JP4565529B2 - Metal scavenger - Google Patents
Metal scavenger Download PDFInfo
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- JP4565529B2 JP4565529B2 JP2000062973A JP2000062973A JP4565529B2 JP 4565529 B2 JP4565529 B2 JP 4565529B2 JP 2000062973 A JP2000062973 A JP 2000062973A JP 2000062973 A JP2000062973 A JP 2000062973A JP 4565529 B2 JP4565529 B2 JP 4565529B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、廃水、焼却灰、煤塵、鉱滓、汚泥、土壌、シュレッダーダスト等の固体状廃棄物中に存在する有害な金属等を固定化したり、廃ガス中の金属を捕集除去して、廃水や固体状廃棄物、廃ガスを無害化することのできる金属捕集剤に関する。
【０００２】
【従来の技術】
工場や研究施設等から排出される廃水、ゴミ焼却場等で生じる焼却灰や煤塵、鉱山から排出される鉱滓、廃水処理の際に用いられる活性汚泥、汚染された土壌等の固体状廃棄物、或いはゴミ焼却場から排出される排煙の如き廃ガス中には種々の金属が含有されており、水銀、カドミウム、鉛、亜鉛、銅、クロム等の人体に有害な重金属が多量に含有されている場合も多い。金属を含む固体状廃棄物から溶出した金属による地下水、河川、海水の汚染や、金属を含む廃ガスによる大気汚染も大きな社会問題となっている。
【０００３】
このため従来より、廃水、固体状廃棄物、廃ガス等を放出したり投棄する前に金属捕集剤で処理することが提案されており、金属捕集剤としては水銀やカドミウム等の捕集力に優れたジチオカルバミン酸型の官能基を有する化合物が広く利用されている。このようなジチオカルバミン酸型の金属捕集剤としては、アミン類に二硫化炭素を反応させて、ジチオカルバミン酸基やその塩を形成した化合物が広く知られている。
【０００４】
【発明が解決しようとする課題】
しかしながら、ジチオカルバミン酸型の官能基を有する従来の金属捕集剤は、水銀やカドミウム等の金属に対する捕集力は優れるものの、鉛や亜鉛等の金属に対する捕集力が低く、これらを含む場合には充分な処理が行い難かった。また固体状廃棄物中の金属は、金属捕集剤によって固定化され、固体状廃棄物中から溶出しないように処理するものであり、金属捕集剤で処理した固体状廃棄物は、そのまま或いは更にコンクリート等で固めた後に最終処分される。しかしながら従来より広く用いられているジチオカルバミン酸型の官能基を有する金属捕集剤は酸性条件下での金属に対する結合力が弱く、このため処理後の固体状廃棄物が酸性雨等に晒された場合、金属捕集剤と金属との結合が外れて固体状廃棄物中から金属が溶出して環境汚染を生じる虞れがあった。
【０００５】
本発明は上記課題を解決するためになされたもので、水銀やカドミウム等の金属に対する捕集力に優れるとともに、鉛や亜鉛等の金属に対する結合力に優れ、しかも、酸性条件下における金属との結合力に優れた金属捕集剤を提供することを目的とする。
【０００６】
【課題を解決するための手段】
即ち、本発明は、ポリアルキレンポリアミンの窒素原子に結合した活性水素と置換した金属捕集性の官能基を有する金属捕集剤であって、官能基としてアルキレン基を介した尿素基と、ジチオ酸基又はジチオ酸基の塩とを有する下記（１）式で示される金属捕集剤である。
【化２】
【０００７】
【発明の実施の形態】
本発明金属処理剤は、下記一般式（１）で示される構造を有する、ポリアルキレンポリアミンの窒素原子に結合した活性水素と置換して導入された置換基として、アルキレン基を介した尿素基の少なくとも１種と、ジチオ酸基、ジチオ酸基の塩の少なくとも１種とを有する化合物である。
【０００９】
【化３】
上記一般式（１）において、Ｒ 4 、Ｒ5、Ｒ6、Ｒ7は、水素、アルキレン基を介した尿素基、ジチオ酸基、ジチオ酸基の塩、あるいはアルキル基、アルキレンカルボン酸基、アルキレンカルボン酸基の塩、アルキレンリン酸基、アルキレンリン酸基の塩である。一般式（１）において、Ｒ4、Ｒ5、Ｒ6、Ｒ7は同一であっても相互に異なっていても良く、またｎの数で示される繰り返し単位毎に異なっていても良いが、一分子中に少なくとも１つのアルキレン基を介した尿素基と、少なくとも１つのジチオ酸基またはジチオ酸基の塩が含まれていることが必要である。また一般式（１）におけるＲ8は炭素数１〜２０のアルキレン基、脂環状化合物を示し、ｎは１以上の整数を示す。
【００１１】
上記（１）で示される構造の化合物は、例えばアルキルアミンとチオ尿素又は尿素とアルデヒド化合物とを反応させた後、アルカリの存在下で二硫化炭素を反応させることにより得られる。アルキルアミンとしては、例えばメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ラウリルアミン等のアルキルアミン、アニリン、ナフチルアミン、アントリルアミン等の芳香族アミンが挙げられる。アルデヒド化合物としては、例えばホルムアルデヒド、グルタルアルデヒドが挙げられる。
