JP3391173B2 - Method for immobilizing heavy metals in fly ash and agent for immobilizing heavy metals - Google Patents

Method for immobilizing heavy metals in fly ash and agent for immobilizing heavy metals

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Publication number
JP3391173B2
JP3391173B2 JP31384595A JP31384595A JP3391173B2 JP 3391173 B2 JP3391173 B2 JP 3391173B2 JP 31384595 A JP31384595 A JP 31384595A JP 31384595 A JP31384595 A JP 31384595A JP 3391173 B2 JP3391173 B2 JP 3391173B2
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Japan
Prior art keywords
piperazine
fly ash
salt
acid
heavy metals
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Japanese (ja)
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JPH08224560A (en
Inventor
裕 粟野
晃宏 野村
満 高橋
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東ソー株式会社
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Description

【発明の詳細な説明】Detailed Description of the Invention
【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から排出される飛灰を処理するに際
し、飛灰中に含有される鉛、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。
TECHNICAL FIELD The present invention relates to lead, mercury, chromium, cadmium, zinc, copper, etc. contained in fly ash when treating fly ash discharged from an incinerator plant such as municipal waste and industrial waste. The present invention relates to a method which makes it possible to more easily immobilize harmful heavy metals and immobilize them.
【0002】[0002]
【従来の技術】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、ポチ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
る方法が特開平5−50055号公報に開示され、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
使用する方法が特開平6−79254号公報に開示され
ている。
2. Description of the Related Art Fly ash discharged from an incineration plant for municipal waste, industrial waste, etc. is collected by an electric dust collector (EP) or a bag filter (BF) and then landfilled or dumped in the ocean. However, these fly ash contains a lot of harmful heavy metals, and elution of lead, mercury, etc. from landfill by rainwater etc. may cause environmental pollution. For this reason, fly ash is designated as a specially controlled waste, and after being subjected to any of the "cement solidification method", "acid or other solvent extraction method", "melt fixation method" or "chemical addition method" , Must be discarded. Among them, the drug addition method is generally studied in various ways because it is simpler in equipment and handling than other methods. For example, a method of using an inorganic sulfide in combination with a dithiocarbamate salt obtained from a polyamine such as pothiethyleneimine is disclosed in JP-A-5-50055, and a method using a dithiocarbamate salt obtained from diethylenetriamine is disclosed in JP-A-5-005555. No. 6-79254.
【0003】[0003]
【発明が解決しようとする課題】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は、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するために、
混練処理手順及び方法に十二分に配慮する必要があっ
た。
[Problems to be Solved by the Invention] Regarding fly ash treatment,
In addition to soot and dust measures such as EP or BF trapping, it is necessary to take measures against exhaust gas and dioxins, and the properties of the fly ash obtained by these measures will differ greatly, and particularly in highly alkaline fly ash, the amount of heavy metal elution will increase. It has been known. In order to immobilize such heavy metals in fly ash, the amount of conventional agents used should be greatly increased, or a combination method with a pH adjusting agent such as ferric chloride or other agents such as cement. And the cost of processing chemicals increases,
Alternatively, there is a problem that the processing method becomes complicated. further,
Since the dithiocarbamic acid is decomposed by kneading with a pH adjusting agent or heat depending on the amine used as a raw material,
It was necessary to give due consideration to the kneading procedure and method.
【0004】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、飛灰中に含まれる重金属を安定性
の高いキレート剤を用いることにより簡便に固定化でき
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 an object thereof is to provide a method for easily immobilizing heavy metals contained in fly ash by using a highly stable chelating agent. Is.
【0005】[0005]
【課題を解決するための手段】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、ピペラジンカルボ
ジチオ酸又はその塩は、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、かつ熱的に安定であることを見出し、
本発明を完成するに至った。
Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, piperazine carbodithioic acid or a salt thereof has a high chelating ability for heavy metals, and even in highly alkaline fly ash. We found that heavy metals can be immobilized with a small amount of addition, and that they are thermally stable,
The present invention has been completed.
【0006】すなわち本発明は、飛灰に水とピペラジン
カルボジチオ酸又はその塩を添加し、混練する事を特徴
とする飛灰中の重金属の固定化方法である。
That is, the present invention is a method for immobilizing heavy metals in fly ash, which comprises adding water and piperazine carbodithioic acid or a salt thereof to the fly ash and kneading them.
