JP4696475B2 - Dithiocarbamate aqueous solution, production method thereof, heavy metal immobilization agent and heavy metal immobilization treatment method - Google Patents
Dithiocarbamate aqueous solution, production method thereof, heavy metal immobilization agent and heavy metal immobilization treatment method Download PDFInfo
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本発明は都市ゴミや産業廃棄物等の焼却プラントから排出される飛灰や、土壌等の固体廃棄物を処理するに際し、固体廃棄物中に含有される鉛、水銀、クロム、カドミウム、亜鉛及び銅等の有害な重金属をより簡便に固定化し不溶出化することを可能にする方法に関するものである。 The present invention, when processing fly ash discharged from incineration plants such as municipal waste and industrial waste, and solid waste such as soil, lead, mercury, chromium, cadmium, zinc and The present invention relates to a method that makes it possible to more easily fix and not elute harmful heavy metals such as copper.
都市ゴミや産業廃棄物等の焼却プラントから排出される飛灰は電気集塵機（ＥＰ）やバグフィルター（ＢＦ）で捕集されたのち埋め立てや海洋投棄されている。しかし、これら飛灰は有害な重金属を多く含んでおり、埋め立て地からの雨水等による鉛、水銀等の溶出は環境汚染の可能性がある。このため飛灰は特別管理廃棄物に指定され、「セメント固化法」、「酸その他の溶剤による抽出法」、「溶融固定化法」又は「薬剤添加法」のいずれかの処理を施した後、廃棄することが義務づけられている。このうち薬剤添加法は他の方法に比べ、一般に、装置及び取扱いが簡便なため種々検討されている。例えば、ポリエチレンイミン等のポリアミンを原料とするジチオカルバミン酸塩に無機硫化物を併用する方法が開示され（例えば、特許文献１）、ジエチレントリアミンを原料とするジチオカルバミン酸塩を使用する方法が開示されている（例えば、特許文献２）。また、ジチオカルバミン酸塩水溶液中にチオ炭酸塩を含有させ、保存時、重金属固定処理時に二硫化炭素ガス、アミンの発生を抑制する方法が開示されている（例えば、特許文献３）。 Fly ash discharged from incineration plants, such as municipal waste and industrial waste, is collected by an electrostatic precipitator (EP) or bag filter (BF) and then landfilled or dumped into the ocean. However, these fly ash contains a lot of harmful heavy metals, and elution of lead, mercury, etc. from rainwater from landfills may cause environmental pollution. For this reason, fly ash is designated as a specially managed waste, and after being treated with one of the following methods: “cement solidification method”, “extraction method with acid or other solvent”, “melt fixation method” or “chemical addition method” It is obliged to dispose of it. Of these, the drug addition method has been studied in various ways because it is generally easier to handle and handle than other methods. For example, a method of using an inorganic sulfide in combination with a dithiocarbamate salt made from polyamine such as polyethyleneimine is disclosed (for example, Patent Document 1), and a method using a dithiocarbamate salt made from diethylenetriamine is disclosed. (For example, patent document 2). In addition, a method is disclosed in which a thiocarbonate is contained in an aqueous dithiocarbamate solution to suppress generation of carbon disulfide gas and amine during storage and heavy metal fixing treatment (for example, Patent Document 3).
飛灰処理に関しては、ＥＰ又はＢＦ捕集等によるばいじん対策以外に、排ガス及びダイオキシン対策が必要であり、これらの対策によっては得られる飛灰の性状が大きく異なり、特に高アルカリ性飛灰においては重金属溶出量が多くなることが知られている。このような飛灰の重金属固定化のためには、従来の薬剤ではその使用量を大幅に増加するか、又は塩化第二鉄等のｐＨ調整剤、又はセメント等の他の薬剤との併用法を取らざるを得ず、処理薬剤費が増大し、又は処理方法が複雑化する等の問題があった。さらに、前記ジチオカルバミン酸塩は、その製造方法によっては、また原料とするアミンによっては、ｐＨ調整剤との混練又は熱により分解し、Ｈ２Ｓ、ＣＳ２等のガスを発生させる場合がある。 Regarding fly ash treatment, it is necessary to take measures against exhaust gas and dioxin in addition to dust and dust countermeasures by collecting EP or BF, etc. The properties of fly ash obtained by these measures differ greatly, especially in the case of highly alkaline fly ash It is known that the amount of elution increases. In order to immobilize heavy metals in such fly ash, the amount of use of conventional agents is greatly increased, or a pH regulator such as ferric chloride, or a combination method with other agents such as cement. Therefore, there is a problem that the cost of processing chemicals increases or the processing method becomes complicated. Furthermore, the dithiocarbamate may be decomposed by kneading with a pH adjuster or by heat depending on the production method or amine used as a raw material to generate a gas such as H 2 S or CS 2 .
