JP5678401B2 - Heavy metal treating agent and method for treating heavy metal contaminants using the same - Google Patents
Heavy metal treating agent and method for treating heavy metal contaminants using the same Download PDFInfo
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本発明は、重金属を含有する固体廃棄物、例えば、ゴミ焼却場から排出される焼却灰及び飛灰、重金属に汚染された土壌、排水処理後に生じる汚泥、工場から排出される排水等に含有される鉛、カドミウム、水銀、ヒ素、セレン、六価クロム等の有害な重金属を簡便、かつ高効率で安定的に固定化することのできる重金属処理剤、並びに重金属汚染物の処理方法に関するものである。 The present invention is contained in solid waste containing heavy metals, for example, incineration ash and fly ash discharged from garbage incineration plants, soil contaminated with heavy metals, sludge generated after wastewater treatment, wastewater discharged from factories, etc. Heavy metal treatment agent that can stably and efficiently fix harmful heavy metals such as lead, cadmium, mercury, arsenic, selenium and hexavalent chromium, and a method for treating heavy metal contaminants .
都市ゴミ焼却工場などから排出される飛灰は重金属含有率が高く、重金属の溶出を抑制する処理を施すことが必要である。その様な処理方法のひとつとして薬剤処理法があり、キレート系薬剤等の重金属処理剤を添加して重金属を不溶化する方法が用いられている。 Fly ash discharged from municipal waste incineration plants and the like has a high heavy metal content and needs to be treated to suppress elution of heavy metals. As one of such treatment methods, there is a drug treatment method, and a method of insolubilizing heavy metals by adding a heavy metal treatment agent such as a chelate-type drug is used.
キレート系薬剤としてはアミン誘導体のカルボジチオ酸塩が主に用いられている。特にピペラジンカルボジチオ酸塩は他のアミン誘導体と比較しても硫化水素及び二硫化炭素等の有害ガス発生が少ないことが、重金属処理剤として広く用いられている。（例えば特許文献１参照）しかし、重金属汚染物質に含有されるヒ素、セレン、六価クロム等はアニオン種の形態で存在し、アミン誘導体のカルボジチオ酸塩などのキレート系薬剤で処理することは困難であった。 As chelating agents, carbodithioates of amine derivatives are mainly used. In particular, piperazine carbodithioate is widely used as a heavy metal treating agent because it produces less harmful gases such as hydrogen sulfide and carbon disulfide than other amine derivatives. However, arsenic, selenium, hexavalent chromium, etc. contained in heavy metal contaminants are present in the form of anionic species and are difficult to treat with chelating agents such as carbodithioates of amine derivatives. Met.
それに対して、重金属汚染物質を硫化鉄で処理する方法が知られている。（例えば特許文献２）しかし、硫化鉄を用いてもヒ素、セレン、六価クロム等のアニオン種に関して効果が不十分な場合があり、さらには硫化鉄では鉛やカドミウム、水銀といったカチオン種に対しても効果が弱いという問題があった。 On the other hand, a method of treating heavy metal contaminants with iron sulfide is known. (For example, Patent Document 2) However, even if iron sulfide is used, the effect on anion species such as arsenic, selenium, and hexavalent chromium may be insufficient. Further, iron sulfide is effective against cationic species such as lead, cadmium, and mercury. However, there was a problem that the effect was weak.
一方、各種重金属の処理にタンニン（タンニン酸）を用いて処理する方法が知られている。（特許文献３、４、５参照）しかし、従来タンニン成分を用いる方法では、タンニンを多量に用いることが必要である上に、処理性能がｐＨに左右され、弱酸性から中性領域ではある程度性能を発現するが、アルカリ性においては処理性能が不十分となる問題があった。 On the other hand, a method of treating various heavy metals with tannin (tannic acid) is known. However, in the conventional method using a tannin component, it is necessary to use a large amount of tannin, and the processing performance depends on the pH, so that the performance is slightly improved from weakly acidic to neutral regions. However, there is a problem that the processing performance is insufficient in the case of alkalinity.