【００１２】
上記（１）式で示す化合物は、例えばポリアルキレンポリアミンと、尿素とアルデヒド化合物とを反応させた後、アルカリの存在下で二硫化炭素を反応させることにより得ることができる。ポリアルキレンポリアミンとしては、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、ジエチレントリアミン、ジプロピレントリアミン、ジブチレントリアミン、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、テトラプロピレンペンタミン、テトラブチレンペンタミン、ペンタエチレンヘキサミン、ペンタプロピレンヘキサミン、ペンタブチレンヘキサミン、ヘキサエチレンヘプタミン、ヘキサプロピレンヘプタミン、ヘキサブチレンヘプタミン等や、ピペラジンが挙げられる。
【００１３】
本発明で用いるポリアルキレンポリアミンは、カルボン酸基、アルキル基、ヒドロキシアルキル基等の側鎖を有するものでも良い。またアルキルアミンまたはポリアルキレンポリアミンを更にホルムアルデヒド、ジアルデヒド化合物、ジカルボン酸化合物、ポリグリシジルエーテル化合物、ジイソシアネート化合物等で縮合した縮合アミン化合物も用いることができる。
【００１４】
本発明の金属捕集剤は、１分子中にアルキレン基を介した尿素基と、ジチオ酸基、ジチオ酸基の塩の少なくとも１種とを、各々少なくとも１個ずつ有していることが必要であるが、これらの基はアミン類の置換可能な活性水素のうちの１０〜１００％と置換して導入されていることが好ましい。また、アルキレン基を介した尿素基、ジチオ酸基、ジチオ酸基の塩以外の錯形成性の官能基を有していても良い。このような官能基としては、例えばアミン類の窒素原子に結合したアルキレンカルボン酸基やその塩、アルキレンリン酸基やその塩等が挙げられ、これらの基は２種以上がアルキレン基を介した尿素基とジチオ酸基やジチオ酸基の塩と共に、アミン類の窒素原子に結合していても良い。
【００１５】
本発明の金属捕集剤が処理対象とする廃棄物は、廃水や、例えばゴミ焼却場において生成する焼却灰や煤塵、鉱滓、汚泥、土壌、シュレッダーダスト等の固体状廃棄物、ゴミ焼却場においてゴミを焼却した際に生じる廃ガス等が挙げられる。
【００１６】
廃水を処理する場合、処理しようとする廃水に本発明の金属捕集剤をそのまま、又は水に溶解ないし分散させた状態で添加し、金属捕集剤が金属を捕集して生成したフロックを沈殿除去する方法が採用される。また集塵された焼却灰や煤塵、鉱滓、汚泥、土壌、シュレッダーダスト等の固体状廃棄物を処理する場合、これらの廃棄物に本発明の金属捕集剤を液状又は粉末状のまま添加したり、水溶液等として添加したり噴霧し、混練する等の方法が採用される。固体状廃棄物中の金属は本発明の金属捕集剤と反応して固定化される。また煤塵や廃ガスの場合、焼却炉における焼却工程中、例えば煙路に本発明の金属捕集剤の溶液等を噴霧する等によって、本発明の捕集剤と煤塵とを接触させ、処理後の煤塵をバグフィルターで集塵する等の方法を採用することができる。廃ガスと煤塵とが存在する煙路内に本発明の金属捕集剤を噴霧する等の方法で供給すると、廃ガス中に含まれる金属（主として水銀等のガス化し易い金属）を捕集して廃ガス中から分離できるとともに、煤塵中に含まれる金属の固定化も行うことができる。
【００１７】
本発明の金属捕集剤により廃水、固体状廃棄物、廃ガス等を処理する際に、本発明の所期の目的を阻害しない範囲において、従来の金属捕集剤を併用しても良い。尚、金属捕集剤の添加量は、固体状廃棄物等に含まれる金属等の量によっても異なるが、一般に、本発明の金属捕集剤の添加量は、廃水の場合０．５〜１００ｍｇ／ｌ、固体状廃棄物の場合には０．１〜５０重量％、廃ガスの場合には０．５〜２０００ｍｇ／Ｎｍ3 程度が好ましい。
【００１８】
本発明の金属捕集剤によって処理した廃水は、フロックを分離除去後、河川に放流することができる。また焼却灰や煤塵、鉱滓、土壌、シュレッダーダスト、汚泥等の固体状廃棄物や、廃ガス処理後の煤塵等の廃棄物は、必要に応じて処理後の廃棄物をセメントで固めて投棄する等の最終処分を行うことができる。本発明の金属捕集剤で処理後の廃棄物をセメント等で固めて最終処分する場合、従来の金属捕集剤によって処理した場合に比べ、セメントの使用量が少ない場合でも、廃棄物中の金属が再溶出して二次汚染を生じる等の虞れが少ない。
【００１９】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。尚、以下の実施例、比較例で用いた金属捕集剤は以下の通りである。
【００２２】
金属捕集剤１（本発明品）：ジエチレントリアミン１モル当たり、尿素１．５モル、ホルムアルデヒド１．５モルを反応させた後、二硫化炭素１．５モルを水酸化ナトリウムの存在下で反応させ、ジエチレントリアミンの窒素原子にアルキレン基を介した尿素基１．５個（平均）と、ジチオ酸基のナトリウム塩１．５個（平均）を導入した化合物。