本発明は上記の課題に鑑みてなされたものであり、その目的は、固体廃棄物、特に飛灰中に含まれる重金属を、Ｈ２Ｓ、ＣＳ２等の有害ガスの発生を抑えつつ、安定性の高いキレート剤を用いることにより簡便に処理できる方法を提供することである。 The present invention has been made in view of the above problems, and its purpose is to stabilize solid waste, particularly heavy metals contained in fly ash, while suppressing generation of harmful gases such as H 2 S and CS 2. It is to provide a method that can be easily processed by using a highly chelating agent.
本発明者等は上記の課題を解決すべく鋭意検討を重ねた結果、チオ炭酸塩を０．０３重量％未満含有し、かつアミノ基をジチオカルバミン酸基に対して２．０モル％以下含有することを特徴とするジチオカルバミン酸塩水溶液を重金属固定化処理剤として用いると、Ｈ２Ｓ、ＣＳ２等のガス発生を極微量に抑制でき、かつ、重金属に対するキレート能力が高く、高アルカリ性飛灰においても、少量の添加量で重金属を固定化できることを見出した。また、このジチオカルバミン酸水溶液は、アミン化合物と二硫化炭素とアルカリ金属化合物を反応させるジチオカルバミン酸塩水溶液の製造方法において、アミン化合物中のアミノ基に対する二硫化炭素のモル比を０．９８〜１．０とすることにより得られる。また、好ましくは、二硫化炭素に対するアルカリ金属化合物の反応モル比を１．０〜１．３とし、更に好ましくは、アミン化合物と二硫化炭素とアルカリ金属化合物を反応させる際に、アミン化合物の水溶液に、反応させる二硫化炭素の一部を添加し反応・熟成させた後、反応させるアルカリ金属化合物の一部を添加し反応・熟成させる操作を３回以上繰り返すことにより製造す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。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain less than 0.03% by weight of thiocarbonate and 2.0 mol% or less of amino groups with respect to dithiocarbamic acid groups. When a dithiocarbamate aqueous solution characterized by the above is used as a heavy metal immobilizing agent, gas generation of H 2 S, CS 2 and the like can be suppressed to a very small amount, and chelating ability for heavy metals is high, and in high alkaline fly ash It was also found that heavy metals can be immobilized with a small amount of addition. Further, this dithiocarbamic acid aqueous solution has a molar ratio of carbon disulfide to amino groups in the amine compound of 0.98 to 1 in a method for producing a dithiocarbamate aqueous solution in which an amine compound, carbon disulfide and an alkali metal compound are reacted. It is obtained by setting it to zero. Preferably, the reaction molar ratio of the alkali metal compound to carbon disulfide is 1.0 to 1.3, and more preferably, when the amine compound, carbon disulfide, and alkali metal compound are reacted, an aqueous solution of the amine compound. In addition, it is found that a part of the carbon disulfide to be reacted can be added and reacted / ripened, and then a part of the alkali metal compound to be reacted can be added and reacted / ripened three times or more. The present invention has been completed.
以下に本発明をさらに詳細に説明する。 The present invention is described in further detail below.
本発明のジチオカルバミン酸塩水溶液は、チオ炭酸塩を０．０３重量％未満含有し、かつアミノ基をジチオカルバミン酸基に対して２．０モル％以下含有する。 The dithiocarbamate aqueous solution of the present invention contains less than 0.03% by weight of thiocarbonate and 2.0 mol% or less of amino groups with respect to dithiocarbamate groups.
本発明のジチオカルバミン酸塩は、１級アミノ基又は２級アミノ基を有するアミン化合物から誘導されるジチオカルバミン酸塩が挙げられる。 Examples of the dithiocarbamate of the present invention include dithiocarbamate derived from an amine compound having a primary amino group or a secondary amino group.
