after use.
本発明のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物の重金属処理剤は重金属処理能を有する成分の含有率が高く、保存時の重量変化や固結の問題がないため輸送性、保存安定性に優れ、重金属含有物と直接混合によって重金属処理が可能であり、保存時及び使用時に有害ガスの発生がなく、なおかつ有害な鉛への反応選択性が高い。   Since the heavy metal treating agent of piperazine-N, N′-biscarbodithioate potassium dihydrate of the present invention has a high content of components having heavy metal treating ability, there is no problem of weight change or consolidation during storage. It is excellent in transportability and storage stability, can be treated with heavy metals by direct mixing with heavy metal containing materials, does not generate harmful gases during storage and use, and has high reaction selectivity to harmful lead.
ピペラジン−N,N’−ビスカルボジチオ酸カリウムの無水和物、2水和物のX線回折図を示す。図の横軸(X軸)はX線回折における2θ値(単位はdeg)を示し、縦軸(Y軸)はX線回折におけるピークの強度を示し、スケールは任意である。2水和物は高い結晶性を有する。The X-ray diffraction pattern of the anhydrous piperazine-N, N'-biscarbodithioate dihydrate and dihydrate is shown. In the figure, the horizontal axis (X axis) represents 2θ values (unit: deg) in X-ray diffraction, the vertical axis (Y axis) represents peak intensity in X-ray diffraction, and the scale is arbitrary. Dihydrate has high crystallinity. ピペラジン−N,N’−ビスカルボジチオ酸カリウムの無水和物、2水和物と塩化鉛及び純水(塩化鉛とピペラジン−N,N’−ビスカルボジチオ酸カリウムの水和物の総固形分に対して20重量%)を混合した際の鉛錯体の生成をX線回折で評価した図である。Piperazine-N, N'-biscarbodithioate anhydrate, dihydrate, lead chloride and pure water (lead chloride and piperazine-N, N'-biscarbodithioate hydrate total solid It is the figure which evaluated the production | generation of the lead complex at the time of mixing 20 weight% with respect to a part by X-ray diffraction. ピペラジン−N,N’−ビスカルボジチオ酸カリウムの無水和物、2水和物と塩化銅及び純水(塩化銅とピペラジン−N,N’−ビスカルボジチオ酸カリウムの水和物の総固形分に対して20重量%)を混合した際の銅錯体の生成をX線回折で評価した図である。Piperazine-N, N'-biscarbodithioate anhydrate, dihydrate and copper chloride and pure water (total solid of copper chloride and piperazine-N, N'-biscarbodithioate hydrate It is the figure which evaluated the production | generation of the copper complex at the time of mixing 20 weight% with respect to a minute by X-ray diffraction.
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68.45g、純水123.58g、二硫化炭素121.01g、48%水酸化カリウム186.96gとし、ピペラジンを純水に40℃で溶解させた後、窒素気流中で攪拌しながら二硫化炭素と48%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、ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物が析出したスラリー溶液が得られた。
Example 1
Piperazine 68.45 g, pure water 123.58 g, carbon disulfide 121.01 g, 48% potassium hydroxide 186.96 g, and piperazine was dissolved in pure water at 40 ° C., and then disulfide with stirring in a nitrogen stream. Carbon and 48% potassium hydroxide were added dropwise, alternately divided into 4 parts. After completion of the dropwise addition, a slurry solution in which piperazine-N, N′-biscarbodithioic acid potassium dihydrate was precipitated was obtained.
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ろ別し、真空乾燥機で付着水分を除去、乾燥した。   Precipitated potassium piperazine-N, N′-biscarbodithioate was filtered off, and the adhering moisture was removed with a vacuum dryer, followed by drying.
得られたピペラジン−N,N’−ビスカルボジチオ酸カリウムは熱分析の結果、2水和物であり、X線回折パターンは図1に示す通り高い結晶性を有するものであった。   The obtained potassium piperazine-N, N′-biscarbodithioate was found to be dihydrate as a result of thermal analysis, and its X-ray diffraction pattern had high crystallinity as shown in FIG.
得られたピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を純水に溶解し、13C−NMR測定を行った結果、ピペラジン及びピペラジン−N−ビスカルボジチオ酸カリウムは検出されなかった。 The obtained piperazine-N, N′-biscarbodithioate dihydrate was dissolved in pure water and subjected to 13 C-NMR measurement. As a result, piperazine and piperazine-N-biscarbodithioate potassium were detected. Was not.
