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JPH0199679A - Method for fixing heavy metals in soil or solid waste - Google Patents

Method for fixing heavy metals in soil or solid waste

Info

Publication number
JPH0199679A
JPH0199679A JP62256061A JP25606187A JPH0199679A JP H0199679 A JPH0199679 A JP H0199679A JP 62256061 A JP62256061 A JP 62256061A JP 25606187 A JP25606187 A JP 25606187A JP H0199679 A JPH0199679 A JP H0199679A
Authority
JP
Japan
Prior art keywords
group
heavy metals
soil
solid waste
heavy
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.)
Pending
Application number
JP62256061A
Other languages
Japanese (ja)
Inventor
Masafumi Moriya
雅文 守屋
Kazuo Hosoda
和夫 細田
Akira Nishimura
朗 西村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Miyoshi Yushi KK
Miyoshi Oil and Fat Co Ltd
Original Assignee
Miyoshi Yushi KK
Miyoshi Oil and Fat Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Miyoshi Yushi KK, Miyoshi Oil and Fat Co Ltd filed Critical Miyoshi Yushi KK
Priority to JP62256061A priority Critical patent/JPH0199679A/en
Publication of JPH0199679A publication Critical patent/JPH0199679A/en
Pending legal-status Critical Current

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  • Processing Of Solid Wastes (AREA)

Abstract

PURPOSE:To make heavy metals or heavy metal compds. insoluble and to prevent pollution by the metals by adding an aq. soln. of a specified metal capturing agent to soil or solid waste contg. the heavy metals or heavy metal compds. CONSTITUTION:An aq. soln. of a metal capturing agent having -RX [where X is COOH and R is (CH2)n (n is an integer of 1-4), CH2CH(CH3) or CH2CH (CH2COOH)] or a salt thereof, a hydroxyalkyl group, at least one dithiocarboxy group, etc., as substituents for active hydrogen atoms. in polyamines per 1mol. of the polyamines is prepd. and added to soil or waste solid contg. heavy metals or heavy metal compds. The heavy metals or heavy metal compds. are fixed and made insoluble.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は土壌やEP灰、重金属スラフジ等の固体状廃棄
物中の重金属類の固定化方法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for immobilizing heavy metals in solid waste such as soil, EP ash, and heavy metal sludge.

〔従来の技術及び 発明が解決しようとする問題点〕[Conventional technology and Problems that the invention attempts to solve]

近年、工場等の廃水による河川、海等の汚染が問題とな
るにつれて、廃水による汚染防止のための規制が強化さ
れ、廃水中に含有される金属類を所定濃度以下とするこ
とが義務づけられており、水銀、カドミウム、亜鉛、鉛
、銅、クロム等の人体に有害な重金属類に対しては特に
厳しい規制が設けられている。このため廃水中の金属類
を除去するための種々の方法が提案されており、例えば
、廃水中にアルカリを投入して金属類を水酸化物とした
後、高分子凝集剤により凝集沈澱して除去する中和凝集
沈澱法が知られているが、生成した重金属水酸化物のス
ラッジは廃棄の仕方によっては再溶解して二次公害を生
じるという問題があった。
In recent years, as the pollution of rivers, oceans, etc. by wastewater from factories has become a problem, regulations to prevent pollution by wastewater have been strengthened, and it is now mandatory to keep metals contained in wastewater below a specified concentration. Particularly strict regulations are in place for heavy metals that are harmful to the human body, such as mercury, cadmium, zinc, lead, copper, and chromium. For this reason, various methods have been proposed to remove metals from wastewater. For example, after adding alkali to wastewater to convert metals into hydroxides, the metals are coagulated and precipitated using a polymer flocculant. A neutralization coagulation-sedimentation method for removal is known, but there is a problem that the generated heavy metal hydroxide sludge may re-dissolve depending on how it is disposed of, causing secondary pollution.

また、重金属やその化合物の生産工場ではこれまで長期
間に亘って重金属やその化合物を含有する廃棄物をコン
クリート詰め等の処置を施して埋立地に投棄する等の処
理を行ってきたが、重金属やその化合物が長年の間に微
量ずつ溶出して土壌を汚染するという問題が生じている
In addition, factories that produce heavy metals and their compounds have been disposing of waste containing heavy metals and their compounds for a long time by filling them in concrete and dumping them in landfills. A problem has arisen in which small amounts of soil and its compounds have been leached out over many years and contaminated the soil.

