JP2002194328A - Heavy metal fixing agent and method for fixing heavy metal using the same - Google Patents
Heavy metal fixing agent and method for fixing heavy metal using the sameInfo
- Publication number
- JP2002194328A JP2002194328A JP2000395181A JP2000395181A JP2002194328A JP 2002194328 A JP2002194328 A JP 2002194328A JP 2000395181 A JP2000395181 A JP 2000395181A JP 2000395181 A JP2000395181 A JP 2000395181A JP 2002194328 A JP2002194328 A JP 2002194328A
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- Japan
- Prior art keywords
- heavy metal
- fixing agent
- acid
- agent
- fixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、都市ゴミや産業廃
棄物等の焼却プラントで発生する飛灰、焼却灰や廃棄物
処理場から排出される汚泥、工場跡地等の汚染された土
壌、埋立処分場から排出される廃水、工場廃水等に含有
している有害な重金属類の溶出を防止する重金属固定化
剤及び重金属固定化方法に関する。The present invention relates to fly ash generated in an incineration plant for municipal garbage and industrial waste, incinerated ash and sludge discharged from a waste disposal site, contaminated soil such as a factory site, and landfill. The present invention relates to a heavy metal fixing agent and a heavy metal fixing method for preventing elution of harmful heavy metals contained in wastewater discharged from a disposal site, factory wastewater, and the like.
【０００２】[0002]
【従来の技術】都市ゴミや産業廃棄物の焼却プラントか
ら発生する飛灰等の廃棄物中には人体に有害な重金属類
が多量に含まれており、特に鉛、カドミウム、水銀等は
埋立地において雨水などにより溶出することが問題とさ
れている。近年、重金属含有廃棄物中の重金属を不溶
化、固定化する処理剤として、ジチオカルバミン酸系化
合物が種々報告されている。例えば、特開平３−２３１
９２１、特開平５−５００５５、特開平６−７９２５
４、特開平７−２８４７４８、特開平９−２３４４５０
等が挙げられる。2. Description of the Related Art Waste such as fly ash generated from an incineration plant for municipal garbage and industrial waste contains a large amount of heavy metals harmful to the human body. In particular, lead, cadmium and mercury are landfilled. It is problematic to elute with rainwater or the like. In recent years, various dithiocarbamic acid-based compounds have been reported as treatment agents for insolubilizing and immobilizing heavy metals in heavy metal-containing wastes. For example, Japanese Patent Application Laid-Open No. 3-231
921, JP-A-5-50055, JP-A-6-7925
4, JP-A-7-284748, JP-A-9-234450
And the like.
【０００３】[0003]
【発明が解決しようとする課題】ジチオカルバミン酸ア
ルカリ金属塩系の化合物は製造後、使用までの間、通常
水溶液の形で保存されているが、短期間の保存において
も不溶物の沈殿、浮遊物の発生が避けられないという問
題があった。また、ジチオカルバミン酸アルカリ金属塩
系の処理剤を飛灰などに混練する場合には、水により適
切な濃度に希釈して、飛灰等に噴霧される。希釈水に
は、水道水、河川水、地下水、工業用水等、種々の水が
使用されているが、これらの希釈水で希釈すると多量の
不溶物が発生し、希釈槽の底部への不溶物の沈殿、薬液
供給配管、電磁弁、噴霧ノズルの閉塞やスケール付着
等、種々の不具合が発生するという問題があった。従っ
て、これらの不具合の発生しない重金属固定化剤の開発
が望まれていた。The compound of the alkali metal dithiocarbamate is usually stored in the form of an aqueous solution until it is used after its production. There was a problem that occurrence of unavoidable. When the alkali metal dithiocarbamate-based treating agent is kneaded with fly ash or the like, the treatment agent is diluted to an appropriate concentration with water and sprayed on the fly ash or the like. Various waters such as tap water, river water, groundwater, and industrial water are used as the dilution water, but when diluted with these dilution waters, a large amount of insoluble matter is generated, and the insoluble matter at the bottom of the dilution tank is generated. There is a problem that various problems occur, such as sedimentation of the solution, clogging of a chemical solution supply pipe, a solenoid valve, and a spray nozzle and adhesion of scale. Therefore, development of a heavy metal fixing agent that does not cause these problems has been desired.