重金属汚染物質、特に六価クロム等のアニオン種の重金属の処理では、アルカリ性においては処理が困難であり、主にアルカリ性で処理されるカチオン種の重金属と同時に処理をすることができなかった。 In the treatment of heavy metal contaminants, particularly heavy metals of anionic species such as hexavalent chromium, the treatment is difficult in the alkalinity, and the treatment cannot be performed at the same time as the heavy metals of the cationic species that are mainly treated in the alkaline manner.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、重金属汚染物質の処理においてタンニンと、珪酸塩及び鉄化合物及び／又はマグネシウム塩を含んでなる重金属処理剤では、従来処理が困難であったアニオン種の六価クロムの高レベルの除去（環境基準０．０５ｍｇ／Ｌ以下でさらには０．０１ｍｇ／Ｌレベル）が可能であり、当該重金属処理剤はアルカリ性で高い性能を発揮するため、鉛等のカチオン種の重金属処理に用いられるアミンのジチオカルバミン酸塩と直接併用することによりアニオン種とカチオン種の両者を同時に除去することが可能であることを見出し、本発明を完成するに到ったものである。 As a result of intensive studies to solve the above-described problems, the present inventors have conducted conventional treatments with heavy metal treatment agents comprising tannin and silicates and iron compounds and / or magnesium salts in the treatment of heavy metal contaminants. High level removal of hexavalent chromium, an anionic species that was difficult to achieve (environmental standard 0.05 mg / L or less, and further 0.01 mg / L level), the heavy metal treating agent is alkaline and has high performance. As a result, it was found that it is possible to remove both anionic species and cationic species at the same time by directly using dithiocarbamate of amine used for heavy metal treatment of cationic species such as lead, and completed the present invention. This is what it came to.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の重金属処理剤はタンニン、珪酸塩、及び鉄化合物及び／又はマグネシウム塩を含んでなるものである。 The heavy metal treating agent of the present invention comprises tannin, silicate, iron compound and / or magnesium salt.
タンニン（ｔａｎｎｉｎ）は、酸、アルカリ、酵素で多価フェノール酸と多価アルコールに加水分解する加水分解型と複数分子のカテキンが炭素−炭素結合で縮合する縮合型に大別され、タンパク質、アルカロイド、金属イオン等と結合し得る難溶性の塩を形成する水溶性化合物で、複数のフェノール性ヒドロキシ基を持つ芳香族化合物である。分子量としては５００程度の低分子化合物から２００００に達する巨大な物まであるが、いずれも用いることができる。タンニン酸と称されることもある。タンニンは従来革製品に工業的に用いられており、例えばケブラッチョ（木材）から抽出されたケブラッチョタンニン等が例示できる。 Tannins are broadly classified into hydrolyzed forms that hydrolyze polyhydric phenol acids and polyhydric alcohols with acids, alkalis, and enzymes, and condensed forms in which multiple molecules of catechins are condensed with carbon-carbon bonds. A water-soluble compound that forms a sparingly soluble salt that can bind to metal ions and the like, and is an aromatic compound having a plurality of phenolic hydroxy groups. The molecular weight ranges from a low molecular weight compound of about 500 to a huge material reaching 20000, any of which can be used. Sometimes called tannic acid. Tannin is conventionally used industrially for leather products, and examples thereof include quebrach tannin extracted from quebratcho (wood).
珪酸塩としては珪酸カルシウム、珪酸マグネシウム、珪酸ナトリウム、酸化ケイ素を用いることができるが、処理性能に優れた珪酸カルシウム及び／又は珪酸マグネシウムが好ましい。 As the silicate, calcium silicate, magnesium silicate, sodium silicate, and silicon oxide can be used, and calcium silicate and / or magnesium silicate excellent in processing performance is preferable.
鉄化合物としては塩化第一鉄、塩化第二鉄、硫酸第一鉄、硫酸第二鉄をもちいることができるが、中でも塩化第一鉄、塩化第二鉄が好ましい。 As the iron compound, ferrous chloride, ferric chloride, ferrous sulfate and ferric sulfate can be used, among which ferrous chloride and ferric chloride are preferable.
マグネシウム塩としては、硫酸塩、塩酸塩、硝酸塩、炭酸塩、水酸化物が上げられるが、価格から硫酸塩及び／又は塩酸塩を用いることが好ましい。 Examples of magnesium salts include sulfates, hydrochlorides, nitrates, carbonates, and hydroxides, but sulfates and / or hydrochlorides are preferably used from the viewpoint of cost.
タンニンはそれ単独で金属と結合して難溶性の化合物を形成するが、タンニン自身が金属と結合したものでは金属が再溶解し易いため、それ単独を用いた場合には重金属をある程度処理（固定化）することはできても、重金属処理剤としては不十分である。またタンニンと珪酸塩、又はタンニンと鉄化合物或いはマグネシウム塩だけを組合せて用いても重金属処理能は不十分である。本発明では、タンニン（成分１）、珪酸塩（成分２）及び鉄化合物及び／又はマグネシウム塩（成分３）の３成分を必須の成分として用いることにより、少量のタンニンによって高度の重金属処理が可能となるものである。 Tannin alone binds to a metal to form a poorly soluble compound. However, when tannin itself binds to a metal, the metal is easy to redissolve. However, it is insufficient as a heavy metal treating agent. Further, even if a combination of tannin and silicate, or tannin and iron compound or magnesium salt is used in combination, the heavy metal treatment ability is insufficient. In the present invention, by using three components of tannin (component 1), silicate (component 2) and iron compound and / or magnesium salt (component 3) as essential components, a high level of heavy metal treatment is possible with a small amount of tannin. It will be.