【0007】以下に本発明をさらに詳細に説明する。The present invention will be described in more detail below.
【0008】本発明の方法において使用される飛灰は、
特に限定するものではないが、通常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。
The fly ash used in the method of the present invention is
Although not particularly limited, it is usually discharged from an incineration plant such as municipal waste and industrial waste.
【0009】本発明のピペラジンカルボジチオ酸として
は、ピペラジン−N−カルボジチオ酸又はピペラジン−
N,N’−ビスカルボジチオ酸のいずれか一方、又はこ
れらの混合物として使用できる。ピペラジン−N−カル
ボジチオ酸を使用する場合には、ジチオカルバミン酸基
当量を、ピペラジン−N,N’−ビスカルボジチオ酸を
使用する場合における該官能基当量と同等にすることに
より、ピペラジン−N,N’−ビスカルボジチオ酸を使
用した場合と同様の効果を得ることができる。従って、
これらの混合物として使用する場合における混合比は任
意に選択できる。但し、酸化等によりジスルフィド結合
が生成するような環境のもとで使用又は保存せざるを得
ない場合等においては、二分子間でのジスルフィド結合
が生成しても重金属を捕捉できるジチオカルバミン酸基
が残存可能なピペラジン−N,N’−ビスカルボジチオ
酸を使用することが好ましい。
The piperazinecarbodithioic acid of the present invention includes piperazine-N-carbodithioic acid or piperazine-
Either N, N'-biscarbodithioic acid or a mixture thereof can be used. When piperazine-N-carbodithioic acid is used, the dithiocarbamic acid group equivalent is made equal to the functional group equivalent when piperazine-N, N′-biscarbodithioic acid is used, whereby piperazine-N, The same effect as when N'-biscarbodithioic acid is used can be obtained. Therefore,
When used as a mixture of these, the mixing ratio can be arbitrarily selected. However, in the case where it must be used or stored in an environment where a disulfide bond is formed by oxidation or the like, a dithiocarbamic acid group that can capture a heavy metal even if a disulfide bond between two molecules is formed is necessary. It is preferred to use the residual piperazine-N, N'-biscarbodithioic acid.
【0010】本発明のピペラジンカルボジチオ酸塩は、
前記したピペラジンカルボジチオ酸のアルカリ金属、ア
ルカリ土類金属又はアンモニウムの塩が使用できる。こ
のうち水に溶解し得るリチウム、ナトリウム、カリウ
ム、マグネシム、カルシウム、アンモニウムの塩が好ま
しい。さらに、熱的に安定でかつ安価なナトリウム塩又
はカリウム塩が特に好ましい。
The piperazine carbodithioate of the present invention is
Alkali metal, alkaline earth metal or ammonium salts of the above-mentioned piperazine carbodithioic acid can be used. Of these, salts of lithium, sodium, potassium, magnesium, calcium and ammonium which are soluble in water are preferable. Furthermore, the sodium salt or potassium salt, which is thermally stable and inexpensive, is particularly preferable.
【0011】本発明のピペラジンカルボジチオ酸又はそ
の塩の使用量は、処理する飛灰中の重金属の含有量や重
金属の形態により異なり特に限定するものではないが、
通常飛灰に対して0.01〜5重量%の範囲で使用され
る。
The amount of piperazine carbodithioic acid or a salt thereof used in the present invention depends on the content of heavy metal and the form of heavy metal in the fly ash to be treated, and is not particularly limited.
It is usually used in the range of 0.01 to 5% by weight with respect to fly ash.
【0012】本発明の方法において使用する水の量は、
特に限定するものではないが、処理した飛灰の廃棄を容
易にするため、通常処理する飛灰に対して5〜50重量
%の範囲で使用される。5重量%以下では、薬剤との混
練状態が充分でない場合があり、50重量%以上使用し
た場合には、処理して得られる飛灰が液状となる等して
廃棄が困難となる場合がある。
The amount of water used in the method of the present invention is
Although not particularly limited, in order to facilitate disposal of the treated fly ash, it is usually used in the range of 5 to 50% by weight based on the treated fly ash. If it is 5% by weight or less, the kneading state with the chemicals may not be sufficient, and if it is 50% by weight or more, the fly ash obtained by the treatment may be liquid and the disposal may be difficult. .