【０００４】[0004]
【課題を解決するための手段】本発明者らは前記課題を
解決すべく鋭意検討を重ねた結果、（ａ）ジチオカルバ
ミン酸アルカリ金属塩基を有する化合物、（ｂ）アミノ
ポリカルボン酸型キレート剤、（ｃ）水、を必須成分と
して含有する重金属固定化剤には、従来見られたような
不具合が発生しないことを見出し、本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that (a) a compound having an alkali metal dithiocarbamate, (b) an aminopolycarboxylic acid type chelating agent, The present inventors have found that the heavy metal fixing agent containing (c) water as an essential component does not have the disadvantages conventionally seen, and arrived at the present invention.
【０００５】本発明の第１は、（ａ）ジチオカルバミン
酸アルカリ金属塩基を有する化合物、（ｂ）アミノポリ
カルボン酸型キレート剤、（ｃ）水、を必須成分として
含有することを特徴とする重金属固定化剤に関する。A first aspect of the present invention is to provide a heavy metal comprising, as essential components, (a) a compound having an alkali metal dithiocarbamate, (b) an aminopolycarboxylic acid type chelating agent, and (c) water. It relates to a fixing agent.
【０００６】本発明の第２は、（ｂ）アミノポリカルボ
ン酸型キレート剤が、ニトリロ三酢酸、エチレンジアミ
ン四酢酸、ジエチレントリアミン五酢酸、アスパラギン
酸二酢酸、エチレンジアミンジコハク酸及びこれらのア
ルカリ金属塩（好ましくはナトリウム塩やカリウム
塩）、アンモニウム塩よりなる群から選ばれた少なくと
も１種のキレート剤である請求項１記載の重金属固定化
剤に関する。A second aspect of the present invention is that (b) the aminopolycarboxylic acid type chelating agent comprises nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic diacetate, ethylenediaminedisuccinic acid, and alkali metal salts thereof ( The heavy metal fixing agent according to claim 1, which is at least one chelating agent selected from the group consisting of ammonium salts and sodium salts.
【０００７】本発明の第３は、請求項１〜２のいずれか
記載の重金属固定化剤を重金属含有廃棄物に配合するこ
とを特徴とする重金属固定化方法に関する。A third aspect of the present invention relates to a method for immobilizing a heavy metal, which comprises mixing the heavy metal immobilizing agent according to any one of claims 1 to 2 into a heavy metal-containing waste.
【０００８】本発明の第４は、請求項３記載の重金属含
有廃棄物が飛灰または廃水である重金属固定化方法に関
する。A fourth aspect of the present invention relates to a method for immobilizing heavy metals, wherein the heavy metal-containing waste according to claim 3 is fly ash or wastewater.
【０００９】本発明で用いられるジチオカルバミン酸ア
ルカリ金属塩基を有する化合物としては、二硫化炭素と
アミン化合物から誘導されるものであり、特に限定され
ないが、好ましくはジエチルジチオカルバミン酸、ジブ
チルジチオカルバミン酸、ジエチレントリアミンビス
（ジチオカルバミン酸）、テトラエチレンペンタミンテ
トラキス（ジチオカルバミン酸）のナトリウム塩、カリ
ウム塩、リチウム塩などが挙げられる。特にナトリウム
塩、カリウム塩が好ましい。これらのジチオカルバミン
酸アルカリ金属塩基を有する化合物は単独で用いても良
いし、二種類以上を混合して用いても良い。The compound having an alkali metal dithiocarbamate used in the present invention is a compound derived from carbon disulfide and an amine compound, and is not particularly limited. (Dithiocarbamic acid), and sodium, potassium, and lithium salts of tetraethylenepentaminetetrakis (dithiocarbamic acid). Particularly, a sodium salt and a potassium salt are preferable. These compounds having an alkali metal dithiocarbamate may be used alone or in combination of two or more.
【００１０】ジチオカルバミン酸アルカリ金属塩基を有
する化合物の含有量としては、５〜８０重量％、好まし
くは１０〜６０重量％、特に好ましくは１５〜５５重量
％である。The content of the compound having an alkali metal dithiocarbamate is 5 to 80% by weight, preferably 10 to 60% by weight, particularly preferably 15 to 55% by weight.