本発明におけるタンニン（成分１）、珪酸塩（成分２）及び鉄化合物及び／又はマグネシウム塩（成分３）の組合せ比としては、これらの成分が含まれていれば特に限定はないが、（成分１）／（成分２）／（成分３）の重量比で１：１：１〜１：１０：１０の範囲が例示でき、特に（成分１）よりも（成分２）及び（成分３）の比率の大きい１：５：５、より好ましくは１：４：２等の組合せ比がより好ましい比として例示できる。 The combination ratio of tannin (component 1), silicate (component 2) and iron compound and / or magnesium salt (component 3) in the present invention is not particularly limited as long as these components are included. 1) / (Component 2) / (Component 3) can be exemplified by a weight ratio of 1: 1: 1 to 1:10:10, and more particularly (Component 2) and (Component 3) than (Component 1). A combination ratio such as 1: 5: 5 having a large ratio, more preferably 1: 4: 2, can be exemplified as a more preferable ratio.
本発明の重金属処理剤は、水溶液、スラリ−又は固相混合体のいずれの形態でも適用できるが、水溶性でない珪酸塩を用いる場合は固相混合体を用いることが好ましい。 The heavy metal treating agent of the present invention can be applied in any form of an aqueous solution, a slurry, or a solid phase mixture. However, when a silicate that is not water-soluble is used, it is preferable to use a solid phase mixture.
本発明の重金属処理剤はｐＨが７以上として用いることが好ましく、さらにｐＨ１０以上、特にｐＨ１２以上で用いることが好ましい。酸性領域ではアニオン種の重金属、特に六価クロムの処理能力が低下する傾向がある。 The heavy metal treating agent of the present invention is preferably used at a pH of 7 or more, more preferably at a pH of 10 or more, particularly preferably at a pH of 12 or more. In the acidic region, the processing capacity of anionic heavy metals, particularly hexavalent chromium, tends to decrease.
本発明の重金属処理剤は、さらにアミンのジチオカルバミン酸塩と併用することによりアニオンとカチオン両方の重金属を同時に処理することが可能である。 The heavy metal treating agent of the present invention can treat both anionic and cationic heavy metals at the same time by using it together with an amine dithiocarbamate.
アミンのジチオカルバミン酸塩は特に限定はなく、アミンとしてはモノアミンのジエチルアミンや、ポリアミンのジエチレントリアミン、テトラエチレンペンタミン等の鎖状アミンや、ピペラジン等の環状アミンが例示できる。中でもアミンのジチオカルバミン酸塩がピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸塩及び／又はピペラジン―Ｎ―カルボジチオ酸塩では、ｐＨが弱アルカリ性となっても硫化水素や二硫化炭素等の有害ガスの発生がないため、特に好ましい。 The amine dithiocarbamate is not particularly limited, and examples of the amine include monoamine diethylamine, polyamine diethylenetriamine, chain amines such as tetraethylenepentamine, and cyclic amines such as piperazine. Among them, the amine dithiocarbamate is piperazine-N, N′-biscarbodithioate and / or piperazine-N-carbodithioate, which is a harmful substance such as hydrogen sulfide or carbon disulfide even if the pH becomes weakly alkaline. Since there is no generation | occurrence | production, it is especially preferable.
ピペラジンカルボジチオ酸塩としては、ピペラジン−Ｎ−カルボジチオ酸塩、ピペラジ
ン−Ｎ，Ｎ’−ビスカルボジチオ酸塩、又はそれらの混合物が例示できる。特にピペラジ
ン−Ｎ，Ｎ’−ビスカルボジチオ酸塩、又はその比率の高いものが好ましい。これらの塩
としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、鉄等の金属錯体が用いられる。特に水溶性が必要な場合にはナトリウム塩、カリウム塩が好ましい。
Examples of the piperazine carbodithioate include piperazine-N-carbodithioate, piperazine-N, N′-biscarbodithioate, or a mixture thereof. In particular, piperazine-N, N′-biscarbodithioate or a compound having a high ratio thereof is preferable. As these salts, metal complexes such as alkali metal salts, alkaline earth metal salts, ammonium salts, and iron are used. In particular, when water solubility is required, sodium salt and potassium salt are preferable.