本発明のジチオカルバミン酸塩の原料に使用されるアミン化合物としては、１級アミノ基又は２級アミノ基を有するアミン化合物であれば特に限定されるものではないが、脂肪族アミン化合物、芳香族アミン化合物が挙げられ、例えば、エチルアミン，ｎ−プロピルアミン，ｉ−プロピルアミン，ｎ−ブチルアミン，ｉ−ブチルアミン，ｓｅｃ−ブチルアミン，アミルアミン，２−エチルヘキシルアミン，シクロヘキシルアミン，ベンジルアミン，キシレンジアミン等の１級アミン類、ジエチルアミン，ジ−ｎ−プロピルアミン，ジ−ｉ−プロピルアミン，ジ−ｎ−ブチルアミン，ジ−ｉ−ブチルアミン，ジ−ｓｅｃ−ブチルアミン，ジアミルアミン，ジ−２−エチルヘキシルアミン等の２級アミン類、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，ヘキサエチレンヘプタミン，ヘプタエチレンオクタミン，トリエチレンジアミン等のポリエチレンポリアミン類、ピペリジン，ピロリジン，ピペラジン，Ｎ−アミノエチルピペラジン等の環状ポリアミン類等を挙げることができる。 The amine compound used as a raw material for the dithiocarbamate of the present invention is not particularly limited as long as it is an amine compound having a primary amino group or a secondary amino group, but is not limited to an aliphatic amine compound or an aromatic amine. Compounds such as ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, amylamine, 2-ethylhexylamine, cyclohexylamine, benzylamine, xylenediamine, etc. Secondary amines such as amines, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, diamylamine, di-2-ethylhexylamine , Ethylenediamine, diethylenetria Polyethylene polyamines such as ethylene, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, triethylenediamine, and cyclic polyamines such as piperidine, pyrrolidine, piperazine, N-aminoethylpiperazine, etc. Can be mentioned.
上記のアミン化合物の内、窒素数４以上のポリエチレンポリアミン又は窒素数２以上の環状ポリアミンから合成されたジチオカルバミン酸塩は、固体廃棄物中の重金属を固定化処理する際にＨ２Ｓ、ＣＳ２等のガス発生を微量に抑制でき、固体廃棄物中に含まれる重金属の固定化能が高いため好ましい。更に、２級アミノ基のみを有するピペラジンから合成されるピペラジンジチオカルバミン酸塩は、Ｈ２Ｓ、ＣＳ２等のガス発生を極めて微量に抑制でき、飛灰中に含まれる重金属の固定化能が極めて高いため、本発明において特に好適である。 Among the above amine compounds, dithiocarbamate synthesized from a polyethylene polyamine having 4 or more nitrogen atoms or a cyclic polyamine having 2 or more nitrogen atoms is H 2 S, CS 2 when the heavy metal in the solid waste is fixed. It is preferable because the generation of gases such as the above can be suppressed in a very small amount and the ability to immobilize heavy metals contained in solid waste is high. Furthermore, piperazine dithiocarbamate synthesized from piperazine having only a secondary amino group can suppress the generation of gases such as H 2 S and CS 2 to a very small amount, and has an extremely high ability to immobilize heavy metals contained in fly ash. Since it is high, it is particularly suitable in the present invention.
本発明のジチオカルバミン酸塩としては、例えば、上記のジチオカルバミン酸のアルカリ金属塩又はアンモニウム塩が挙げられる。これらのうち水に溶解し得るリチウム、ナトリウム、カリウム、アンモニウムの塩が好ましい。更に、熱的に安定でかつ安価なことからナトリウム塩又はカリウム塩が特に好ましい。 Examples of the dithiocarbamate of the present invention include the alkali metal salts or ammonium salts of the above dithiocarbamic acids. Of these, lithium, sodium, potassium, and ammonium salts that are soluble in water are preferred. Furthermore, a sodium salt or a potassium salt is particularly preferable because it is thermally stable and inexpensive.
これらのジチオカルバミン酸塩は、１種単独又は２種以上の混合物として使用することができる。 These dithiocarbamates can be used singly or as a mixture of two or more.
前記ジチオカルバミン酸塩の中でも、溶解度が高く、熱的にも安定でかつ安価なピペラジンジチオカルバミン酸のカリウム塩又はナトリウム塩が、特に好ましい。 Among the dithiocarbamates, the potassium salt or sodium salt of piperazine dithiocarbamic acid, which has high solubility, is thermally stable and is inexpensive, is particularly preferable.
ジチオカルバミン酸はアミノ基と当量の二硫化炭素の反応により得られるが、二硫化炭素の添加量を少なくすることにより、未反応のアミノ基を存在させることができる。本発明のジチオカルバミン酸塩水溶液は、アミノ基をジチオカルバミン酸基に対して２．０モル％以下、好ましくは０．１〜１．８モル％含有する。この範囲でアミノ基を含有すると、ジチオカルバミン酸は安定に存在し、固体廃棄物中の重金属を固定化処理する際に、Ｈ２Ｓ、ＣＳ２等のガス発生を抑制できる。アミノ基をジチオカルバミン酸基に対して２．０％を越えて含有すると、重金属の固定化能が低下する。前記ピペラジンジチオカルバミン酸塩の場合、ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸塩を９６モル％以上含有し、残りはピペラジン−Ｎ−ジチオカルバミン酸塩である。 Although dithiocarbamic acid is obtained by the reaction of an amino group and an equivalent amount of carbon disulfide, an unreacted amino group can be present by reducing the amount of carbon disulfide added. The dithiocarbamate aqueous solution of the present invention contains 2.0 mol% or less, preferably 0.1 to 1.8 mol% of amino groups with respect to the dithiocarbamic acid groups. When the amino group is contained in this range, dithiocarbamic acid is stably present, and generation of gas such as H 2 S and CS 2 can be suppressed when the heavy metal in the solid waste is fixed. If the amino group is contained in an amount exceeding 2.0% with respect to the dithiocarbamic acid group, the ability to immobilize heavy metals decreases. In the case of the piperazine dithiocarbamate, piperazine-N, N′-bisdithiocarbamate is contained in an amount of 96 mol% or more, and the rest is piperazine-N-dithiocarbamate.