【0013】本発明の方法において、水とピペラジンカ
ルボジチオ酸又はその塩を加える方法については特に制
限されない。例えば、前記した水使用量の範囲内におい
て飛灰を混練したのち、予めピペラジンカルボジチオ酸
又はその塩を溶解した水溶液を用いて処理する方法、又
は使用する水の全量に所定量のピペラジンカルボジチオ
酸又はその塩を溶解して処理する方法等が採用できる。
In the method of the present invention, the method of adding water and piperazine carbodithioic acid or a salt thereof is not particularly limited. For example, after kneading the fly ash in the range of the amount of water used above, a method of treating with an aqueous solution in which piperazine carbodithioic acid or a salt thereof is previously dissolved, or a predetermined amount of piperazine carbodithione to the total amount of water used. A method of dissolving an acid or a salt thereof and treating it can be adopted.
【0014】本発明の方法において、固定化される飛灰
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、
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、亜鉛、銅についてはキレート効果が高
いことから好ましい。
In the method of the present invention, the heavy metal in the fly ash to be immobilized is generally a metal that can be insolubilized from an aqueous solution by chelating a dithiocarbamic acid group,
Lead, mercury, chromium, cadmium, zinc, copper, nickel,
Examples include arsenic and selenium. Particularly, lead, mercury, chromium, cadmium, zinc, and copper are preferable because of their high chelating effect.
【0015】[0015]
【実施例】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。
EXAMPLES Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
【0016】合成例1 ピペラジン−N,N’−ビスカ
ルボジチオ酸ナトリウム(化合物No.1)の合成 ガラス製容器中に窒素雰囲気下、ピペラジン172重量
部、NaOH167重量部、水1512重量部を入れ、
この混合溶液中に撹拌しながら45℃で二硫化炭素29
2部を4時間かけて滴下した。滴下終了後、同温度にて
約2時間熟成を行った。反応液に窒素を吹き込み未反応
の二硫化炭素を留去したところ、黄色透明の液体を得
た。
Synthesis Example 1 Piperazine-N, N'-sodium biscarbodithioate (Compound No. 1) was placed in a synthetic glass container under a nitrogen atmosphere in an amount of 172 parts by weight of piperazine, 167 parts by weight of NaOH and 1512 parts by weight of water. ,
Carbon disulfide 29 at 45 ° C with stirring in this mixed solution
2 parts was added dropwise over 4 hours. After completion of dropping, aging was carried out at the same temperature for about 2 hours. When nitrogen was blown into the reaction solution to distill off unreacted carbon disulfide, a yellow transparent liquid was obtained.
【0017】この乾固物の重水(D2O)中でのH1−N
MRスペクトル(内部標準:Sodium 3−Tri
methylsilylpropionate −2,
2,3,3−d4 (TSP))は4.41ppm
(S)であり、C13−NMRスペクトル(内部標準:T
SP)は40.23ppm、199.11ppmであっ
た。さらに燃焼後にイオンクロマトグラフィー(IC)
によりSO4 2-量を測定したところジチオカルバミン酸
基由来と考えられる硫黄の含有率は10.8%(計算値
10.6%)であった。以上の結果からこのものはピペ
ラジン−N,N’−ビスカルボジチオ酸ナトリウムと推
定された。ヨード滴定により測定した結果、得られた水
溶液中のピペラジン−N,N’−ビスカルボジチオ酸ナ
トリウムの濃度は25wt%であった。
H 1 -N in this dry solid in heavy water (D 2 O)
MR spectrum (internal standard: Sodium 3-Tri
methylsilylpropionate-2
2,3,3-d4 (TSP)) is 4.41ppm
(S) and C 13 -NMR spectrum (internal standard: T
SP) was 40.23 ppm and 199.11 ppm. Ion chromatography (IC) after combustion
When the amount of SO 4 2− was measured by the method, the content of sulfur considered to be derived from the dithiocarbamate group was 10.8% (calculated value 10.6%). From the above results, this was presumed to be sodium piperazine-N, N'-biscarbodithioate. As a result of measurement by iodometric titration, the concentration of sodium piperazine-N, N′-biscarbodithioate in the obtained aqueous solution was 25 wt%.