【００１１】アミノポリカルボン酸型キレート剤として
は、ニトリロ三酢酸、エチレンジアミン四酢酸、ジエチ
レントリアミン五酢酸、アスパラギン酸二酢酸、エチレ
ンジアミンジコハク酸及びこれらの金属塩、アンモニウ
ム塩などが挙げられる。これらの中で特に、エチレンジ
アミン四酢酸、ジエチレントリアミン五酢酸、アスパラ
ギン酸二酢酸のナトリウム塩が好ましい。Examples of the aminopolycarboxylic acid type chelating agent include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic diacetate, ethylenediaminedisuccinic acid, and metal salts and ammonium salts thereof. Of these, the sodium salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and aspartic diacetate are particularly preferred.
【００１２】アミノポリカルボン酸型キレート剤の含有
量としては、０．０１〜２０重量％、好ましくは０．１
〜１０重量％である。０．０１重量％未満では不溶物の
抑制効果が不十分であり、２０重量％を越えると、重金
属固定化性能が低下する場合がある。The content of the aminopolycarboxylic acid type chelating agent is 0.01 to 20% by weight, preferably 0.1 to 20% by weight.
-10% by weight. If it is less than 0.01% by weight, the effect of suppressing insolubles is insufficient, and if it exceeds 20% by weight, the performance of immobilizing heavy metals may be reduced.
【００１３】本発明の重金属固定化剤を配合する方法と
しては、被処理物が廃水の場合は、添加するだけあるい
は添加、撹拌する方法が挙げられるが、被処理物が飛灰
等の固体の場合は、使用前に水で適切な濃度に希釈して
飛灰等の被処理物質に添加混練する方法が挙げられる。
例えば、本発明の重金属固定化剤１〜１００重量部を水
１〜１００重量部に希釈した重金属固定化剤の希釈液１
〜７０重量部を飛灰１００重量部に均一に添加混練す
る。このとき用いられる希釈水は水道水、河川水、地下
水、工業用水、再生水、イオン交換水、蒸留水などを用
いることができ、いずれを用いた場合でも不溶物の沈殿
等を生ずることはない。As a method of blending the heavy metal fixing agent of the present invention, when the substance to be treated is wastewater, a method of adding only or adding and stirring can be mentioned. In this case, a method of diluting to an appropriate concentration with water before use and adding and kneading to a substance to be treated such as fly ash may be mentioned.
For example, the diluent 1 of the heavy metal fixing agent obtained by diluting 1 to 100 parts by weight of the heavy metal fixing agent of the present invention into 1 to 100 parts by weight of water.
７０70 parts by weight is uniformly added and kneaded to 100 parts by weight of fly ash. As the dilution water used at this time, tap water, river water, groundwater, industrial water, reclaimed water, ion-exchanged water, distilled water, or the like can be used, and any of them does not cause precipitation of insolubles or the like.
【００１４】また、本発明において対象となる重金属含
有廃棄物は特に限定されないが、例えば都市ゴミや産業
廃棄物等の焼却施設から排出される飛灰、焼却灰、廃棄
物処理場から排出される汚泥、工場跡地等の汚染された
土壌、埋立処分場から排出される廃水、工場廃水等に適
用できる。特に焼却施設から排出される飛灰に有効であ
る。The heavy metal-containing waste to be treated in the present invention is not particularly limited. For example, fly ash discharged from an incineration facility for municipal garbage and industrial waste, incinerated ash, and discharged from a waste disposal plant. The present invention can be applied to sludge, contaminated soil such as a factory site, wastewater discharged from a landfill site, factory wastewater, and the like. It is especially effective for fly ash discharged from incineration facilities.
【００１５】[0015]
【実施例】以下に本発明を実施例により説明するが、本
発明は以下の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 the following examples.
【００１６】（１）保存中の安定性試験（実施例１〜
９、及び比較例１〜４） 表１記載の組成の重金属固定化剤を作成し、２５℃で放
置し、水溶液中に沈殿物が発生するまでの期間を測定し
た。その結果を表１に示す。(1) Stability test during storage (Examples 1 to 3)
9, and Comparative Examples 1 to 4) A heavy metal fixing agent having the composition shown in Table 1 was prepared, left at 25 ° C., and a period until a precipitate was generated in the aqueous solution was measured. Table 1 shows the results.