〔問題点を解決するための手段〕[Means for solving problems]

本発明は上記の点に鑑みなされたもので、土壌やスラッ
ジ、EP灰等の固体状廃棄物中に含有される重金属類を
固定化して水不溶性とすることによって重金属公害の発
生を防止できる土壌又は固体状廃棄物中の重金属類の固
定化方法を提供することを目的とする。
The present invention was made in view of the above points, and is a soil that can prevent heavy metal pollution by immobilizing heavy metals contained in solid waste such as soil, sludge, and EP ash and making them water-insoluble. Another object of the present invention is to provide a method for immobilizing heavy metals in solid waste.

即ち本発明は、ポリアミン類1分子当たり、該ポリアミ
ン類の活性水素原子と置換した置換基として、−RX(
ただしXはC0OH,Rは(CH2)、  (ただしn
は1〜4の整数) 、CH2Cll(CH3)、又はC
1(2−CH(C112−COoH) )あるいはこれ
らの塩か、ヒドロキシアルキル基の少なくとも一方を少
なくとも1個有し、且つ少なくとも1個のジチオカルボ
キシ基あるいはその塩を置換基として有する金属捕集剤
の水溶液を、重金属或いはその化合物を含有する土壌又
は固体状廃棄物に添加し、土壌又は固体状廃棄物中の重
金属或いはその化合物を不溶化することを特徴とする土
壌又は固体状廃棄物中の重金属類の固定化方法を要旨と
するものである。
That is, the present invention provides -RX(
However, X is C0OH, R is (CH2), (however, n
is an integer from 1 to 4), CH2Cll(CH3), or C
1(2-CH(C112-COoH) ) or a salt thereof, or at least one hydroxyalkyl group, and at least one dithiocarboxy group or a salt thereof as a substituent. Heavy metals in soil or solid waste, characterized by adding an aqueous solution of the above to soil or solid waste containing heavy metals or their compounds to insolubilize the heavy metals or their compounds in the soil or solid waste. The gist of this article is the immobilization method of the following types.

本発明において用いる金属捕集剤としてはポリアミン類
と、ハロゲン置換アルキル基の炭素数が1〜4のモノハ
ロゲン化カルボン酸あるいは不飽和アルキル基の炭素数
が2〜4の不飽和カルボン酸とを反応せしめて(CII
2)、 C00II基、CH2Cl (CH3)−C0
0I+基、あるいはCHzCIl (CHzCOOtl
) C0OH基等のカルボン酸誘導体基を導入した後、
二硫化炭素を反応せしめてジチオカルボキシ基を導入す
るか、または二硫化炭素を反応せしめてジチオカルボキ
シ基を4人した後、モノハロゲン化カルボン酸あるいは
不飽和カルボン酸を反応せしめて、(C11□)n C
0OH基、CHzCH(CH3)C0OH基、CHzC
!I(CHz−COOH)COoH基等のカルボン酸誘
導体基を導入して得られる化合物;ポリアミン類にエポ
キシアルカンを開環付加させてβ−ヒドロキシアルキル
基等のヒドロキシアルキル基をN−置換基として導入し
た後、二硫化炭素を反応させてジチオカルボキシ基を導
入するか、ポリアミン類に二硫化炭素を反応せしめた後
、エポキシアルカンを開環付加させてヒドロキシアルキ
ル基を導入して得られる化合物;上記と同様にして(C
H2)−C0OH基、CH,Cl−(CH3)C00H
基、あるいはCH2Cl!(CIl□C00H)COO
11基等のカルボン酸誘導体基の少なくとも1個とヒド
ロキシアルキル基の少なくとも1個及びジチオカルボキ
シ基の少なくとも1個とを導入して得た化合物;あるい
は上記(CI+2) −C0011基、Cll2CH(
C1+3)−C00H基、CHzCH(CHzCOOl
l)COoH基等のカルボン酸誘導体基の塩、ジチオカ
ルボキシ基の塩を置換基として有する化合物が挙げられ
る。
The metal scavenger used in the present invention includes polyamines and a monohalogenated carboxylic acid whose halogen-substituted alkyl group has 1 to 4 carbon atoms or an unsaturated carboxylic acid whose unsaturated alkyl group has 2 to 4 carbon atoms. Let it react (CII
2), C00II group, CH2Cl (CH3)-C0
0I+ group, or CHzCIl (CHzCOOtl
) After introducing a carboxylic acid derivative group such as a C0OH group,
Either react with carbon disulfide to introduce a dithiocarboxy group, or react with carbon disulfide to form a dithiocarboxy group, and then react with a monohalogenated carboxylic acid or an unsaturated carboxylic acid (C11□ ) n C
0OH group, CHzCH(CH3)C0OH group, CHzC
! Compounds obtained by introducing carboxylic acid derivative groups such as I(CHz-COOH)COoH groups; ring-opening addition of epoxyalkanes to polyamines to introduce hydroxyalkyl groups such as β-hydroxyalkyl groups as N-substituents Compounds obtained by reacting carbon disulfide and introducing a dithiocarboxy group, or reacting polyamines with carbon disulfide, and then ring-opening and adding an epoxyalkane to introduce a hydroxyalkyl group; In the same way as (C
H2)-C0OH group, CH, Cl-(CH3)C00H
group, or CH2Cl! (CIl□C00H)COO
A compound obtained by introducing at least one carboxylic acid derivative group such as 11 groups, at least one hydroxyalkyl group, and at least one dithiocarboxy group; or the above (CI+2) -C0011 group, Cll2CH(
C1+3)-C00H group, CHzCH(CHzCOOl
l) Compounds having a salt of a carboxylic acid derivative group such as a COoH group, or a salt of a dithiocarboxy group as a substituent.