【0018】合成例2 ピペラジン−N,N’−ビスカ
ルボジチオ酸カリウム(化合物No.2)の合成 ガラス製容器中に窒素雰囲気下、ピペラジン112重量
部、KOH48.5%水溶液316重量部、水395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316部を4時間かけて滴下した。滴下終了
後、同温度にて約2時間熟成を行った。反応液に窒素を
吹き込み未反応の二硫化炭素を留去したところ、黄色透
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’−ビスカルボジチオ酸
カリウム濃度は40wt%であった。
Synthesis Example 2 Piperazine-N, N'-potassium biscarbodithioate (Compound No. 2) in a synthetic glass container under a nitrogen atmosphere, 112 parts by weight of piperazine, 316 parts by weight of KOH 48.5% aqueous solution, and water. 395 parts by weight was added, and 316 parts of carbon disulfide was added dropwise to this mixed solution at 40 ° C. over 4 hours while stirring. After completion of dropping, aging was carried out at the same temperature for about 2 hours. When nitrogen was blown into the reaction solution to distill off unreacted carbon disulfide, a yellow transparent liquid was obtained. As a result of measurement by iodometric titration, the concentration of potassium piperazine-N, N′-biscarbodithioate in this aqueous solution was 40 wt%.
【0019】合成例3 エチレンジアミン−N,N’−
ビスカルボジチオ酸ナトリウム(化合物No.3)の合
成 合成例1と同様の装置を用いエチレンジアミン39重量
部、NaOH53重量部、水920重量部を入れ、48
℃にて二硫化炭素99重量部を滴下、反応させて目的の
化合物を含む溶液を得た。ヨード滴定により測定した結
果、この水溶液中のエチレンジアミン−N,N’−ビス
カルボジチオ酸ナトリウム濃度は15wt%であった。
Synthesis Example 3 Ethylenediamine-N, N'-
Synthesis of Sodium Biscarbodithioate (Compound No. 3) Using the same device as in Synthesis Example 1, 39 parts by weight of ethylenediamine, 53 parts by weight of NaOH, and 920 parts by weight of water were added, and
At 90 ° C., 99 parts by weight of carbon disulfide was added dropwise and reacted to obtain a solution containing the target compound. As a result of measurement by iodine titration, the concentration of sodium ethylenediamine-N, N′-biscarbodithioate in this aqueous solution was 15 wt%.
【0020】合成例4 ジエチレントリアミン−N,
N’,N”−トリスカルボジチオ酸ナトリウム(化合物
No.4)の合成 合成例1と同様の装置を用いジエチレントリアミン20
6重量部、NaOH250重量部、水1001重量部を
入れ、48℃にて二硫化炭素415重量部を滴下、反応
させて目的の化合物を含む溶液を得た。IC測定による
ジチオカルバミン酸基による硫黄の含有率は19.4%
(計算値19.3%)であった。ヨード滴定により測定
した結果、この水溶液中のジエチレントリアミン−N,
N’,N”−トリスカルボジチオ酸ナトリウム濃度は4
2wt%であった。
Synthesis Example 4 Diethylenetriamine-N,
Synthesis of N ', N "-sodium triscarbodithioate (Compound No. 4) Using the same apparatus as in Synthesis Example 1, diethylenetriamine 20
6 parts by weight, 250 parts by weight of NaOH and 1001 parts by weight of water were added, and 415 parts by weight of carbon disulfide was added dropwise at 48 ° C. and reacted to obtain a solution containing the target compound. Sulfur content due to dithiocarbamic acid group measured by IC is 19.4%.
(Calculated value 19.3%). As a result of measurement by iodine titration, diethylenetriamine-N,
N ', N "-sodium triscarbodithioate concentration is 4
It was 2 wt%.
【0021】参考例1〜参考例4 安定性試験 得られた化合物No.1〜4の水溶液を65℃に加温し
て硫化水素ガスの発生について調べた。さらに水溶液に
pH調整剤として塩化第二鉄(FeCl3、38%水溶
液)を20重量%添加して硫化水素ガスの発生について
も調べた。結果を表1に示す。
Reference Examples 1 to 4 Stability Test Obtained Compound No. Generation of hydrogen sulfide gas was examined by heating the aqueous solutions 1 to 4 to 65 ° C. Further, 20 wt% of ferric chloride (FeCl 3 , 38% aqueous solution) was added to the aqueous solution as a pH adjuster, and the generation of hydrogen sulfide gas was also examined. The results are shown in Table 1.