【００２４】
金属捕集剤２（本発明品）：テトラエチレンペンタミン１モル当たり、アクリル酸メチル１モルを反応させ、次いでケン化してカルボン酸基のナトリウム塩を導入した後、尿素１モル、ホルムアルデヒド１モルを反応させた後、更に二硫化炭素２モルを水酸化ナトリウムの存在下で反応させ、テトラエチレンペンタミンの窒素原子に、アルキレン基を介した尿素基１．５個（平均）と、ジチオ酸基のナトリウム塩１．５個（平均）を導入した化合物。
【００２６】
金属捕集剤３（本発明品）：ピペラジン１モル当たり、尿素１モル、ホルムアルデヒド１モルを反応させた後、二硫化炭素１モルをアルカリの存在下で反応させ、ピペラジンの窒素原子にアルキレン基を介した尿素基１個と、ジチオ酸基のナトリウム塩１個を導入した化合物。
【００２８】
金属捕集剤４（従来品）：テトラエチレンペンタミン１モル当たり、二硫化炭素４モルをアルカリの存在下で反応させ、テトラエチレンペンタミンの窒素原子に、ジチオ酸基のナトリウム塩４個を導入した化合物。
【００２９】
実施例１〜３、比較例１
亜鉛６７０ｍｇ／ｋｇ、鉛１１５０ｍｇ／ｋｇ、水銀２８０ｍｇ／ｋｇを含む煤塵１００ｇ当たりに対し、表１に示す金属捕集剤の水溶液（又は分散液）を、金属捕集剤の添加量が２ｇ（固形分換算）となるように添加し、１５０〜１８０℃で３０分間混練した。各捕集剤で処理済の煤塵と未処理の煤塵各５０ｇを、ｐＨ＝６．０とｐＨ＝３．５の水５００ｍｌ中で常温にて６時間振とうし、水中に溶出した金属濃度を測定した。水中に溶出した金属の濃度は原子吸光分析法により測定した。結果を表１に示す。
【００３０】
【表１】
実施例４〜６、比較例２
鉛４８５ｍｇ／ｋｇ、亜鉛１５３０ｍｇ／ｋｇ、カドミウム２１０ｍｇ／ｋｇを含有する鉱滓１００ｇ当たりに対し、表２に示す金属捕集剤の水溶液（又は分散液）を添加量が３ｇ（固形分換算）となるように添加し、８０〜１２０℃で３０分間混練した。各捕集剤で処理済の鉱滓と未処理の鉱滓各５０ｇを用い、実施例１〜３と同様にして水中に溶出した金属濃度を測定した。結果を表２に示す。
【００３２】
【表２】
実施例７〜９、比較例３
鉛３２ｍｇ／ｋｇ、水銀７ｍｇ／ｋｇ、カドミウム６２４ｍｇ／ｋｇを含有する土壌１００ｇ当たりに対し、表３に示す金属捕集剤の水溶液（又は分散液）を添加量が１ｇ（固形分換算）となるように添加し、８０〜１２０℃で２０分間混練した。各捕集剤で処理済の土壌と未処理の土壌各５０ｇを用い、実施例１〜３と同様にして水中に溶出した金属濃度を測定した。結果を表３に示す。
【００３４】
【表３】
実施例１０〜１２、比較例４
水銀１ｍｇ／Ｎｍ3 、鉛３ｍｇ／Ｎｍ3、ダスト２ｇ／Ｎｍ3 を含むゴミ焼却場の廃ガス（１４０００Ｎｍ3 ／時間、２８０℃）に、表４に示す金属捕集剤の水溶液を、金属捕集剤が固型分として２５０ｍｇ／Ｎｍ3 の割合で供給されるように煙道中に噴霧し、廃ガス中の水銀と金属捕集剤とを反応させた後、バグフィルターにて集塵した。バグフィルター通過後の廃ガス中に残存する水銀の濃度を測定した結果を表４に示す。また、バグフィルターにて集塵された煤塵５０ｇを用い、実施例１〜３と同様にして水中に溶出した金属濃度を測定した。結果を表４に示す。
【００３６】
【表４】
実施例１３〜１５、比較例５
鉛２３ｍｇ／ｋｇ、水銀５ｍｇ／ｋｇ、亜鉛３ｍｇ／ｋｇを含有する廃水１リットル当たりに対し、表５に示す金属捕集剤の水溶液（又は分散液）を添加量が５ｍｇ（固形分換算）となるように添加して２０℃で３０分間撹拌し、次いで静置した後、生成したフロックを分離して除去した。フロック除去後の廃水中の残存金属濃度を測定した結果を表５に示す。
【００３８】
【表５】
【発明の効果】
以上説明したように本発明の金属捕集剤は、従来のジチオカルバミン酸型金属捕集剤と同様に水銀やカドミウムに対して優れた捕集力を発揮するとともに、鉛や亜鉛に対しても優れた捕集力を有するため、本発明の金属捕集剤によれば、鉛や亜鉛を含む廃水、固体状廃棄物、廃ガスを効果的に処理することができる。また本発明の金属捕集剤は、酸性条件下においても金属に対して優れた結合力を有するため、本発明捕集剤で処理した固体状廃棄物は、酸性雨等に晒された場合でも、固体状廃棄物中から金属が再溶出する虞れがない等の効果を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention immobilizes harmful metals present in solid waste such as waste water, incinerated ash, dust, slag, sludge, soil, shredder dust, or collects and removes metal in waste gas, The present invention relates to a metal scavenger capable of detoxifying waste water, solid waste, and waste gas.