上記ポリアミン類とは、窒素原子に1個または2個の活
性水素原子が結合してなるイミノ基またはアミノ基を2
個以上有する化合物であり、例えばエチレンジアミン、
プロピレンジアミン、ブチレンジアミン、ヘキサメチレ
ンジアミン、ジエチレントリアミン、ジプロピレントリ
アミン、ジエチレントリアミン、トリエチレンテトラミ
ン、トリプロピレンテトラミン、トリブチレンテトラミ
ン、テトラエチレンペンタミン、テトラエチレンペンタ
ミン、テトラブチレンペンタミン、ペンタエチレンへキ
サミン等のポリアルキレンポリアミン;フェニレンジア
ミン、キシレンジアミン、メタキシレンジアミン、イミ
ノビスプロピルアミン、モノメチルアミノプロピルアミ
ン、メチルイミノビスプロピルアミン、1,3−ビス(
アミノメチル)シクロヘキサン、3,5−ジアミノクロ
ロベンゼン、メラミン、1−アミノエチルピペラジン、
ピペラジン、ジアミノフェニルエーテル、3.3′−ジ
クロロベンジジン、トリジンベース、m−1−ルイレン
ジアミン等やポリエチレンポリイミン(好ましくは平均
分子量300以上)等が挙げられる。また上記のポリア
ミン類の他に、これらのポリアミン類にアルキルハライ
ドあるいは脂肪酸類を反応せしめる等により得られるN
−アルキルポリアミンあるいはN−アシルポリアミン等
を用いることもできる。N−アルキルポリアミンとして
はN−アルキルエチレンジアミン、N−アルキルプロピ
レンジアミン、N−アルキルへキサメチレンジアミン、
N−アルキルフェニレンジアミン、N−アルキルキシレ
ンジアミン、N−アルキルジエチレントリアミン、N−
アルキルトリエチレンテトラミン、N−アルキルテトラ
エチレンペンタミン、N−アルキルペンタエチレンへキ
サミン等を用いることができる。上記N−置換アルキル
基の炭素数は2〜18が好ましい。またN−アシルポリ
アミンのアシル基は炭素数2〜24が好ましく、該アシ
ル基としては例えばアセチル基、プロピオニル基、ブチ
リル基、カプロイル基、ラウロイル基、オレオイル基、
ミリスチロイル基、ステアロイル基、ベヘロイル基等が
挙げられる。
The above polyamines refer to an imino group or an amino group formed by bonding one or two active hydrogen atoms to a nitrogen atom.
For example, ethylenediamine,
Propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, diethylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetraethylenepentamine, tetrabutylenepentamine, pentaethylenehexamine, etc. polyalkylene polyamine; phenylene diamine, xylene diamine, metaxylene diamine, iminobispropylamine, monomethylaminopropylamine, methyliminobispropylamine, 1,3-bis(
(aminomethyl) cyclohexane, 3,5-diaminochlorobenzene, melamine, 1-aminoethylpiperazine,
Examples include piperazine, diaminophenyl ether, 3,3'-dichlorobenzidine, tolidine base, m-1-lylene diamine, and polyethylene polyimine (preferably having an average molecular weight of 300 or more). In addition to the polyamines mentioned above, N which can be obtained by reacting these polyamines with alkyl halides or fatty acids
-Alkyl polyamines, N-acyl polyamines, etc. can also be used. N-alkylpolyamines include N-alkylethylenediamine, N-alkylpropylenediamine, N-alkylhexamethylenediamine,
N-alkylphenylenediamine, N-alkylxylenediamine, N-alkyldiethylenetriamine, N-
Alkyltriethylenetetramine, N-alkyltetraethylenepentamine, N-alkylpentaethylenehexamine, etc. can be used. The number of carbon atoms in the N-substituted alkyl group is preferably 2 to 18. The acyl group of the N-acylpolyamine preferably has 2 to 24 carbon atoms, and examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a caproyl group, a lauroyl group, an oleoyl group,
Examples include myristyroyl group, stearoyl group, beheroyl group, and the like.