【0022】[0022]
【表1】 [Table 1]
【0023】実施例1 重金属固定化能試験 BF灰(Ca=30.9%、Na=1.5%、K=1.
8%、Pb=2100ppm、Zn=5800ppm、
Cu=150ppmを含む)100重量部に対し、水3
0重量部を加え、さらにピペラジン−N,N’−ビスカ
ルボジチオ酸ナトリウムを0.5部(固形分換算)とな
るように添加(化合物No.1の水溶液を飛灰に対し2
wt%添加)、混練し、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。
Example 1 Heavy metal immobilization ability test BF ash (Ca = 30.9%, Na = 1.5%, K = 1.
8%, Pb = 2100 ppm, Zn = 5800 ppm,
100 parts by weight of water (including Cu = 150 ppm), water 3
0 parts by weight was added, and further 0.5 parts by weight of sodium piperazine-N, N'-biscarbodithioate (solid content conversion) was added (compound No. 1 aqueous solution to fly ash to 2 parts).
wt% addition), kneading, and dissolution test were conducted according to the Environmental Agency Notification No. 13 test. Table 2 shows the lead elution results.
【0024】[0024]
【表2】 [Table 2]
【0025】鉛以外の重金属については、いずれの薬剤
添加量においても、亜鉛は3ppm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。
With respect to heavy metals other than lead, zinc is 3 ppm or less and chromium is less than 0.
05 ppm or less, and 0.01 ppm or less for cadmium, mercury, copper, and nickel.
【0026】実施例2 ピペラジン−N,N’−ビスカルボジチオ酸ナトリウム
を0.74部(固形分換算)となるように添加(化合物
No.1の水溶液を飛灰に対し2.96wt%添加)す
る以外は実施例1と同様にして、重金属捕捉能試験を行
った。結果を表2に合わせて示す。
Example 2 Piperazine-N, N'-sodium biscarbodithioate was added so as to be 0.74 parts (solid content conversion) (the compound No. 1 aqueous solution was added 2.96 wt% with respect to the fly ash). A heavy metal capturing ability test was conducted in the same manner as in Example 1 except that the above was performed. The results are also shown in Table 2.
【0027】実施例3 ピペラジン−N,N’−ビスカルボジチオ酸カリウムを
0.4部(固形分換算)となるように添加(化合物N
o.2の水溶液を飛灰に対し1wt%添加)する以外は
実施例1と同様にして、重金属捕捉能試験を行った。結
果を表2に合わせて示す。
Example 3 Potassium piperazine-N, N'-biscarbodithioate was added so as to be 0.4 part (solid content conversion) (compound N).
o. A heavy metal capturing ability test was conducted in the same manner as in Example 1 except that the aqueous solution of 2 was added to the fly ash at 1 wt%. The results are also shown in Table 2.
【0028】実施例4 ピペラジン−N,N’−ビスカルボジチオ酸カリウムを
0.8部(固形分換算)となるように添加(化合物N
o.2の水溶液を飛灰に対し2wt%添加)する以外は
実施例1と同様にして、重金属捕捉能試験を行った。結
果を表2に合わせて示す。
Example 4 Potassium piperazine-N, N'-biscarbodithioate was added so as to be 0.8 part (solid content conversion) (compound N).
o. A heavy metal capturing ability test was conducted in the same manner as in Example 1 except that 2 wt% of the aqueous solution of 2 was added to the fly ash. The results are also shown in Table 2.
【0029】比較例1 ピペラジン−N,N’−ビスカルボジチオ酸ナトリウム
を使用しない以外は実施例1と同様にして、重金属捕捉
能試験を行った。結果を表2に合わせて示す。
Comparative Example 1 A heavy metal scavenging ability test was conducted in the same manner as in Example 1 except that sodium piperazine-N, N'-biscarbodithioate was not used. The results are also shown in Table 2.