[0002]
[Prior art]
Solid waste such as wastewater discharged from factories and research facilities, incineration ash and dust generated at garbage incinerators, mines discharged from mines, activated sludge used in wastewater treatment, contaminated soil, Or waste gas such as smoke emitted from garbage incinerators contains various metals, and contains a large amount of heavy metals harmful to the human body such as mercury, cadmium, lead, zinc, copper, and chromium. There are many cases. Contamination of groundwater, rivers and seawater caused by metal eluted from solid waste containing metal, and air pollution caused by waste gas containing metal are also major social problems.
[0003]
For this reason, it has been proposed to treat with a metal scavenger before releasing or dumping waste water, solid waste, waste gas, etc., and as a metal scavenger, mercury or cadmium is collected. A compound having a dithiocarbamic acid type functional group excellent in strength is widely used. As such a dithiocarbamic acid type metal scavenger, compounds in which dithiocarbamic acid groups and salts thereof are formed by reacting amines with carbon disulfide are widely known.
[0004]
[Problems to be solved by the invention]
However, the conventional metal scavengers having a dithiocarbamic acid type functional group have excellent scavenging power for metals such as mercury and cadmium, but have low scavenging power for metals such as lead and zinc. It was difficult to perform sufficient processing. The metal in the solid waste is fixed by the metal scavenger and is processed so as not to elute from the solid waste. The solid waste treated with the metal scavenger is left as it is or Furthermore, it is disposed of after being hardened with concrete. However, metal collectors having dithiocarbamic acid type functional groups, which have been widely used in the past, have a weak binding force to metals under acidic conditions, so that the solid waste after treatment was exposed to acid rain, etc. In this case, the bond between the metal scavenger and the metal may be removed, and the metal may be eluted from the solid waste to cause environmental pollution.