更にこれらのポリアミン類とエピクロルヒドリン、エピ
ブロムヒドリン、エピヨードヒドリン、ブロモメチルオ
キシラン等のエピハロヒドリンとが重縮合した重縮合ポ
リアミン類も用いることができる。これらポリアミン類
は単独または二種以上混合して用いることができる。尚
、エピハロヒドリンによる重縮合は、(C1h)nC0
011基、C11zCIl(CH:+)COOH基、C
HzCH(CHzCOOll) C0OH基等のカルボ
ン酸誘導体基あるいはヒドロキシアルキル基またはこれ
らの塩等の置換基導入後、これら置換基の少なくとも1
種とジチオカルボキシ基あるいはその塩を導入後、ジチ
オカルボキシ基またはその塩のみを置換基として導入し
た後のいずれの反応過程においても行うことができる。
Furthermore, polycondensed polyamines obtained by polycondensing these polyamines with epihalohydrins such as epichlorohydrin, epibromohydrin, epiiodohydrin, and bromomethyloxirane can also be used. These polyamines can be used alone or in combination of two or more. In addition, polycondensation with epihalohydrin is (C1h)nC0
011 group, C11zCIl(CH:+)COOH group, C
HzCH (CHzCOOll) After introducing a substituent such as a carboxylic acid derivative group such as a C0OH group or a hydroxyalkyl group or a salt thereof, at least one of these substituents
It can be carried out in any reaction process after introducing a species and a dithiocarboxy group or a salt thereof, or after introducing only a dithiocarboxy group or a salt thereof as a substituent.

(CH2)、 CO叶基、C11ZCII(CI(:+
)COOH恭、あるいはCH2CII(CH2COOH
)CO叶基等のカルボン酸誘導体基を導入するために用
いられるモノハロゲン化カルボン酸、不飽和カルボン酸
としては、例えばモノクロロ酢酸、モノクロロプロピオ
ン酸、モノクロロ酪酸、アクリル酸、メタクリル酸、イ
タコン酸等が挙げられる。またヒドロキシアルキル基を
導入するために用いられるエポキシアルカンとして好ま
しいものは、エチレンオキシド、プロピレンオキシド、
ブチレンオキシドや炭素数6〜28のα−オレフィンオ
キシドで、導入されるヒドロキシアルキル基としては例
えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒ
ドロキシブチル基、β−ヒドロキシドデシル基、β−ヒ
ドロキシテトラデシル基、β−ヒドロキシヘキサデシル
基、β−ヒドロキシオクタデシル基、β−ヒドロキジオ
クタコシル基等が挙げられる。
(CH2), CO Kanoki, C11ZCII (CI(:+
) COOH Kyo, or CH2CII (CH2COOH
) Examples of monohalogenated carboxylic acids and unsaturated carboxylic acids used to introduce carboxylic acid derivative groups such as CO groups include monochloroacetic acid, monochloropropionic acid, monochlorobutyric acid, acrylic acid, methacrylic acid, itaconic acid, etc. can be mentioned. Preferred epoxyalkanes used for introducing hydroxyalkyl groups are ethylene oxide, propylene oxide,
Examples of the hydroxyalkyl group introduced in butylene oxide and α-olefin oxide having 6 to 28 carbon atoms include hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, β-hydroxydodecyl group, β-hydroxytetradecyl group, Examples include β-hydroxyhexadecyl group, β-hydroxyoctadecyl group, β-hydroxydioctacyl group, and the like.