実施例2
実施例1でピペラジン−N,N’−ビスカルボジチオ酸カリウムを濾別した濾液(ピペラジン−N,N’−ビスカルボジチオ酸カリウムの飽和水溶液)300gにさらにピペラジン30.42gと純水31.00gを加え、40℃で溶解し、窒素気流中で攪拌しながら二硫化炭素53.78gと48%水酸化カリウム84.80gをそれぞれ交互に2分割して滴下した。滴下終了後、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。
Example 2
In addition, 300.42 g of piperazine-N, N′-biscarbodithioate in Example 1 (saturated aqueous solution of piperazine-N, N′-biscarbodithioate) and 30.42 g of piperazine and 31. 00 g was added, dissolved at 40 ° C., and 53.78 g of carbon disulfide and 84.80 g of 48% potassium hydroxide were alternately added in two portions while stirring in a nitrogen stream. After completion of the dropping, a slurry solution in which potassium piperazine-N, N′-biscarbodithioate was precipitated was obtained.
飽和溶液を繰り返し用いて、ピペラジン−N,N’−ビスカルボジチオ酸カリウム塩が得られることが確認された。   It was confirmed that piperazine-N, N′-biscarbodithioic acid potassium salt was obtained by repeatedly using the saturated solution.
比較例1
実施例1の2水和物をさらに乾燥機中100℃で乾燥し、無水和物を得た。図1に示す通り、無水和物は2水和物と結晶性が異なり、なおかつ結晶性が低いものであった。
Comparative Example 1
The dihydrate of Example 1 was further dried at 100 ° C. in a dryer to obtain an anhydrous product. As shown in FIG. 1, the anhydrate was different from the dihydrate in crystallinity and had low crystallinity.
比較例2
ピペラジンをテトラエチレンペンタミンとし、テトラエチレンペンタミン88.11g、純水128.11g、二硫化炭素127.50g、48%水酸化ナトリウム156.28gとした以外は実施例1と同様の操作を行ったが、固体状のカルボジチオ酸塩は得られなかった。
Comparative Example 2
The same operation as in Example 1 was conducted except that piperazine was changed to tetraethylenepentamine, and 88.11 g of tetraethylenepentamine, 128.11 g of pure water, 127.50 g of carbon disulfide, and 156.28 g of 48% sodium hydroxide were used. However, a solid carbodithioate was not obtained.
(保存安定性評価1 重量変化)
実施例1及び比較例1で得られたピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物及び無水和物を大気中に放置し、重量変化の経時変化を測定した。結果を表2に示す。
(Storage stability evaluation 1 Change in weight)
Piperazine-N, N′-biscarbodithioate potassium dihydrate and anhydrate obtained in Example 1 and Comparative Example 1 were allowed to stand in the air, and the change with time in weight change was measured. The results are shown in Table 2.
無水和物は重量変化したが、2水和物では重量変化がなく、大気中の保存で安定であることが確認された。 The non-hydrate changed in weight, but the dihydrate did not change in weight, and it was confirmed that it was stable when stored in the atmosphere.
大気中放置後、2水和物は固結が認められなかったが、無水和物は流動性の低下、容器への付着が認められた。   After standing in the air, the dihydrate was not consolidated, but the anhydride was found to have decreased fluidity and adhered to the container.
(重金属固定化試験)
飛灰A(Pb=2500ppm)50重量部に対し、実施例1のピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物0.5部(無水和物換算)を水25重量部に溶解して灰と混練、及び2水和物0.5重量部(無水和物換算)を直接灰に添加した後25重量の水を灰に添加して混練した。その後、環境庁告示第13号試験に従い溶出試験を行った。
(Heavy metal immobilization test)
For 50 parts by weight of fly ash A (Pb = 2500 ppm), 0.5 parts of piperazine-N, N′-biscarbodithioate potassium dihydrate of Example 1 (in terms of anhydrate) is 25 parts by weight of water. Then, 0.5 parts by weight of dihydrate (anhydrous equivalent) was directly added to the ash, and then 25 weights of water was added to the ash and kneaded. Thereafter, a dissolution test was conducted according to the Environmental Agency Notification No. 13 test.
鉛の溶出はいずれも0.05ppm未満であり、環境基準を満たすものであった。   The elution of lead was less than 0.05 ppm and met the environmental standards.