[0005]
The present invention has been made in order to solve the above-mentioned problems, and has an excellent ability to collect metals such as mercury and cadmium, and also has an excellent binding force to metals such as lead and zinc, and also has a high affinity for metals under acidic conditions. It aims at providing the metal scavenger excellent in bond strength.
[0006]
[Means for Solving the Problems]
That is, the present onset Ming, a metal scavenger having a polyalkylene polyamine bonded to active hydrogen and substituted metal trapping functional group to the nitrogen atom of the urea group through an alkylene group as a functional group, A metal scavenger represented by the following formula (1) having a dithioic acid group or a salt of a dithioic acid group .
[Chemical 2]
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention metal treatment agent has a structure represented by the following following general formula (1), as a substituent group introduced to replace the bound active hydrogen to the nitrogen atom of the polyalkylene polyamines, a urea group through an alkylene group And a compound having at least one of a dithioic acid group and a salt of a dithioic acid group.
[0009]
[Chemical 3]
In the general formula (1), R 4, R 5, R 6, R 7 is hydrogen, urine via an alkylene group containing group, dithio group, salts of dithio acid or an alkyl group, alkylene carboxylic acid A salt of an alkylene carboxylic acid group, an alkylene phosphoric acid group, or a salt of an alkylene phosphoric acid group. In the general formula ( 1 ), R 4 , R 5 , R 6 and R 7 may be the same or different from each other, and may be different for each repeating unit represented by the number of n. It is necessary for one molecule to contain a urea group via at least one alkylene group and at least one dithioic acid group or a salt of a dithioic acid group. The R 8 in the general formula (1) represents an alkylene group having 1 to 20 carbon atoms, alicyclic compounds, n represents an integer of 1 or more.
[0011]
The compound having the structure represented by the above (1) can be obtained, for example, by reacting an alkylamine and thiourea or urea and an aldehyde compound and then reacting carbon disulfide in the presence of an alkali. Examples of the alkylamine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine and laurylamine, and aromatic amines such as aniline, naphthylamine and anthrylamine. Examples of the aldehyde compound include formaldehyde and glutaraldehyde.
[0012]
Compound represented by (1) above formula, for example a polyalkylene polyamine, after reacting the aldehyde compound urea can be obtained by reacting carbon disulfide in the presence of an alkali. Examples of the polyalkylene polyamine include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, tetrabutylene. pentamine, pentaethylene hexamine, pentapropylene hexamine, penta butylene hexamine, hexaethyleneheptamine, hexapropylene heptamine, and hexa-butylene heptamine like, piperazine Ru mentioned.
[0013]
The polyalkylene polyamine used in the present invention may have a side chain such as a carboxylic acid group, an alkyl group, or a hydroxyalkyl group. A condensed amine compound obtained by further condensing an alkylamine or polyalkylenepolyamine with formaldehyde, a dialdehyde compound, a dicarboxylic acid compound, a polyglycidyl ether compound, a diisocyanate compound, or the like can also be used.
[0014]
Metal scavenger of the present invention, needs to have a urea group through an alkylene group in a molecule, dithio acid, and at least one salt of dithiophosphoric acid, respectively, at least one by one However, it is preferable that these groups are introduced by replacing 10 to 100% of the substitutable active hydrogens of amines. Further , it may have a complex-forming functional group other than a salt of urea group, dithioic acid group, or dithioic acid group via an alkylene group. Examples of such a functional group include an alkylene carboxylic acid group bonded to a nitrogen atom of an amine or a salt thereof, an alkylene phosphate group or a salt thereof, and two or more of these groups are mediated by an alkylene group. A urea group and a dithioic acid group or a salt of a dithioic acid group may be bonded to the nitrogen atom of the amine.
[0015]
The waste to be treated by the metal scavenger of the present invention is waste water, solid waste such as incinerated ash and dust generated in a garbage incinerator, mines, sludge, soil, shredder dust, etc., in a garbage incinerator. Examples include waste gas generated when garbage is incinerated.