また、本発明のジチオカルバミン酸塩水溶液は、チオ炭酸塩を０．０３重量％未満、好ましくは０．０２重量％未満含有する。チオ炭酸塩は固体廃棄物中の重金属を固定化処理する際に、Ｈ２Ｓ、ＣＳ２等のガス発生の原因となるため、これを含まないことが好ましい。チオ炭酸塩を０．０３重量％以上含有すると、固体廃棄物中の重金属を固定化処理する際に、Ｈ２Ｓ、ＣＳ２等のガス発生を抑制できなくなる。 The dithiocarbamate aqueous solution of the present invention contains thiocarbonate less than 0.03% by weight, preferably less than 0.02% by weight. Since thiocarbonate causes gas generation of H 2 S, CS 2 and the like when immobilizing heavy metals in solid waste, it is preferable not to include them. When the thiocarbonate is contained in an amount of 0.03% by weight or more, generation of gases such as H 2 S and CS 2 cannot be suppressed when the heavy metal in the solid waste is fixed.
本発明のジチオカルバミン酸塩水溶液は、従来上記アミン化合物を水に溶解させ、これに二硫化炭素並びにアルカリ金属化合物を添加して反応させる等の方法により製造されている。しかしながら、原料となる二硫化炭素並びにアルカリ金属化合物の仕込み方法によっては、アミノ基の含有量がジチオカルバミン酸基に対して２．０モル％を越え、また、チオ炭酸塩が０．０３重量％以上となった結果、固体廃棄物中の重金属を固定化処理する際に、Ｈ２Ｓ、ＣＳ２等のガス発生が極めて高いものになったり、固体廃棄物中に含まれる重金属の固定化能が低下する場合を生じる。 The aqueous dithiocarbamate solution of the present invention is conventionally produced by a method in which the above amine compound is dissolved in water, and carbon disulfide and an alkali metal compound are added thereto to react. However, depending on the preparation method of carbon disulfide and alkali metal compound used as raw materials, the content of amino groups exceeds 2.0 mol% with respect to dithiocarbamic acid groups, and the thiocarbonate content is 0.03% by weight or more. As a result, when immobilizing heavy metals in solid waste, gas generation such as H 2 S and CS 2 becomes extremely high, and the ability to immobilize heavy metals contained in solid waste The case where it falls is produced.
本発明のジチオカルバミン酸塩水溶液は、アミン化合物と二硫化炭素とアルカリ金属化合物を反応させるジチオカルバミン酸塩水溶液の製造方法において、アミン化合物中のアミノ基に対する二硫化炭素のモル比を０．９８〜１．０、好ましくは０．９９〜１．０とすることにより製造することができる。アミン化合物中のアミノ基量に対する二硫化炭素のモル比が０．９８未満では、アミノ基の含有量がジチオカルバミン酸基に対して２．０モル％を越え、また１．０を超えるとチオ炭酸塩が０．０３重量％以上となる。 The dithiocarbamate aqueous solution of the present invention is a method for producing a dithiocarbamate aqueous solution in which an amine compound, carbon disulfide, and an alkali metal compound are reacted. The molar ratio of carbon disulfide to amino groups in the amine compound is 0.98 to 1. 0.0, preferably 0.99 to 1.0. When the molar ratio of carbon disulfide to the amount of amino groups in the amine compound is less than 0.98, the content of amino groups exceeds 2.0 mol% with respect to the dithiocarbamic acid group, and when it exceeds 1.0, The salt is 0.03% by weight or more.
また、最終的に二硫化炭素に対するアルカリ金属化合物のモル比を１．０〜１．３、好ましくは１．０〜１．２となるようアルカリ金属化合物を反応させることにより、ジチオカルバミン酸塩は水溶液中で安定に存在する。 In addition, the dithiocarbamate is dissolved in an aqueous solution by reacting the alkali metal compound so that the molar ratio of the alkali metal compound to carbon disulfide is finally 1.0 to 1.3, preferably 1.0 to 1.2. It exists in the stable.