【００１７】[0017]
【表１】 （注１）ＤＥＤＴ−Ｋ＝ジエチルジチオカルバミン酸Ｋ
塩、 ＴＥＰＡ−４Ｎａ＝テトラエチレンペンタミンテトラキ
ス（ジチオカルバミン酸）四Ｎａ塩、 ＤＥＴＡ−２Ｎａ＝ジエチレントリアミンビス（ジチオ
カルバミン酸）二Ｎａ塩 （注２）ＥＤＴＡ−４Ｎａ＝エチレンジアミン四酢酸四
Ｎａ塩、 ＤＴＰＡ−５Ｎａ＝ジエチレントリアミン五酢酸五Ｎａ
塩、 ＡＳＤＡ−２Ｎａ＝アスパラギン酸二酢酸二Ｎａ塩、 ＮＴＡ−３Ｎａ＝ニトリロ三酢酸三Ｎａ塩[Table 1] (Note 1) DEDT-K = diethyldithiocarbamic acid K
Salt, TEPA-4Na = tetraethylenepentaminetetrakis (dithiocarbamic acid) tetraNa salt, DETA-2Na = diethylenetriaminebis (dithiocarbamic acid) diNa salt (Note 2) EDTA-4Na = ethylenediaminetetraacetic acid tetraNa salt, DTPA-5Na = Diethylenetriaminepentaacetic acidpentaNa
Salt, ASDA-2Na = Na salt of aspartic diacetate, NTA-3Na = TriNa salt of nitrilotriacetic acid
【００１８】（２）希釈液の安定性試験（実施例１０〜
１８、及び比較例５〜８） 表１記載の組成をもつ重金属固定化剤（製造直後）を表
２記載の希釈水で希釈後、２５℃で放置し、水溶液中に
沈殿物が発生するまでの期間を測定した。その結果を表
２に示す。(2) Stability test of diluent (Examples 10 to 10)
18, and Comparative Examples 5 to 8) After diluting the heavy metal fixing agent having the composition shown in Table 1 (immediately after production) with the dilution water shown in Table 2, the mixture was allowed to stand at 25 ° C. until a precipitate was formed in the aqueous solution. Was measured. Table 2 shows the results.
【００１９】[0019]
【表２】 [Table 2]
【００２０】（３）重金属固定化試験（実施例１９〜２
７、及び比較例９〜１２） 飛灰（Ｐｂ含有量４１００ｍｇ／ｋｇ、Ｃｄ含有量３５
ｍｇ／ｋｇ）１００重量部に対し、表３記載の重金属固
定化剤の希釈組成物（希釈後６０日間経過したものであ
り、添加量は表３記載）及び必要に応じて水道水を添加
混練した。２４時間室温養生後、環境庁告示１３号に基
づく溶出試験を行った。その結果を表３に示す。(3) Heavy metal immobilization test (Examples 19 to 2)
7, and Comparative Examples 9 to 12) Fly ash (Pb content 4100 mg / kg, Cd content 35)
(mg / kg) 100 parts by weight of the heavy metal fixing agent diluent composition shown in Table 3 (60 days after dilution, the amount added is shown in Table 3) and tap water as needed. did. After curing at room temperature for 24 hours, a dissolution test based on Notification No. 13 of the Environment Agency was performed. Table 3 shows the results.
【００２１】[0021]
【表３】 [Table 3]
【００２２】表３の実施例では、鉛・カドミウムの溶出
量が十分低い値となっており、これは有効成分であるジ
チオカルバミン酸基を有する化合物（ａ）の沈殿等が抑
えられているためと考えられる。一方、比較例では、鉛
・カドミウムの溶出量が高くなっており、これはジチオ
カルバミン酸基を有する化合物（ａ）の濃度が沈殿等に
より低下しているためと考えられる。In the examples of Table 3, the elution amount of lead and cadmium is a sufficiently low value, because the precipitation of the compound (a) having a dithiocarbamic acid group as an active ingredient is suppressed. Conceivable. On the other hand, in the comparative example, the elution amount of lead / cadmium was high, which is considered to be because the concentration of the compound (a) having a dithiocarbamic acid group was reduced due to precipitation or the like.