[0016]
When treating wastewater, the metal scavenger of the present invention is added to the wastewater to be treated as it is or dissolved or dispersed in water, and the floc produced by the metal scavenger collecting the metal is added. A method for removing the precipitate is adopted. Also, when treating solid waste such as incinerated ash, dust, slag, sludge, soil, and shredder dust, the metal scavenger of the present invention is added to these wastes in liquid or powder form. Or a method such as adding as an aqueous solution or spraying and kneading. The metal in the solid waste reacts with the metal scavenger of the present invention and is immobilized. Also, in the case of dust and waste gas, during the incineration process in the incinerator, for example, by spraying the solution of the metal scavenger of the present invention on the flue, etc. It is possible to adopt a method such as collecting dust with a bag filter. When supplied by a method such as spraying the metal scavenger of the present invention into a flue where waste gas and dust are present, the metal contained in the waste gas (mainly metal that is easily gasified such as mercury) is collected. Thus, it can be separated from the waste gas, and the metal contained in the dust can be fixed.
[0017]
When treating waste water, solid waste, waste gas or the like with the metal scavenger of the present invention, a conventional metal scavenger may be used in combination as long as the intended purpose of the present invention is not impaired. In addition, although the addition amount of a metal scavenger also changes with the quantity of the metal etc. which are contained in solid waste etc., generally the addition amount of the metal scavenger of this invention is 0.5-100 mg in the case of wastewater. / L, 0.1 to 50% by weight in the case of solid waste, and 0.5 to 2000 mg / Nm 3 in the case of waste gas.
[0018]
The wastewater treated with the metal scavenger of the present invention can be discharged into a river after separating and removing floc. In addition, solid waste such as incineration ash, dust, mines, soil, shredder dust, sludge, etc., and waste such as soot after waste gas treatment, dump the treated waste with cement as necessary. Final disposal such as can be performed. When the waste after treatment with the metal scavenger of the present invention is solidified with cement or the like and finally disposed, even if the amount of cement used is small compared to the case of treating with a conventional metal scavenger, There is little risk of re-elution of metals and secondary contamination.
[0019]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the metal scavengers used in the following examples and comparative examples are as follows.
[0022]
Metal scavenger 1 (Invention product): After reacting 1.5 mol of urea and 1.5 mol of formaldehyde per 1 mol of diethylenetriamine, 1.5 mol of carbon disulfide is reacted in the presence of sodium hydroxide. The compound which introduce | transduced 1.5 urea groups (average) through the alkylene group into the nitrogen atom of diethylenetriamine and 1.5 sodium salts (average) of the dithioic acid group.
[0024]
Metal scavenger 2 (Product of the present invention): 1 mol of methyl acrylate is reacted per 1 mol of tetraethylenepentamine, then saponified to introduce sodium salt of carboxylic acid group, 1 mol of urea, 1 mol of formaldehyde Then, 2 moles of carbon disulfide is further reacted in the presence of sodium hydroxide, and 1.5 nitrogen groups (average) via an alkylene group are added to the nitrogen atom of tetraethylenepentamine, and dithioacid. A compound into which 1.5 sodium groups (average) were introduced.
[0026]
Metal scavenger 3 (Product of the present invention): After reacting 1 mole of urea and 1 mole of formaldehyde per mole of piperazine, 1 mole of carbon disulfide is reacted in the presence of alkali, and an alkylene group is added to the nitrogen atom of piperazine. and one urea group through, compounds obtained by introducing one sodium salt of dithio groups.
[0028]
Metal scavenger 4 (Conventional product): 4 mol of carbon disulfide is reacted in the presence of alkali per 1 mol of tetraethylenepentamine, and 4 sodium salts of dithioic acid groups are added to the nitrogen atom of tetraethylenepentamine. Introduced compound.
[0029]
Examples 1 to 3 and Comparative Example 1
With respect to 100 g of dust containing 670 mg / kg of zinc, 1150 mg / kg of lead, and 280 mg / kg of mercury, the amount of the metal scavenger shown in Table 1 is 2 g (solid) And the mixture was kneaded at 150 to 180 ° C. for 30 minutes. Shake 50g each of the dust treated with each scavenger and untreated soot in 500ml of water with pH = 6.0 and pH = 3.5 at room temperature for 6 hours, and adjust the metal concentration eluted in water. It was measured. The concentration of metal eluted in water was measured by atomic absorption spectrometry. The results are shown in Table 1.
