JP2005089563A - Heavy metal-immobilizing treatment agent and method for immobilizing heavy metal in solid substance - Google Patents
Heavy metal-immobilizing treatment agent and method for immobilizing heavy metal in solid substance Download PDFInfo
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- JP2005089563A JP2005089563A JP2003323017A JP2003323017A JP2005089563A JP 2005089563 A JP2005089563 A JP 2005089563A JP 2003323017 A JP2003323017 A JP 2003323017A JP 2003323017 A JP2003323017 A JP 2003323017A JP 2005089563 A JP2005089563 A JP 2005089563A
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- heavy metal
- homopiperazine
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 80
- 239000007787 solid Substances 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 230000003100 immobilizing effect Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- -1 homopiperazinecarbodithioic acid compound Chemical group 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010881 fly ash Substances 0.000 claims description 14
- QBIGTYKVSINMJS-UHFFFAOYSA-N 1,4-diazepane-1-carbodithioic acid Chemical compound SC(=S)N1CCCNCC1 QBIGTYKVSINMJS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- XUGXCQNSPPKJPC-UHFFFAOYSA-N 1,4-diazepane-1,4-dicarbodithioic acid Chemical compound SC(=S)N1CCCN(C(S)=S)CC1 XUGXCQNSPPKJPC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- PNKGVPLMWAEASD-UHFFFAOYSA-N piperazine-1,4-dicarbodithioic acid Chemical compound SC(=S)N1CCN(C(S)=S)CC1 PNKGVPLMWAEASD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- IDIICHZCEIGXGB-UHFFFAOYSA-N 1-piperazinecarbodithioic acid Chemical compound SC(=S)N1CCNCC1 IDIICHZCEIGXGB-UHFFFAOYSA-N 0.000 description 1
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 description 1
- PGRIFQPYXARIHV-UHFFFAOYSA-N [K].N1(CCNCCC1)C(=S)S Chemical compound [K].N1(CCNCCC1)C(=S)S PGRIFQPYXARIHV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GOFXTABLQPHBFX-UHFFFAOYSA-L dipotassium 1,4-diazepane-1,4-dicarbodithioate Chemical compound C1CN(CCN(C1)C(=S)[S-])C(=S)[S-].[K+].[K+] GOFXTABLQPHBFX-UHFFFAOYSA-L 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- IKLQMIKLCHYTOY-UHFFFAOYSA-L disodium 1,4-diazepane-1,4-dicarbodithioate Chemical compound [Na+].[Na+].[S-]C(=S)N1CCCN(C([S-])=S)CC1 IKLQMIKLCHYTOY-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
本発明は、重金属固定化処理剤及びこの処理剤を用いた固体状物質中の重金属固定化処理方法に関する。 The present invention relates to a heavy metal immobilization treatment agent and a heavy metal immobilization treatment method in a solid substance using the treatment agent.
ゴミ焼却場等で生じる飛灰や焼却灰、煤塵、鉱山から排出される鉱滓、廃水処理の際に生じる活性汚泥、化学工場跡地等の汚染された土壌のような固体状物質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がある。固体状物質から重金属が地下水、河川、海水に溶出すると重大な環境汚染を生じることが問題となっている。 There are various types of solid substances such as fly ash and incineration ash generated at garbage incinerators, dust, mines discharged from mines, activated sludge generated during wastewater treatment, and contaminated soil such as ruins of chemical factories. It contains metals and may contain a large amount of heavy metals that are harmful to the human body, such as mercury, cadmium, lead, zinc, copper, and chromium. When heavy metals are eluted from solid substances into groundwater, rivers and seawater, serious environmental pollution is a problem.