本発明の重金属処理剤は、本発明の重金属処理剤の構成成分であるタンニン、珪酸塩及び鉄化合物及び／又はマグネシウム塩を個別に重金属汚染物に添加することもできるが、所望とする組成比で事前に固相混合して一剤化したものを添加してもよい。 In the heavy metal treating agent of the present invention, tannin, silicate and iron compound and / or magnesium salt, which are constituents of the heavy metal treating agent of the present invention, can be individually added to heavy metal contaminants, but the desired composition ratio In addition, it is also possible to add a mixture obtained by solid phase mixing in advance.
アミンのジチオカルバミン酸塩はｐＨが弱アルカリ性となった場合、硫化水素や二硫化炭素等の有害ガスが発生する場合があるが、本発明の重金属処理剤は水存在下でｐＨが８以上を呈するため、アミンのジチオカルバミン酸塩と直接混合して処理できる。 When the pH of the amine dithiocarbamate becomes weakly alkaline, harmful gases such as hydrogen sulfide and carbon disulfide may be generated. However, the heavy metal treating agent of the present invention exhibits a pH of 8 or more in the presence of water. Therefore, it can be processed by directly mixing with the dithiocarbamate of amine.
本発明の重金属処理剤とアミンのジチオカルバミン酸塩は、いずれもアルカリ性で高性能を発揮するため、アルカリ性で鉛等のカチオン種の重金属固定化と六価クロム等のアニオン種の固定化が同時に処理できるものである。また、本発明の効果を損なわない範囲で、他の助剤を添加して用いてもよい。 Both the heavy metal treating agent of the present invention and the amine dithiocarbamate are alkaline and exhibit high performance, so that the alkaline heavy metal immobilization of cation species such as lead and the immobilization of anionic species such as hexavalent chromium are treated simultaneously. It can be done. Moreover, you may add and use another adjuvant in the range which does not impair the effect of this invention.
本発明の重金属処理剤は重金属汚染物と混合することにより重金属の固定化処理に用いることができる。重金属汚染物質は、特に限定されるものではないが、例えば焼却飛灰、排水、土壌、地下水等が例示できる。 The heavy metal treating agent of the present invention can be used for immobilizing heavy metals by mixing with heavy metal contaminants. Heavy metal contaminants are not particularly limited, and examples include incinerated fly ash, drainage, soil, and groundwater.
重金属汚染物質に対する使用量は、汚染物質中の重金属含有量によっても異なるため一概に規定できないが、均一に分散し易い水系処理物（排水、地下水）に対してはタンニンとして０．１〜１重量％、混合しにくい固形物系処理物（灰、土壌）に対してはタンニンとして０．５〜５％の範囲で混合することが好ましい。 The amount used for heavy metal pollutants varies depending on the heavy metal content in the pollutants and cannot be specified unconditionally. However, it is 0.1 to 1 weight as tannin for water-based treated products (drainage, groundwater) that are easily dispersed uniformly. %, It is preferable to mix in the range of 0.5 to 5% as tannins for solid processed products (ash, soil) that are difficult to mix.
本発明の重金属処理剤は、六価クロム等のアニオン種の重金属をアルカリ性領域で高度に処理でき、更に、アミンのジチオカルバミン酸塩水溶液からなるカチオン種の重金属処理剤と混合して用いることによりアニオン種とカチオン種を一度に高度に処理することが可能となる。 The heavy metal treating agent of the present invention is capable of highly treating heavy metals of anionic species such as hexavalent chromium in an alkaline region, and further mixed with a cationic heavy metal treating agent consisting of an aqueous solution of an amine dithiocarbamate. Species and cationic species can be processed at a high degree at once.
以下本発明を実施例で説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
タンニン（ケブラッチョタンニン）、珪酸カルシウム、塩化第二鉄を１：４：２の比率（重量比）に混合し、六価クロム１００ｐｐｍ含有する水溶液１００ｍＬ中に添加し、３０分間攪拌処理後、ろ過して溶液中に残存する六価クロム濃度を測定した。その際に水溶液のｐＨを４〜１２まで水酸化ナトリウムを用いて変化させた。結果を図１に示す。
Example 1
Tannin (Quebraccio tannin), calcium silicate, and ferric chloride are mixed at a ratio of 1: 4: 2 (weight ratio), added to 100 mL of an aqueous solution containing 100 ppm of hexavalent chromium, stirred for 30 minutes, and filtered. Then, the hexavalent chromium concentration remaining in the solution was measured. At that time, the pH of the aqueous solution was changed from 4 to 12 using sodium hydroxide. The results are shown in FIG.