上記(CH2)IICOOtl基、CH□Cll (C
H3) CO叶基、あるいはC11□CH(CIIzC
OOtl)COOII基等のカルボン酸誘導体基、ジチ
オカルボキシ基の塩としては、カリウム塩、ナトリウム
塩、リチウム塩等のアルカリ金属塩;カルシウム塩、マ
グネシウム塩、バリウム塩等のアルカリ土類金属塩;ア
ンモニウム塩等が挙げられる。これら塩型の置換基を導
入する方法としては、前記したハロゲン化カルボン酸、
不飽和カルボン酸の塩をポリアミン類と反応させる方法
、(C11□)n C0OH基等の酸型の置換基を導入
した後、アルカリ金属水酸化物、アルカリ土類金属水酸
化物、アンモニア等のアルカリで処理するか、あるいは
ハロゲン化カルボン酸、不飽和カルボン酸とポリアミン
類との反応をアルカリの存在下で行う方法、あるいは前
記ハロゲン化カルボン酸、不飽和カルボン酸又はこれら
の塩のかわりにアクリル酸メチル等の低級アルコールエ
ステルを用い、ケン化、酸分解等により前記酸型の置換
基あるいはその塩類とする方法等が挙げられる。またジ
チオカルボキシ基の塩を置換基として導入する方法とし
ては二硫化炭素を反応せしめてジチオカルボキシ基を導
入した後、上記と同様のアルカリで処理するか、あるい
はアルカリの存在下で二硫化炭素を反応せしめる方法が
挙げられる。
The above (CH2)IICOOtl group, CH□Cll (C
H3) CO base, or C11□CH (CIIzC
OOtl) Salts of carboxylic acid derivative groups such as COOII groups and dithiocarboxy groups include alkali metal salts such as potassium salts, sodium salts, and lithium salts; alkaline earth metal salts such as calcium salts, magnesium salts, and barium salts; ammonium salts; Examples include salt. Methods for introducing these salt-type substituents include the above-mentioned halogenated carboxylic acid,
A method in which a salt of an unsaturated carboxylic acid is reacted with polyamines, after introducing an acid type substituent such as (C11□)n C0OH group, alkali metal hydroxide, alkaline earth metal hydroxide, ammonia, etc. A method of treating with an alkali, or a method of reacting a halogenated carboxylic acid, an unsaturated carboxylic acid, and a polyamine in the presence of an alkali, or a method of treating with an alkali in place of the halogenated carboxylic acid, unsaturated carboxylic acid, or a salt thereof. Examples include a method in which a lower alcohol ester such as methyl acid is used to form the acid type substituent or its salt by saponification, acid decomposition, or the like. In addition, methods for introducing a salt of a dithiocarboxy group as a substituent include reacting carbon disulfide to introduce a dithiocarboxy group, and then treating it with an alkali similar to the above, or adding carbon disulfide in the presence of an alkali. One example is a method of causing a reaction.

上記、(C112)fiCOOH基、C11□CH(C
I−13)COOII基、CHzCIl(CHzCOO
H)COOtl基等のカルボン酸誘導体基あるいはこれ
らの塩、ジチオカルボキシ基あるいはその塩及びヒドロ
キシアルキル基は通常ポリアミン類の窒素原子に結合し
たN−置換基であるが、ポリアミン類としてエピハロヒ
ドリンと重縮合した重縮合ポリアミンを用いた場合には
、ジチオカルボキシ基あるいはその塩は窒素原子のみに
結合している場合に限らず、エピハロヒドリン骨格部分
に生じる水酸基の水素原子と置換し、酸素原子に結合し
ていても良い。
Above, (C112)fiCOOH group, C11□CH(C
I-13) COOII group, CHzCIl (CHzCOO
H) Carboxylic acid derivative groups such as COOtl groups or their salts, dithiocarboxy groups or their salts, and hydroxyalkyl groups are usually N-substituents bonded to the nitrogen atom of polyamines, but they can be polycondensed with epihalohydrin as polyamines. When a polycondensed polyamine is used, the dithiocarboxy group or its salt does not only bond to the nitrogen atom, but also replaces the hydrogen atom of the hydroxyl group that occurs in the epihalohydrin skeleton and bonds to the oxygen atom. It's okay.

本発明方法では上記金属捕集剤の水溶液を土壌又はEP
灰、重金属スラッジ等の固体状廃棄物に添加して、土壌
又は固体状廃棄物中の重金属或いは、その化合物を固定
化するが、土壌又は固体状廃棄物中の水含有量が少なす
ぎると金属捕集剤と重金属類との反応が不完全となり、
逆に水含有量が多すぎると固定化処理後の廃棄処理の作
業性を悪化させるため、元々含まれていた水分と、金属
捕集剤水溶液添加による水分の合計量が10〜90重景
%程度の範囲に保持されるように金属捕集剤水溶液の濃
度、添加量を調節して添加することが好ましい。
In the method of the present invention, the aqueous solution of the metal scavenger is applied to soil or EP.
It is added to solid waste such as ash and heavy metal sludge to immobilize heavy metals or their compounds in soil or solid waste, but if the water content in soil or solid waste is too low, metals The reaction between the scavenger and heavy metals becomes incomplete,
On the other hand, if the water content is too high, the workability of waste treatment after immobilization will deteriorate, so the total amount of water originally contained and water due to the addition of the metal scavenger aqueous solution will be 10 to 90%. It is preferable to adjust the concentration and amount of the metal scavenger aqueous solution so as to maintain the concentration within a certain range.