【0030】比較例2、比較例3 ピペラジン−N,N’−ビスカルボジチオ酸ナトリウム
を使用する代わりにエチレンジアミン−N,N’−ビス
カルボジチオ酸ナトリウムを0.8部及び1.2部(固
形分換算)となるように添加(化合物No.3の水溶液
を飛灰に対し5.3wt%及び8wt%添加)する以外
は実施例1と同様にして、重金属捕捉能試験を行った。
結果を表2に合わせて示す。
Comparative Examples 2 and 3 Instead of using sodium piperazine-N, N'-biscarbodithioate, 0.8 parts and 1.2 parts of sodium ethylenediamine-N, N'-biscarbodithioate ( A heavy metal trapping ability test was conducted in the same manner as in Example 1 except that the aqueous solution of compound No. 3 was added (5.3 wt% and 8 wt% based on the fly ash) so that the solid content was calculated.
The results are also shown in Table 2.
【0031】比較例4、比較例5 ピペラジン−N,N’−ビスカルボジチオ酸ナトリウム
を使用する代わりにジエチレントリアミン−N,N’,
N”−トリスカルボジチオ酸ナトリウムを0.76部及
び1.15部(固形分換算)となるように添加(化合物
No.4の水溶液を飛灰に対し1.8wt%及び2.7
4wt%添加)する以外は実施例1と同様にして、重金
属捕捉能試験を行った。結果を表2に合わせて示す。
Comparative Examples 4 and 5 Instead of using sodium piperazine-N, N'-biscarbodithioate, diethylenetriamine-N, N ',
Sodium N "-triscarbodithioate was added so as to be 0.76 parts and 1.15 parts (solid content conversion) (the aqueous solution of compound No. 4 was 1.8 wt% and 2.7% with respect to the fly ash).
A heavy metal capturing ability test was conducted in the same manner as in Example 1 except that 4 wt% was added). The results are also shown in Table 2.
【0032】[0032]
【発明の効果】本発明の方法によれば、ピペラジンカル
ボジチオ酸又はその塩は重金属固定化能が高く、かつ熱
的にも安定であることから、重金属溶出量の多い高アル
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。
EFFECTS OF THE INVENTION According to the method of the present invention, piperazine carbodithioic acid or a salt thereof has a high ability to immobilize heavy metals and is also thermally stable, so that even in highly alkaline fly ash with a large amount of heavy metal elution. However, it is economically effective because it is effective even if added in a small amount, and is industrially very useful because it can be carried out by a safe and simple treatment method when using other auxiliary agents.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平1−99679(JP,A) 特開 平3−231921(JP,A) 特開 平4−267982(JP,A) 特開 平5−50055(JP,A) (58)調査した分野(Int.Cl.7,DB名) B09B 3/00 - 5/00 A62D 3/00 C09K 3/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-1-99679 (JP, A) JP-A-3-231921 (JP, A) JP-A-4-267982 (JP, A) JP-A-5- 50055 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B09B 3/00-5/00 A62D 3/00 C09K 3/00

Claims (10)

    (57)【特許請求の範囲】(57) [Claims]
  1. 【請求項1】 飛灰に水と、ピペラジン−N−カルボジ
    チオ酸もしくはピペラジン−N,N’−ビスカルボジチ
    オ酸のいずれか一方もしくはこれらの混合物又はこれら
    の塩を添加し、混練することを特徴とする飛灰中の重金
    属の固定化方法。
    1. Fly ash with water and piperazine-N-carbodi
    Thioic acid or piperazine-N, N'-biscarboditi
    A method for immobilizing heavy metals in fly ash, which comprises adding any one of oleic acid, a mixture thereof, or a salt thereof and kneading.
  2. 【請求項2】 ピペラジン−N−カルボジチオ酸塩もし
    くはピペラジン−N,N’−ビスカルボジチオ酸塩が、
    アルカリ金属、アルカリ土類金属塩又はアンモニウム塩
    であることを特徴とする請求項1に記載の方法。
    2. Piperazine-N-carbodithioate salt
    Kuha piperazine-N, N'-biscarbodithioate
    Alkali metal, alkaline earth metal salt or ammonium salt
    The method of claim 1, wherein:
  3. 【請求項3】 ピペラジン−N,N’−ビスカルボジチ
    オ酸塩がピペラジン−N,N’−ビスカルボジチオ酸ナ
    トリウムであることを特徴とする請求項2に記載の方
    法。
    3. Piperazine-N, N'-biscarboditi
    The oxo acid salt is piperazine-N, N'-biscarbodithioic acid sodium salt.