さらに、アミン化合物と二硫化炭素とアルカリ金属化合物を反応させる際に、アミン化合物の水溶液に、反応させる二硫化炭素の一部を添加し反応・熟成させた後、反応させるアルカリ金属化合物の一部を添加し反応・熟成させる操作（以下、分割添加という）を３回以上繰り返すことが好ましい。この操作では、第一工程としてアルカリ金属化合物を二硫化炭素に対してモル比で０．９７〜１．０、好ましくは０．９８〜１．０添加し反応・熟成させる操作を２回以上繰り返した後、更に第二工程として残りの二硫化炭素を添加し反応・熟成させた後、アルカリ金属化合物を二硫化炭素に対してモル比で１．０以上添加し反応・熟成させることが好ましい。アルカリ金属の量を第一工程で、先に添加した二硫化炭素に対して反応モル比で０．９７〜１．０添加することによりチオ炭酸塩の発生を著しく抑えることが可能となり、第二工程で、添加した二硫化炭素に対して反応モル比で１．０以上添加し、最終的に添加する全二硫化炭素に対する全アルカリ金属化合物の反応モル比を１．０〜１．３にする。 Furthermore, when reacting an amine compound, carbon disulfide, and an alkali metal compound, a part of the carbon disulfide to be reacted is added to the aqueous solution of the amine compound, reacted and aged, and then a part of the alkali metal compound to be reacted It is preferable to repeat the operation of adding and reacting and aging (hereinafter referred to as divided addition) three or more times. In this operation, as a first step, an alkali metal compound is added in a molar ratio of 0.97 to 1.0, preferably 0.98 to 1.0 with respect to carbon disulfide, and the reaction and aging are repeated twice or more. Then, after the remaining carbon disulfide is further added and reacted / ripened in the second step, it is preferable to add the alkali metal compound in a molar ratio of 1.0 or more with respect to carbon disulfide to cause the reaction / ripening. In the first step, the amount of alkali metal added in a reaction molar ratio of 0.97 to 1.0 with respect to the previously added carbon disulfide makes it possible to significantly suppress the generation of thiocarbonate. In the process, a reaction molar ratio of 1.0 or more is added to the added carbon disulfide, and the reaction molar ratio of all alkali metal compounds to all the carbon disulfide to be finally added is set to 1.0 to 1.3. .
添加する二硫化炭素の量は、第一工程ではアミン化合物中のアミノ基に対してモル比で０．３３以下、第二工程では０．５０以下であることが好ましく、添加する総量は前記の０．９８〜１．０とすることが必要である。 The amount of carbon disulfide to be added is preferably 0.33 or less in terms of molar ratio to the amino group in the amine compound in the first step, and 0.50 or less in the second step. It is necessary to set it as 0.98-1.0.
アミン化合物の水溶液に二硫化炭素を好ましくは０．５０等量／分以下、更に好ましくは０．０５０等量／分以下の速度で添加する。 Carbon disulfide is added to the aqueous solution of the amine compound at a rate of preferably 0.50 equivalent / minute or less, more preferably 0.050 equivalent / minute or less.
アミン化合物の水溶液に二硫化炭素添加した結果得られたジチオカルバミン酸水溶液に、アルカリ金属化合物を好ましくは０．１０等量／分以下、更に好ましくは０．０１０等量／分以下の速度で添加する。特に前記３回以上の分割添加のうち少なくとも１回の操作では、０．０１０等量／分以下の速度で添加することが好ましい。 The alkali metal compound is preferably added at a rate of 0.10 equivalent / minute or less, more preferably 0.010 equivalent / minute or less, to the dithiocarbamic acid aqueous solution obtained as a result of adding carbon disulfide to the aqueous solution of the amine compound. . In particular, in at least one of the three or more divided additions, it is preferable to add at a rate of 0.010 equivalent / minute or less.
本発明のジチオカルバミン酸塩水溶液の原料に使用されるアルカリ金属化合物としては、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や炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩が挙げられる。 Examples of the alkali metal compound used as a raw material for the aqueous dithiocarbamate solution of the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate. Examples include carbonates.
本発明のジチオカルバミン酸塩水溶液を工業的に製造するに際しては、原料アミンの濃度を正確に、また簡便に定量することが極めて重要であるが、その定量手段として屈折計が好適に用いられる。また、二硫化炭素の添加量を正確に、また簡便に定量することも合わせて重要であるが、その定量法として質量流量計が好適に用いられる。 In industrially producing the dithiocarbamate aqueous solution of the present invention, it is extremely important to accurately and simply quantify the concentration of the raw material amine, but a refractometer is preferably used as the quantification means. It is also important to accurately and simply quantify the amount of carbon disulfide added, but a mass flow meter is preferably used as the quantification method.