金属捕集剤水溶液は土壌又は固体状廃棄物の表面に単に
散布するだけでもよいが、散布又は単に加えた後に混練
することが好ましい。
The metal scavenger aqueous solution may be simply sprinkled on the surface of the soil or solid waste, but it is preferable to knead it after being sprayed or simply added.

本発明に用いる金属捕集剤は特に水銀、カドミウム、亜
鉛、銅、クロム、砒素、金、銀、白金、バナジウム、タ
リウム等の重金属の捕集性に優れ、特に上記の重金属或
いはその化合物を含有する土壌又は固体状廃棄物の処理
に効果的である。
The metal scavenger used in the present invention has particularly excellent scavenging properties for heavy metals such as mercury, cadmium, zinc, copper, chromium, arsenic, gold, silver, platinum, vanadium, and thallium, and particularly contains the above heavy metals or their compounds. It is effective for treating soil or solid waste.

〔実施例〕〔Example〕

以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.

実施例1〜7 第1表に示すモル比で同表に示すポリアミン類とカルボ
ン酸類及び二硫化炭素を反応せしめて得られた金属捕集
剤の水溶液(金属捕集剤濃度を第1表にあわせて示す。
Examples 1 to 7 Aqueous solutions of metal scavengers obtained by reacting polyamines shown in the same table with carboxylic acids and carbon disulfide at the molar ratios shown in Table 1 (the metal scavenger concentrations are shown in Table 1). Also shown.

)を、処理用スラッジ(6%含水)100g当りに対し
10mj2を添加して万能攪拌ミキサー(小平製作所型
)により15分間攪拌して混練した。処理用スラッジは
環境庁告示第13号の方法でpH=5.8の水を使用し
て溶出試験を行ない、溶出液をJIS  KO102の
方法により分析した結果、溶出液中の金属イオン濃度は
水SJ?0.50ppm、カドミウム0.25 ppm
、クロム2. OI) pmであった。
) was added in an amount of 10 mj2 per 100 g of treatment sludge (6% water content) and stirred and kneaded for 15 minutes using a universal stirring mixer (Kodaira Seisakusho type). The treatment sludge was subjected to an elution test using water with a pH of 5.8 according to the method specified in the Environment Agency Notification No. 13, and the eluate was analyzed using the JIS KO102 method. As a result, the metal ion concentration in the eluate was found to be the same as that of water. SJ? 0.50ppm, cadmium 0.25ppm
, chromium 2. OI) pm.

処理後のスラッジについて同様の溶出試験を行なった後
、同様の方法により溶出重金属の分析を行なった結果を
第3表に示す。
A similar elution test was conducted on the treated sludge, and the eluted heavy metals were analyzed using the same method. The results are shown in Table 3.

実施例8〜14 第2表に示すモル比で同表に示すヒドロキシアルキルポ
リアミンと二硫化炭素を反応せしめて得られた金属捕集
剤の水溶液(金属捕集剤の濃度を第2表に示す。)によ
り実施例1〜7と同様の処理用スラッジを同様にして処
理した。処理後のスラッジについて溶出試験及び溶出重
金属の分析を実施例1〜7と同様の方法により行った結
果を第3表にあわせて示す。
Examples 8 to 14 Aqueous solutions of metal scavengers obtained by reacting hydroxyalkyl polyamines shown in Table 2 with carbon disulfide at the molar ratios shown in Table 2 (concentrations of metal scavengers are shown in Table 2) .) The same treatment sludge as in Examples 1 to 7 was treated in the same manner. The sludge after treatment was subjected to an elution test and an analysis of eluted heavy metals in the same manner as in Examples 1 to 7. The results are also shown in Table 3.

比較例1 エチレンジアミン1モルに二硫化炭素2モルを反応させ
て得た金属捕集剤の水溶液(金属捕集剤濃度1wt%)
を用いて実施例と同様の条件でスラッジの処理を行なっ
た。処理後のスラッジについて実施例と同様の方法で溶
出試験及び分析を行なった結果を第3表にあわせて示す
Comparative Example 1 Aqueous solution of metal scavenger obtained by reacting 1 mole of ethylenediamine with 2 moles of carbon disulfide (metal scavenger concentration 1 wt%)
The sludge was treated under the same conditions as in the example. The treated sludge was subjected to an elution test and analysis in the same manner as in the examples, and the results are also shown in Table 3.