    The method according to claim 2, wherein the method is thorium.
    Law.
  4. 【請求項4】 ピペラジン−N,N’−ビスカルボジチ
    オ酸塩がピペラジン−N,N’−ビスカルボジチオ酸カ
    リウムであることを特徴とする請求項2に記載の方法。
    4. Piperazine-N, N'-biscarbodithi
    The oxo acid salt is piperazine-N, N'-biscarbodithioic acid
    The method according to claim 2, wherein the method is helium.
  5. 【請求項5】 重金属が、鉛、水銀、クロム、カドミウ
    ム、亜鉛及び銅からなる群より選ばれる1種以上である
    ことを特徴とする請求項1乃至請求項のいずれかに記
    載の方法。
    5. heavy metals, lead, mercury, chromium, cadmium, method according to any one of claims 1 to 4, characterized in that at least one selected from the group consisting of zinc and copper.
  6. 【請求項6】 ピペラジン−N−カルボジチオ酸もしく
    はピペラジン−N,N’−ビスカルボジチオ酸のいずれ
    か一方もしくはこれらの混合物又はこれらの塩からなる
    飛灰中の重金属固定化処理剤。
    6. Piperazine-N-carbodithioic acid or
    Is any of piperazine-N, N'-biscarbodithioic acid
    One or more, or a mixture thereof, or a treatment agent for immobilizing heavy metal in fly ash, which comprises these salts.
  7. 【請求項7】 ピペラジン−N−カルボジチオ酸塩もし
    くはピペラジン−N,N’−ビスカルボジチオ酸塩が、
    アルカリ金属、アルカリ土類金属塩又はアンモニウム塩
    であることを特徴とする請求項6に記載の飛灰中の重金
    属固定化処理剤。
    7. Piperazine-N-carbodithioate salt
    Kuha piperazine-N, N'-biscarbodithioate
    Alkali metal, alkaline earth metal salt or ammonium salt
    Heavy metal in fly ash according to claim 6, characterized in that
    Genus immobilization treatment agent.
  8. 【請求項8】 ピペラジン−N,N’−ビスカルボジチ
    オ酸塩がピペラジン−N,N’−ビスカルボジチオ酸ナ
    トリウムであることを特徴とする請求項7に記載の飛灰
    中の重金属固定化処理剤。
    8. Piperazine-N, N′-biscarbodithi
    The oxo acid salt is piperazine-N, N'-biscarbodithioic acid sodium salt.
    The fly ash according to claim 7, which is thorium.
    Heavy metal immobilization treatment agent.
  9. 【請求項9】 ピペラジン−N,N’−ビスカルボジチ
    オ酸塩がピペラジン−N,N’−ビスカルボジチオ酸カ
    リウムであることを特徴とする請求項7に記載 の飛灰中
    の重金属固定化処理剤。
    9. Piperazine-N, N′-biscarbodithi
    The oxo acid salt is piperazine-N, N'-biscarbodithioic acid
    The fly ash according to claim 7, wherein the fly ash is lithium.
    Heavy metal immobilization treatment agent.
  10. 【請求項10】 重金属が、鉛、水銀、クロム、カドミ
    ウム、亜鉛及び銅からなる群より選ばれる1種以上であ
    ることを特徴とする請求項6乃至請求項9のいずれかに
    記載の飛灰中の重金属固定化処理剤。
    10. The heavy metal is lead, mercury, chromium, cadmium.
    One or more selected from the group consisting of um, zinc and copper
    In any one of Claim 6 thru | or 9 characterized by the above-mentioned.
    A treatment agent for fixing heavy metals in fly ash described.
JP31384595A 1994-12-02 1995-12-01 Method for immobilizing heavy metals in fly ash and agent for immobilizing heavy metals Expired - Lifetime JP3391173B2 (en)

Priority Applications (3)

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JP6-299684 1994-12-02
JP29968494 1994-12-02
JP31384595A JP3391173B2 (en) 1994-12-02 1995-12-01 Method for immobilizing heavy metals in fly ash and agent for immobilizing heavy metals

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JP3391173B2 true JP3391173B2 (en) 2003-03-31

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