前記のジチオカルバミン酸塩水溶液は、重金属固定化処理剤として用いることができ、重金属を含有する固体廃棄物に、添加，混錬することにより、重金属を固定化することができる。 The aqueous dithiocarbamate solution can be used as a heavy metal immobilizing agent, and heavy metals can be immobilized by adding and kneading to a solid waste containing heavy metals.
固体廃棄物としては、飛灰、土壌等が挙げられる。飛灰は、特に限定されるものではないが、通常都市ゴミや産業廃棄物等の焼却施設から排出され、ＥＰ、ＢＦ、マルチサイクロン等で捕集された灰塵を指す。 Examples of solid waste include fly ash and soil. Fly ash is not particularly limited, but refers to ash dust that is normally discharged from incineration facilities such as municipal waste and industrial waste and collected by EP, BF, multi-cyclone, and the like.
本発明の重金属の固定化処理方法において、ジチオカルバミン酸塩水溶液の使用量は、処理する固体廃棄物中の重金属の含有量や重金属の形態により異なるが、通常固体廃棄物に対して固形物換算重量で０．００５〜２０重量％の範囲であり、好ましくは０．０１〜１０重量％の範囲である。この範囲に満たない場合は、固体廃棄物中の重金属固定化処理が不十分であったり、また、この範囲を越えた場合には、経済的に不利となる場合がある。 In the heavy metal immobilization treatment method of the present invention, the amount of dithiocarbamate aqueous solution used varies depending on the heavy metal content in the solid waste to be treated and the form of heavy metal, but it is usually a solid equivalent weight relative to the solid waste. In the range of 0.005 to 20% by weight, preferably in the range of 0.01 to 10% by weight. If it is less than this range, the heavy metal immobilization treatment in the solid waste is insufficient, and if it exceeds this range, it may be economically disadvantageous.
固体廃棄物中の重金属の固定化処理方法において使用される水溶液の量は、処理する固体廃棄物に対して５〜５０重量％の範囲で使用される。５重量％未満の量を使用した場合では、薬剤との混練状態が不充分となることがあり、５０重量％を越える量を使用した場合には、処理して得られる固体廃棄物が液状となり、廃棄が困難となることがある。 The amount of the aqueous solution used in the method for immobilizing heavy metals in solid waste is used in the range of 5 to 50% by weight based on the solid waste to be treated. When the amount less than 5% by weight is used, the kneading state with the drug may be insufficient. When the amount exceeding 50% by weight is used, the solid waste obtained by the treatment becomes liquid. Disposal may be difficult.
本発明の重金属の固定化処理方法において、固定化される固体廃棄物中の重金属は、一般にジチオカルバミン酸基がキレートすることによって水溶液から不溶化できる金属であり、具体的には、鉛、水銀、クロム、カドミウム、亜鉛、銅、ニッケル、砒素、セレン等が例示できる。特に、鉛、水銀、クロム、カドミウム、ニッケル、亜鉛、銅についてはキレート効果が高く、除去の効率が良い。 In the heavy metal immobilization treatment method of the present invention, the heavy metal in the solid waste to be immobilized is generally a metal that can be insolubilized from an aqueous solution by chelating a dithiocarbamic acid group. Specifically, lead, mercury, chromium , Cadmium, zinc, copper, nickel, arsenic, selenium and the like. In particular, lead, mercury, chromium, cadmium, nickel, zinc, and copper have high chelating effects and good removal efficiency.
本発明のジチオカルバミン酸塩水溶液は、固体廃棄物中の重金属を固定化処理する際に、Ｈ２Ｓ、ＣＳ２等のガス発生を極微量に抑制でき、かつ、重金属に対するキレート能力が高く、高アルカリ性飛灰においても少量の添加で効果を発揮し経済的であるとともに、他の助剤の使用に際して安全かつ簡便な処理方法にて実施できるので、工業的にも非常に有用である。 The dithiocarbamate aqueous solution of the present invention can suppress the generation of gases such as H 2 S and CS 2 in an extremely small amount when immobilizing heavy metals in solid waste, and has a high chelating ability with respect to heavy metals. Alkaline fly ash is economically effective when added in a small amount, and it can be carried out by a safe and simple treatment method when using other auxiliaries.