第2表 第3表 ※I N−(β−ヒドロキシオクチル)トリエチレンテ
トラミンとエピクロルヒドリン1モルを重縮合せしめた
重縮合ポリアミン。
Table 2 Table 3 *I Polycondensed polyamine obtained by polycondensing N-(β-hydroxyoctyl)triethylenetetramine and 1 mole of epichlorohydrin.

尚、実施例1.2.4.5.6.7.9.10.11.
12.13における金属捕集剤はカルボン酸誘導体基及
びジチオカルボキシ基のいずれもナトリウム塩として用
い、実施例3.8.14は酸型のまま用いた。
In addition, Example 1.2.4.5.6.7.9.10.11.
For the metal scavenger in Example 12.13, both the carboxylic acid derivative group and the dithiocarboxy group were used as sodium salts, and in Example 3.8.14, they were used as they were in the acid form.

〔発明の効果〕〔Effect of the invention〕

以上説明したように本発明方法によれば土壌やEP仄、
重金属スラッジ等の固体状廃棄物中の有害重金属類を確
実に固定化して溶出を防止でき、地中、ii6中等へ廃
棄された固体状廃棄物からの土壌中、海水中への重金属
類の?古川や、土壌中に存在する重金属の生物体内への
移行を確実に防止できる。また本発明方法では金后捕集
剤として、ジチオカルボキシ基の他ニ(Ctlz) 、
IC0011基、CllCl+−(C113)COOH
基、CHZCII (CIl□C00II)Co叶基等
のカルボン酸誘導体基あるいはこれらの塩、ヒドロキシ
アルキル基の少なくとも1個を置換基として有するもの
を用いたことによって、特に含水スラッジ中の重金属又
はそれらの塩に対しても優れた固定製を発揮する等の効
果を有する。
As explained above, according to the method of the present invention, soil, EP,
It is possible to reliably immobilize hazardous heavy metals in solid waste such as heavy metal sludge and prevent their elution, and prevent heavy metals from entering the soil and seawater from solid waste disposed of underground, II6, etc. It is possible to reliably prevent the transfer of heavy metals present in Furukawa and soil into living organisms. In addition, in the method of the present invention, in addition to the dithiocarboxy group, di(Ctlz),
IC0011 group, CllCl+-(C113)COOH
By using a carboxylic acid derivative group such as a CHZCII (CIl□C00II) Co group, or a salt thereof, or a hydroxyalkyl group as a substituent, heavy metals in water-containing sludge or their It also has the effect of exhibiting excellent fixation properties against salt.

Claims (3)

【特許請求の範囲】[Claims] (1)ポリアミン類1分子当たり、該ポリアミン類の活
性水素原子と置換した置換基として、 −RX(ただしXはCOOH、Rは(CH_2)_n〔
ただしnは1〜4の整数〕、CH_2CH(CH_3)
、又はCH_2CH−(CH_2COOH))あるいは
これらの塩か、ヒドロキシアルキル基の少なくとも一方
を少なくとも1個有し、且つ少なくとも1個のジチオカ
ルボキシ基あるいはその塩を置換基として有する金属捕
集剤の水溶液を、重金属或いはその化合物を含有する土
壌又は固体状廃棄物に添加し、土壌又は固体状廃棄物中
の重金属或いはその化合物を不溶化することを特徴とす
る土壌又は固体状廃棄物中の重金属類の固定化方法。
(1) Per polyamine molecule, the substituent substituted with the active hydrogen atom of the polyamine is -RX (where X is COOH and R is (CH_2)_n [
However, n is an integer from 1 to 4], CH_2CH (CH_3)
, or CH_2CH-(CH_2COOH)) or a salt thereof, or an aqueous solution of a metal scavenger having at least one hydroxyalkyl group and at least one dithiocarboxy group or a salt thereof as a substituent. , fixation of heavy metals in soil or solid waste, characterized by adding to soil or solid waste containing heavy metals or their compounds to insolubilize the heavy metals or their compounds in the soil or solid waste. method.
(2)固体状廃棄物がEP灰或いは重金属スラッジであ
る特許請求の範囲第1項記載の重金属類の固定化方法。
(2) The method for immobilizing heavy metals according to claim 1, wherein the solid waste is EP ash or heavy metal sludge.
(3)金属捕集剤がポリアミン類の窒素原子に結合した
N−置換基としてアルキル基、アシル基の少なくとも1
種を有する特許請求の範囲第1項又は第2項記載の重金
属類の固定化方法。
(3) The metal scavenger has at least one alkyl group or acyl group as the N-substituent bonded to the nitrogen atom of the polyamine.
A method for immobilizing heavy metals according to claim 1 or 2, which comprises a species.
JP62256061A 1987-10-09 1987-10-09 Method for fixing heavy metals in soil or solid waste Pending JPH0199679A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62256061A JPH0199679A (en) 1987-10-09 1987-10-09 Method for fixing heavy metals in soil or solid waste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62256061A JPH0199679A (en) 1987-10-09 1987-10-09 Method for fixing heavy metals in soil or solid waste