[0030]
[Table 1]
Examples 4 to 6 and Comparative Example 2
The amount of addition of an aqueous solution (or dispersion) of the metal scavenger shown in Table 2 is 3 g (solid content conversion) per 100 g of iron ore containing 485 mg / kg of lead, 1530 mg / kg of zinc, and 210 mg / kg of cadmium. And kneaded at 80 to 120 ° C. for 30 minutes. The metal concentration eluted in water was measured in the same manner as in Examples 1 to 3 using 50 g of each of the slag treated with each collecting agent and 50 g of untreated slag. The results are shown in Table 2.
[0032]
[Table 2]
Examples 7 to 9 and Comparative Example 3
The amount of addition of an aqueous solution (or dispersion) of the metal scavenger shown in Table 3 is 1 g (solid content conversion) per 100 g of soil containing 32 mg / kg of lead, 7 mg / kg of mercury, and 624 mg / kg of cadmium. And kneaded at 80 to 120 ° C. for 20 minutes. The metal concentration eluted in water was measured in the same manner as in Examples 1 to 3 using 50 g of soil treated with each scavenger and 50 g of untreated soil. The results are shown in Table 3.
[0034]
[Table 3]
Examples 10 to 12 and Comparative Example 4
Mercury 1 mg / Nm 3, lead 3 mg / Nm 3, the waste gas incinerators including dust 2g / Nm 3 (14000Nm 3 / time, 280 ° C.) to the aqueous solution of a metal scavenger as shown in Table 4, metal capturing After spraying in the flue so that the collector was supplied as a solid component at a rate of 250 mg / Nm 3 , the mercury in the waste gas and the metal scavenger were reacted, and then collected with a bag filter. Table 4 shows the result of measuring the concentration of mercury remaining in the waste gas after passing through the bag filter. Further, using 50 g of dust collected by the bag filter, the metal concentration eluted in water was measured in the same manner as in Examples 1 to 3 . The results are shown in Table 4.
[0036]
[Table 4]
Examples 13 to 15 and Comparative Example 5
With respect to 1 liter of wastewater containing 23 mg / kg of lead, 5 mg / kg of mercury, and 3 mg / kg of zinc, the addition amount of an aqueous solution (or dispersion) of the metal scavenger shown in Table 5 is 5 mg (in terms of solid content). The mixture was stirred at 20 ° C. for 30 minutes and then allowed to stand, and then the generated floc was separated and removed. Table 5 shows the results of measuring the residual metal concentration in the wastewater after floc removal.
[0038]
[Table 5]
【The invention's effect】
As described above, the metal scavenger of the present invention exhibits excellent scavenging power for mercury and cadmium as well as conventional dithiocarbamate metal scavengers, and is also excellent for lead and zinc. Therefore, according to the metal scavenger of the present invention, it is possible to effectively treat waste water, solid waste, and waste gas containing lead and zinc. Further, since the metal scavenger of the present invention has an excellent binding force to metals even under acidic conditions, the solid waste treated with the scavenger of the present invention can be exposed to acid rain or the like. In addition, there is an effect that there is no possibility that the metal is re-eluted from the solid waste.
Claims (1)
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| CN103945947A (en) | 2011-10-18 | 2014-07-23 | 塞特克技术公司 | Collector compositions and methods of using the same |
| IN2014CN02934A (en) | 2011-10-18 | 2015-07-03 | Cytec Tech Corp | |
| CA2852681A1 (en) | 2011-10-18 | 2013-04-25 | Cytec Technology Corp. | Froth flotation process utilizing a tertiary or quaternary organic ammonium salt of an organic-sulfur containing acid |
| CN106496404B (en) * | 2016-10-31 | 2018-02-09 | 上海佰奥聚新材料科技有限公司 | Polyacrylate polymer dispersion liquid |
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| JPS5649785A (en) * | 1980-05-09 | 1981-05-06 | Agency Of Ind Science & Technol | Conditioning of contaminated soil |
| JPS63294986A (en) * | 1987-05-26 | 1988-12-01 | Miyoshi Oil & Fat Co Ltd | Treatment of heavy metal-containing waste water |
| JP3912812B2 (en) * | 1995-12-28 | 2007-05-09 | 日本曹達株式会社 | A chelating agent comprising an aqueous metal salt of dithiocarbamate and a method for producing the same |
| JPH1147766A (en) * | 1997-07-31 | 1999-02-23 | Unitika Ltd | Arsenic fixing agent and treatment of drainage containing arsenic |
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