次に、実施例によりさらに詳細に本発明を説明する。但し、本発明は下記実施例によってなんら制限を受けるものではない。 Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
合成例１ ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．１）
ガラス製容器中に、ピペラジン１１重量部、水３７重量部を入れ、この混合溶液中に撹拌しながら４０℃で二硫化炭素を理論モル比の１／４量に相当する４．８重量部を２０分間で滴下し１０分間熟成後にＫＯＨ４８．５％水溶液７重量部を２０分間で滴下し、２０分間熟成させた。上記の操作をさらに３度繰り返した。但し、４度目のＫＯＨ４８．５％水溶液は１１重量部を１００分間で滴下した。滴下終了後、同温度にて約１時間熟成を行ったところ、うす緑色透明の液体を得た。ヨード滴定により測定した結果、この水溶液中のピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム濃度は４０重量％であった。
Synthesis Example 1 Piperazine-N, N′-bisdithiocarbamate potassium (Compound No. 1)
In a glass container, 11 parts by weight of piperazine and 37 parts by weight of water are placed, and 4.8 parts by weight of carbon disulfide corresponding to 1/4 of the theoretical molar ratio is added to this mixed solution at 40 ° C. with stirring. After dropping for 20 minutes and aging for 10 minutes, 7 parts by weight of 48.5% KOH aqueous solution was added dropwise for 20 minutes and aged for 20 minutes. The above operation was repeated three more times. However, 11 parts by weight of the 4th KOH 48.5% aqueous solution was dropped in 100 minutes. After completion of the dropwise addition, the mixture was aged for about 1 hour at the same temperature to obtain a light green transparent liquid. As a result of iodometric titration, the concentration of piperazine-N, N′-bisdithiocarbamate potassium in this aqueous solution was 40% by weight.
合成例２ トリエチレンテトラミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４−テトラジチオカルバミン酸ナトリウム（化合物Ｎｏ．２）
ガラス製容器中に、トリエチレンテトラミン（ジエチレントリアミン含有率０．５％以下）１１重量部、水３９重量部を入れ、この混合液中に撹拌しながら４０℃以下で二硫化炭素を理論モル比の１／４量に相当する７．５重量部を２０分間で滴下し１０分間熟成後にＮａＯＨ４８．０％水溶液８重量部を２０分間で滴下し、２０分間熟成させた。上記の操作をさらに３度繰り返した。但し、４度目のＮａＯＨ４８．０％水溶液は１２重量部を１００分間で滴下した。滴下終了後、同温度にて約２時間熟成を行ったところ、黄褐色透明液体を得た。ヨード滴定により測定した結果、この水溶液中のジチオカルバミン酸塩濃度は４０重量％であった。
Synthesis Example 2 Triethylenetetramine-N1, N2, N3, N4-tetradithiocarbamate sodium (Compound No. 2)
In a glass container, 11 parts by weight of triethylenetetramine (diethylenetriamine content of 0.5% or less) and 39 parts by weight of water are placed, and carbon disulfide is added at a theoretical molar ratio of 40 ° C. or less while stirring in this mixture. 7.5 parts by weight corresponding to ¼ amount was added dropwise over 20 minutes and after aging for 10 minutes, 8 parts by weight of NaOH 48.0% aqueous solution was added dropwise over 20 minutes and aged for 20 minutes. The above operation was repeated three more times. However, 12 parts by weight of the 4th NaOH 48.0% aqueous solution was dropped in 100 minutes. After completion of the dropwise addition, the mixture was aged at the same temperature for about 2 hours to obtain a tan transparent liquid. As a result of iodometric titration, the concentration of dithiocarbamate in this aqueous solution was 40% by weight.
合成例３ ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．３）
ピペラジン９．８重量部を入れた以外は合成例１と全く同じ方法で合成を行ったところ、褐色透明液体を得た。ヨード滴定により測定した結果、この水溶液中のジチオカルバミン酸塩濃度は４０．５重量％であった。
Synthesis Example 3 Piperazine-N, N′-bisdithiocarbamate potassium (Compound No. 3)
The synthesis was performed in exactly the same manner as in Synthesis Example 1 except that 9.8 parts by weight of piperazine was added, and a brown transparent liquid was obtained. As a result of iodometric titration, the dithiocarbamate concentration in this aqueous solution was 40.5% by weight.
合成例４ ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．４）
ピペラジン１２重量部を入れた以外は合成例１と全く同じ方法で合成を行ったところ、褐色透明液体を得た。ヨード滴定により測定した結果、この水溶液中のジチオカルバミン酸塩濃度は４０重量％であった。
Synthesis Example 4 Piperazine-N, N′-bisdithiocarbamate potassium (Compound No. 4)
The synthesis was performed in exactly the same manner as in Synthesis Example 1 except that 12 parts by weight of piperazine was added, and a brown transparent liquid was obtained. As a result of iodometric titration, the concentration of dithiocarbamate in this aqueous solution was 40% by weight.
参考例１〜参考例４
化合物Ｎｏ．１〜４についてジチオカルバミン酸塩水溶液中のアミノ基の濃度をＮＭＲにより測定した。
Reference Example 1 to Reference Example 4
Compound No. About 1-4, the density | concentration of the amino group in the dithiocarbamate aqueous solution was measured by NMR.