(ガス測定1)
テドラーバッグ(容積1L)中に、ピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物2.2g(ピペラジン−N,N’−ビスカルボジチオ酸カリウム換算で2.0g相当)、空気を500mL装填し、室温及び65℃で1時間放置した。放置後、テドラーバッグのヘッドスペースの二硫化炭素濃度を検知管で測定した。
(Gas measurement 1)
In a Tedlar bag (volume 1 L), piperazine-N, N′-biscarbodithioate potassium dihydrate 2.2 g (corresponding to 2.0 g in terms of piperazine-N, N′-biscarbodithioate potassium), air Of 500 ml, and left at room temperature and 65 ° C. for 1 hour. After standing, the carbon disulfide concentration in the head space of the Tedlar bag was measured with a detector tube.
比較のため、ピペラジン−N,N’−ビスカルボジチオ酸カリウムの無水和物を添加(それぞれピペラジン−N,N’−ビスカルボジチオ酸カリウム換算で2水和物と同量)し、二硫化炭素濃度を測定した。結果を表3に示す。   For comparison, anhydrous piperazine-N, N′-biscarbodithioate potassium anhydrate (each equivalent to dihydrate in terms of potassium piperazine-N, N′-biscarbodithioate) and disulfide The carbon concentration was measured. The results are shown in Table 3.
無水物では二硫化炭素の発生が認められたが、2水和物では発生はなかった。   Generation of carbon disulfide was observed in the anhydride, but not in the dihydrate.
(ガス測定2)
テドラーバッグ(容積1L)中に、飛灰B(Pb=2700ppm)30gに対して純水35重量%及びピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を0.7重量%添加し、混合した後空気を500mL装填し、65℃で1時間加熱した。加熱後、テドラーバッグのヘッドスペースの硫化水素及び二硫化炭素濃度を検知管で測定した。
(Gas measurement 2)
In Tedlar bag (volume 1L), 35% by weight of pure water and 0.7% by weight of piperazine-N, N'-biscarbodithioate potassium dihydrate are added to 30g of fly ash B (Pb = 2700ppm). After mixing, 500 mL of air was charged and heated at 65 ° C. for 1 hour. After heating, the hydrogen sulfide and carbon disulfide concentrations in the head space of the Tedlar bag were measured with a detector tube.
飛灰C(Pb=9800ppm)に純水20重量%及びピペラジン−N,N’−ビスカルボジチオ酸カリウム・2水和物を1.1重量%添加し、同様のガス測定を行った。   The same gas measurement was performed by adding 20% by weight of pure water and 1.1% by weight of piperazine-N, N′-biscarbodithioate potassium dihydrate to Fly Ash C (Pb = 9800 ppm).
結果を表5に示す。硫化水素及び二硫化炭素の発生はなかった。   The results are shown in Table 5. There was no generation of hydrogen sulfide or carbon disulfide.
(鉛に対する反応選択性)
ピペラジン−N,N’−ビスカルボジチオ酸カリウムの2水和物及び無水和物をピペラジン−N,N’−ビスカルボジチオ酸カリウム成分換算で10gをそれぞれ塩化鉛8.8g及び塩化銅4.3gと純水(塩化鉛又は塩化銅及びピペラジン−N,N’−ビスカルボジチオ酸カリウムの水和物の総固形分に対して20重量%及び30重量%)とで混合し、混合後の各金属錯体の生成をX線回折で測定した。
(Reactivity selectivity for lead)
Piperazine-N, N′-biscarbodithioate dihydrate and anhydrate thereof are converted into potassium piperazine-N, N′-biscarbodithioate components as 10 g, lead chloride 8.8 g and copper chloride 4. 3 g and pure water (20 wt% and 30 wt% based on the total solid content of lead chloride or copper chloride and piperazine-N, N′-biscarbodithioate hydrate) The formation of each metal complex was measured by X-ray diffraction.
鉛錯体、銅錯体及びピペラジン−N、N’−ビスカルボジチオ酸カリウムの回折角9.4°(鉛錯体由来のピーク(a))、15.1°(銅錯体由来のピーク(b))及び33.1°(ピペラジン−N、N’−ビスカルボジチオ酸カリウム成分由来のピーク(c))の各回折強度に対し、a/cを鉛反応性とし、b/cを銅反応性とし、それらの比を鉛の選択性とした。水分含有量20重量%及び30重量%の場合の結果を表5及び表6に示した。   Lead complex, copper complex and piperazine-N, N′-biscarbodithioate potassium diffraction angle 9.4 ° (lead complex-derived peak (a)), 15.1 ° (copper complex-derived peak (b)) And 33.1 ° (peak (c) derived from piperazine-N, N′-biscarbodithioate potassium component), a / c is lead-reactive and b / c is copper-reactive. These ratios were taken as lead selectivity. Tables 5 and 6 show the results when the water content is 20% by weight and 30% by weight.