ｐＨ７以上において、タンニン添加量が０．５重量％未満において環境基準の０．０５ｍｇ／Ｌ未満が達成された。 Above pH 7, the environmental standard of less than 0.05 mg / L was achieved when the tannin addition amount was less than 0.5% by weight.
実施例２
塩化第二鉄を硫酸マグネシウムに代えた以外は実施例１と同様にして処理を行った。
Example 2
The treatment was performed in the same manner as in Example 1 except that the ferric chloride was replaced with magnesium sulfate .
結果を図２に示す。ｐＨ１２以上においてタンニン添加量が０．５重量％未満において環境基準の０．０５ｍｇ／Ｌ未満が達成された。 The results are shown in FIG. The environmental standard of less than 0.05 mg / L was achieved when the tannin addition amount was less than 0.5% by weight at pH 12 or higher.
比較例１
塩化第二鉄をタンニンの不溶化剤として良く知られているゼラチンに代えた以外は実施例１と同様にして処理を行った。
Comparative Example 1
The treatment was performed in the same manner as in Example 1 except that gelatin, which is well known as a tannin insolubilizer, was used instead of ferric chloride.
結果を図３に示す。いずれのｐＨ領域においても環境基準の０．０５ｍｇ／Ｌ以下は達成されなかった。 The results are shown in FIG. The environmental standard of 0.05 mg / L or less was not achieved in any pH range.
実施例３
六価クロム溶出量（Ｃｒ６＋）が５ｐｐｍ、鉛溶出量（Ｐｂ）が１．７ｐｐｍ、カドミウム溶出量（Ｃｄ）が０．０６ｐｐｍのアルカリ飛灰に、ジチオカルバミン酸塩（ピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム）を成分とする東ソ−（株）製の重金属処理剤ＴＳ−３００を４重量％添加すると共に実施例１の組成の重金属処理剤を用いて、環境庁告示第１３号試験に従い処理した。処理時のｐＨは、１０．５であった。
Example 3
Hexavalent chromium elution amount (Cr 6+ ) of 5 ppm, lead elution amount (Pb) of 1.7 ppm and cadmium elution amount (Cd) of 0.06 ppm were added to alkali fly ash and dithiocarbamate (piperazine-N, N′- 4% by weight of Tosoh Co., Ltd. heavy metal treating agent TS-300 containing potassium biscarbodithioate) as a component and using the heavy metal treating agent having the composition of Example 1 were used. Processed according to the test. The pH during the treatment was 10.5.
添加した重金属処理剤中のタンニン量と六価クロムの処理能力の関係を図４に示した。 The relationship between the amount of tannin in the added heavy metal treating agent and the treatment capacity of hexavalent chromium is shown in FIG.
六価クロムは、タンニン４重量％の添加で固定化され、処理灰における管理基準（１．５ｐｐｍ）を達成した。また、Ｐｂ及びＣｄも０．０１ｐｐｍ以下となり、いずれの重金属元素も飛灰処理に係る判定基準を達成した。 Hexavalent chromium was immobilized by the addition of 4% by weight of tannin and achieved the control standard (1.5 ppm) in the treated ash. Moreover, Pb and Cd were also 0.01 ppm or less, and all the heavy metal elements achieved the determination standard regarding fly ash treatment.
実施例４
実施例１の組成の重金属処理剤を用いてヒ素の三価（Ａｓ３＋）及び五価（Ａｓ５＋）を１０ｐｐｍ含有する水溶液１００ｍＬをそれぞれ調整し、３０分間攪拌処理後、ろ過して溶液中に残存する砒素濃度を測定した。処理時のｐＨは、約１０であった。
Example 4
100 mL of an aqueous solution containing 10 ppm of trivalent (As 3+ ) and pentavalent (As 5+ ) arsenic was prepared using the heavy metal treating agent having the composition of Example 1, and after stirring for 30 minutes, the solution was filtered. The remaining arsenic concentration was measured. The pH during the treatment was about 10.
添加した重金属処理剤中のタンニン量と各ヒ素成分の処理能力の関係を図５に示した。 The relationship between the amount of tannin in the added heavy metal treating agent and the treatment ability of each arsenic component is shown in FIG.
各ヒ素成分は、タンニン０．５重量％で排水基準の０．１ｐｐｍ以下を達成した。 Each arsenic component achieved 0.5 ppm by weight of tannin and 0.1 ppm or less of the waste water standard.
処理剤の添加量と重金属処理能を表１に示す。 Table 1 shows the amount of treatment agent added and the ability to treat heavy metals.
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