【００２３】[0023]
【発明の効果】本発明の重金属固定化剤は、従来課題と
なっていた製品（重金属固定化剤）保存中の不溶物沈殿
等の発生を抑えることができるため、製品を長期保存し
た場合でも重金属固定化性能を保持することが可能とな
る。また、河川水、地下水等により製品を希釈した場合
でも、従来発生していた不溶物沈殿等の生成が見られ
ず、混練装置に及ぼす不具合の解消や重金属固定化性能
の低下を抑制できた。EFFECT OF THE INVENTION The heavy metal fixing agent of the present invention can suppress the occurrence of insoluble precipitates during storage of a product (heavy metal fixing agent), which has been a problem in the past, so that even if the product is stored for a long period of time, Heavy metal fixing performance can be maintained. In addition, even when the product was diluted with river water, ground water, or the like, the generation of insoluble precipitates and the like, which had conventionally occurred, was not observed, and the problem of the kneading apparatus was eliminated, and the deterioration of the heavy metal fixing performance was suppressed.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/62 Ｂ０９Ｂ 3/00 ３０４Ｋ 11/00 (72)発明者 相坂 泰弘 東京都中央区日本橋本町三丁目８番３号 東栄化成株式会社内 Ｆターム(参考） 4D004 AA36 AA37 AA41 AB03 CA34 CC03 CC06 4D038 AA08 AB63 AB71 AB74 AB86 AB87 4D059 AA11 AA14 BH04 BJ00 DB08 DB09 DB10 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C02F 1/62 B09B 3/00 304K 11/00 (72) Inventor Yasuhiro Aizaka Nihonbashi Honcho 3-chome, Chuo-ku, Tokyo No. 8-3 Toei Kasei Co., Ltd. F term (reference) 4D004 AA36 AA37 AA41 AB03 CA34 CC03 CC06 4D038 AA08 AB63 AB71 AB74 AB86 AB87 4D059 AA11 AA14 BH04 BJ00 DB08 DB09 DB10
Claims (4)
塩基を有する化合物、（ｂ）アミノポリカルボン酸型キ
レート剤、（ｃ）水、を必須成分として含有することを
特徴とする重金属固定化剤。1. A heavy metal fixing agent comprising, as essential components, (a) a compound having an alkali metal dithiocarbamate, (b) an aminopolycarboxylic acid type chelating agent, and (c) water.
剤が、ニトリロ三酢酸、エチレンジアミン四酢酸、ジエ
チレントリアミン五酢酸、アスパラギン酸二酢酸、エチ
レンジアミンジコハク酸及びこれらのアルカリ金属塩、
アンモニウム塩よりなる群から選ばれた少なくとも１種
のキレート剤である請求項１記載の重金属固定化剤。(B) the aminopolycarboxylic acid type chelating agent is nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic diacetate, ethylenediaminedisuccinic acid or an alkali metal salt thereof;
The heavy metal fixing agent according to claim 1, which is at least one chelating agent selected from the group consisting of ammonium salts.
定化剤を重金属含有廃棄物に配合することを特徴とする
重金属固定化方法。3. A method for immobilizing heavy metals, comprising mixing the heavy metal immobilizing agent according to claim 1 into heavy metal-containing waste.
または廃水である重金属固定化方法。4. A method for immobilizing heavy metals, wherein the heavy metal-containing waste according to claim 3 is fly ash or wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000395181A JP2002194328A (en) | 2000-12-26 | 2000-12-26 | Heavy metal fixing agent and method for fixing heavy metal using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000395181A JP2002194328A (en) | 2000-12-26 | 2000-12-26 | Heavy metal fixing agent and method for fixing heavy metal using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002194328A true JP2002194328A (en) | 2002-07-10 |
Family
ID=18860687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000395181A Pending JP2002194328A (en) | 2000-12-26 | 2000-12-26 | Heavy metal fixing agent and method for fixing heavy metal using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002194328A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336378A (en) * | 2004-05-28 | 2005-12-08 | Miyoshi Oil & Fat Co Ltd | Heavy metal immobilization treating agent composition |
| JP2008170111A (en) * | 2007-01-12 | 2008-07-24 | Chugoku Electric Power Co Inc:The | Method of inhibiting elution of harmful trace element |
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