Publications (1)

Publication Number Publication Date
JPH0199679A true JPH0199679A (en) 1989-04-18

Family

ID=17287358

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62256061A Pending JPH0199679A (en) 1987-10-09 1987-10-09 Method for fixing heavy metals in soil or solid waste

Country Status (1)

Country Link
JP (1) JPH0199679A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06166862A (en) * 1992-08-19 1994-06-14 Nippon Soda Co Ltd Fixative for heavy metal of fly ash and detoxication method
US5347071A (en) * 1989-12-20 1994-09-13 Miyoshi Yushi Kabushiki Kaisha Process for the removal of heavy metals from contaminants
US5387365A (en) * 1989-12-20 1995-02-07 Miyoshi Yushi Kabushiki Kaisha Metal scavengers for treating waste water
JPH08224560A (en) * 1994-12-02 1996-09-03 Tosoh Corp Fixing of heavy metals in fly ash
JPH091110A (en) * 1995-04-17 1997-01-07 Nippon Soda Co Ltd Stabilizing method of heavy metal immobilizing agent
JPH09122618A (en) * 1995-10-31 1997-05-13 Miyoshi Oil & Fat Co Ltd Treatment agent for solid waste
JP2007105551A (en) * 2005-08-30 2007-04-26 Taisei Corp Early stabilization method for heavy metal-containing waste material
JP2018043234A (en) * 2016-09-08 2018-03-22 東ソー株式会社 Purification agent for nickel-containing aqueous solution, and method of purifying nickel-containing aqueous solution
US10117934B2 (en) 2011-03-28 2018-11-06 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
JP2019000775A (en) * 2017-06-13 2019-01-10 東ソー株式会社 Wastewater purifier for heavy metal-containing aqueous solution
US11414393B2 (en) 2008-11-07 2022-08-16 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5721550A (en) * 1980-07-09 1982-02-04 Mitsubishi Rayon Co Three dimensional nonwoven structure and method
JPS5787881A (en) * 1980-11-21 1982-06-01 Maeda Sekkei Kk Treatment of incineration refuse
JPS6281478A (en) * 1985-10-04 1987-04-14 Miyoshi Oil & Fat Co Ltd Sequestrant and method of sequestration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5721550A (en) * 1980-07-09 1982-02-04 Mitsubishi Rayon Co Three dimensional nonwoven structure and method
JPS5787881A (en) * 1980-11-21 1982-06-01 Maeda Sekkei Kk Treatment of incineration refuse
JPS6281478A (en) * 1985-10-04 1987-04-14 Miyoshi Oil & Fat Co Ltd Sequestrant and method of sequestration

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5347071A (en) * 1989-12-20 1994-09-13 Miyoshi Yushi Kabushiki Kaisha Process for the removal of heavy metals from contaminants
US5387365A (en) * 1989-12-20 1995-02-07 Miyoshi Yushi Kabushiki Kaisha Metal scavengers for treating waste water
JPH06166862A (en) * 1992-08-19 1994-06-14 Nippon Soda Co Ltd Fixative for heavy metal of fly ash and detoxication method
JPH08224560A (en) * 1994-12-02 1996-09-03 Tosoh Corp Fixing of heavy metals in fly ash
JPH091110A (en) * 1995-04-17 1997-01-07 Nippon Soda Co Ltd Stabilizing method of heavy metal immobilizing agent
JPH09122618A (en) * 1995-10-31 1997-05-13 Miyoshi Oil & Fat Co Ltd Treatment agent for solid waste
JP2007105551A (en) * 2005-08-30 2007-04-26 Taisei Corp Early stabilization method for heavy metal-containing waste material
US11414393B2 (en) 2008-11-07 2022-08-16 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US10117934B2 (en) 2011-03-28 2018-11-06 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US10933139B2 (en) 2011-03-28 2021-03-02 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
JP2018043234A (en) * 2016-09-08 2018-03-22 東ソー株式会社 Purification agent for nickel-containing aqueous solution, and method of purifying nickel-containing aqueous solution
JP2019000775A (en) * 2017-06-13 2019-01-10 東ソー株式会社 Wastewater purifier for heavy metal-containing aqueous solution

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