また、チオ炭酸塩濃度をイオンクロマトグラフ測定法により求めた。東ソー製のカラムＴＳＫｇｅｌ ＩＣ−Ａｎｉｏｎ−ＰＷｘｌＰＥＥＫ（長さ７．５ｃｍ、内径４．６ｍｍ）を用い、［５０ｍＭのＮａ２ＣＯ３＋２ｍＭの四ホウ酸ナトリウム］／アセトニトリル＝８／２を溶離液とし、１ｍＭ ＫＯＨで５０００倍に希釈した試料液を１０μｌ注入し、波長２８５ｎｍの紫外線検出器を用い、温度４０℃、毎分１ｍｌの流速で分析した。 Further, the thiocarbonate concentration was determined by an ion chromatographic measurement method. Using Tosoh column TSKgel IC-Anion-PWxlPEEK (length 7.5 cm, inner diameter 4.6 mm), [50 mM Na 2 CO 3 +2 mM sodium tetraborate] / acetonitrile = 8/2 as an eluent, 10 μl of a sample solution diluted 5000 times with 1 mM KOH was injected and analyzed using an ultraviolet detector with a wavelength of 285 nm at a temperature of 40 ° C. and a flow rate of 1 ml per minute.
更に、化合物Ｎｏ．１〜６の水溶液を６５℃に加温して二硫化炭素ガスの発生について調べた。結果を表１に示す。 Furthermore, Compound No. The aqueous solutions 1 to 6 were heated to 65 ° C., and the generation of carbon disulfide gas was examined. The results are shown in Table 1.
重金属処理試験ＢＦ灰（Ｃａ＝３０．７％、Ｎａ＝１．４％、Ｋ＝１．６％、Ｐｂ＝２０００ｐｐｍ、Ｃｕ＝１５０ｐｐｍを含む）１００重量部に対し、水３０重量部を加え、さらにピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．１）を０．４部（固形分換算）添加、混練した後、環境庁告示第１３号試験に従い溶出試験を行った。鉛の溶出結果を表２に示す。鉛以外の重金属については、亜鉛は４ｐｐｍ以下、クロムは０．０５ｐｐｍ以下、カドミウム、水銀、銅、ニッケルについてはいずれも０．０１ｐｐｍ以下であった。
Heavy metal treatment test BF ash (Ca = 30.7%, Na = 1.4%, K = 1.6%, Pb = 2000 ppm, including Cu = 150 ppm) is added to 30 parts by weight of water, Further, 0.4 parts (in terms of solid content) of potassium piperazine-N, N′-bisdithiocarbamate (compound No. 1) was added and kneaded, and then an elution test was conducted according to the Environmental Agency Notification No. 13 test. The lead elution results are shown in Table 2. Regarding heavy metals other than lead, zinc was 4 ppm or less, chromium was 0.05 ppm or less, and cadmium, mercury, copper, and nickel were all 0.01 ppm or less.
実施例２
トリエチレンテトラミン−Ｎ１，Ｎ２，Ｎ３，Ｎ４−テトラジチオカルバミン酸ナトリウム（化合物Ｎｏ．２）１５％水溶液を４部となるように添加する以外は、実施例１と同様にして、重金属処理試験を行った。結果を表２に合わせて示す。鉛以外の重金属については、亜鉛は４ｐｐｍ以下、クロムは０．０５ｐｐｍ以下、カドミウム、水銀、銅、ニッケルについてはいずれも０．０１ｐｐｍ以下であった。
Example 2
A heavy metal treatment test was conducted in the same manner as in Example 1 except that 15% aqueous solution of sodium triethylenetetramine-N1, N2, N3, N4-tetradithiocarbamate (Compound No. 2) was added to 4 parts. It was. The results are shown in Table 2. Regarding heavy metals other than lead, zinc was 4 ppm or less, chromium was 0.05 ppm or less, and cadmium, mercury, copper, and nickel were all 0.01 ppm or less.
比較例１
ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．３）となるように添加する以外は実施例１と同様にして、重金属処理試験を行った。結果を表２に合わせて示す。
Comparative Example 1
A heavy metal treatment test was conducted in the same manner as in Example 1 except that piperazine-N, N′-bisdithiocarbamate potassium (Compound No. 3) was added. The results are shown in Table 2.
比較例２
ピペラジン−Ｎ，Ｎ’−ビスジチオカルバミン酸カリウム（化合物Ｎｏ．４）を使用する以外は、実施例１と同様にして、重金属処理試験を行った。結果を表２に合わせて示す。
Comparative Example 2
A heavy metal treatment test was conducted in the same manner as in Example 1 except that piperazine-N, N′-bisdithiocarbamate potassium (Compound No. 4) was used. The results are shown in Table 2.
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