2水和物は無水和物に比べて鉛に対する反応選択性が高く、その傾向は重金属含有物中の水分含有量が少ない方が顕著であった。   The dihydrate has a higher reaction selectivity to lead than the anhydride, and the tendency is more marked when the water content in the heavy metal-containing material is smaller.
本発明の重金属処理剤は重金属含有物中の重金属の固定化処理に使用することができ、特に大量の鉛を含む飛灰中の重金属処理に好適に使用できる。   The heavy metal treating agent of the present invention can be used for immobilizing heavy metals in a heavy metal-containing material, and particularly suitable for treating heavy metals in fly ash containing a large amount of lead.

Claims (10)

  1. ピペラジン−N,N'−ビスカルボジチオ酸カリウム・2水和物を含んでなる重金属処理剤。 A heavy metal treating agent comprising piperazine-N, N′-biscarbodithioate potassium dihydrate.
  2. 表1のX線回折パターンの結晶性を有するピペラジン−N,N'−ビスカルボジチオ酸カリウム・2水和物を含んでなる請求項1に記載の重金属処理剤
    The heavy metal treating agent according to claim 1, comprising piperazine-N, N'-biscarbodithioate potassium dihydrate having crystallinity of the X-ray diffraction pattern of Table 1.
  3. ピペラジン−N,N'−ビスカルボジチオ酸カリウムを85%以上含有する請求項1又は2に記載の重金属処理剤。 The heavy metal treating agent according to claim 1 or 2, comprising piperazine-N, N'-biscarbodithioate potassium in an amount of 85% or more.
  4. アルカリ水酸化物及び/又はアルカリ土類水酸化物をさらに含んでなる請求項1乃至3のいずれかに記載の重金属処理剤。 The heavy metal treating agent according to any one of claims 1 to 3, further comprising an alkali hydroxide and / or an alkaline earth hydroxide.
  5. ピペラジン、二硫化炭素、水酸化カリウムをピペラジン−N,N'−ビスカルボジチオ酸カリウム塩の飽和水溶液中で反応し、ピペラジン−N,N'−ビスカルボジチオ酸カリウム塩を析出し、当該塩を分離することを特徴とする請求項1乃至4のいずれかに記載の重金属処理剤の製造方法。 Piperazine, carbon disulfide, and potassium hydroxide are reacted in a saturated aqueous solution of piperazine-N, N′-biscarbodithioic acid potassium salt to precipitate piperazine-N, N′-biscarbodithioic acid potassium salt, and the salt The method for producing a heavy metal treating agent according to any one of claims 1 to 4, wherein the process is separated.
  6. ピペラジンを溶解したピペラジン−N,N'−ビスカルボジチオ酸カリウム塩の飽和水溶液中に、二硫化炭素を先に添加し、後から水酸化カリウムを添加することを特徴とする請求項5に記載の製造方法。 6. The carbon disulfide is added first in a saturated aqueous solution of piperazine-N, N′-biscarbodithioic acid potassium salt in which piperazine is dissolved, and potassium hydroxide is added later. Manufacturing method.
  7. ピペラジンを溶解したピペラジン−N,N'−ビスカルボジチオ酸カリウム塩の飽和水溶液中への二硫化炭素の添加と水酸化カリウムの添加を交互に繰り返す請求項5又は6に記載の製造方法。 The method according to claim 5 or 6, wherein the addition of carbon disulfide and the addition of potassium hydroxide are alternately repeated in a saturated aqueous solution of piperazine-N, N'-biscarbodithioic acid potassium salt in which piperazine is dissolved.
  8. 請求項1乃至4のいずれかに記載の重金属処理剤を重金属含有物と直接混合する重金属の処理方法。 The heavy metal processing agent which mixes the heavy metal processing agent in any one of Claims 1 thru | or 4 with a heavy metal containing material directly.
  9. 重金属含有物及び請求項1乃至4のいずれかに記載の重金属処理剤の総固形分に対する水分添加量が10重量%以上50重量%以下である請求項8に記載の重金属の処理方法。 The heavy metal treatment method according to claim 8, wherein the amount of water added to the total solid content of the heavy metal-containing material and the heavy metal treatment agent according to any one of claims 1 to 4 is 10 wt% or more and 50 wt% or less.
  10. 請求項1乃至4のいずれかに記載の重金属処理剤を水に溶解し、当該水溶液と重金属含有物と混合する重金属の処理方法。 The heavy metal processing agent in any one of Claims 1 thru | or 4 is melt | dissolved in water, The processing method of the heavy metal which mixes the said aqueous solution and a heavy metal containing material.
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