このため従来より、固体状物質を最終投棄する前に重金属固定化処理剤で処理することが提案されており、重金属固定化処理剤としては水銀やカドミウム等の捕集力に優れることから、カルボジチオ酸基やその塩（以下、これらを総称してカルボジチオ基と呼ぶことがある。）を官能基として有する化合物が広く利用されている。このようなカルボジチオ基を官能基として有する重金属固定化処理剤としては、アミン類等の如く窒素原子に結合した活性水素を有する化合物に二硫化炭素を反応させ、アミン類等の窒素原子にカルボジチオ基を導入した化合物が広く知られている（特許文献１、特許文献２）。また飛灰を処理するに際して、ピペラジンの窒素原子にカルボジチオ基が結合した構造の、ピペラジン−Ｎ−カルボジチオ酸やピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸等の重金属固定化処理剤を用いることも提案されている（特許文献３）。 For this reason, it has been conventionally proposed to treat with a heavy metal immobilizing agent before final disposal of the solid substance. As a heavy metal immobilizing agent, carbodithio has an excellent ability to collect mercury and cadmium. A compound having an acid group or a salt thereof (hereinafter sometimes collectively referred to as a carbodithio group) as a functional group is widely used. As a heavy metal immobilization treatment agent having such a carbodithio group as a functional group, carbon disulfide is reacted with a compound having active hydrogen bonded to a nitrogen atom such as amines, and a carbodithio group is bonded to the nitrogen atom of amines or the like. The compound which introduce | transduced is known widely (patent document 1, patent document 2). When treating fly ash, a heavy metal immobilizing agent such as piperazine-N-carbodithioic acid or piperazine-N, N′-biscarbodithioic acid having a structure in which a carbodithio group is bonded to the nitrogen atom of piperazine may be used. It has been proposed (Patent Document 3).
しかしながら特許文献１、特許文献２に記載されている重金属固定化処理剤は、飛灰等に添加した際に二硫化炭素を発生し易いという問題があった。最近、厚生労働省は現在用いられている重金属固定化処理剤の殆どから二硫化炭素が発生することが確認されたとして、ゴミ焼却場や重金属固定化処理剤製造メーカー等の関係者に対して注意を喚起し、重金属固定化処理剤を二硫化炭素の発生し難いものに代替する対策を施すように通達しており、二硫化炭素発生が更に少ない重金属固定化剤が要望されている。また特許文献１，２に記載されている重金属固定化処理剤は、特にアルカリ性飛灰に添加して用いた場合、重金属に対する固定化能が不十分となる虞のあるものがあり、しかも重金属との結合力が経時的に著しく低下し易く、固体状物質中から重金属が溶出する虞があった。一方、特許文献３に記載の重金属固定化処理剤も、二硫化炭素の発生を十分に防止できるとは言い難いとともに、重金属固定化能、重金属固定化能の長期安定性も十分とは言い難かった。 However, the heavy metal immobilizing agent described in Patent Document 1 and Patent Document 2 has a problem that carbon disulfide is easily generated when added to fly ash or the like. Recently, the Ministry of Health, Labor and Welfare has confirmed that carbon disulfide is generated from most of the heavy metal immobilization treatment agents currently used. Therefore, a heavy metal fixing agent that generates less carbon disulfide has been demanded to take measures to replace the heavy metal fixing treatment agent with one that does not easily generate carbon disulfide. In addition, the heavy metal immobilization treatment agent described in Patent Documents 1 and 2 may have insufficient immobilization ability for heavy metals, particularly when added to alkaline fly ash, and with heavy metals. The bond strength of the metal tends to decrease remarkably over time, and heavy metals may be eluted from the solid substance. On the other hand, the heavy metal immobilization treatment agent described in Patent Document 3 cannot be said to sufficiently prevent the generation of carbon disulfide, and the long-term stability of the heavy metal immobilization ability and the heavy metal immobilization ability is also not sufficient. It was.
本発明は上記の点に鑑みなされたもので、上記従来の課題を解決した重金属固定化処理剤及びこの重金属固定化処理剤を用いた固体状物質中の重金属固定化方法を提供することを目的とする。 The present invention has been made in view of the above points, and an object of the present invention is to provide a heavy metal immobilization treatment agent that solves the above-described conventional problems and a method for immobilizing a heavy metal in a solid substance using the heavy metal immobilization treatment agent. And
即ち本発明は、
（１）下記構造式（１）で示されるホモピペラジンの窒素に結合したカルボジチオ酸基又はその塩を官能基として有するホモピペラジンカルボジチオ酸系化合物よりなることを特徴とする重金属固定化処理剤、
That is, the present invention
(1) A heavy metal immobilization treatment agent comprising a homopiperazine carbodithioic acid compound having a carbodithioic acid group or a salt thereof bonded to nitrogen of homopiperazine represented by the following structural formula (1) as a functional group,
（２）ホモピペラジンカルボジチオ酸系化合物が、ホモピペラジン−Ｎ−カルボジチオ酸又はその塩、ホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸又はその塩より選ばれた１種又は２種以上である上記（１）記載の重金属固定化処理剤、 (2) The homopiperazine carbodithioic acid compound is one or more selected from homopiperazine-N-carbodithioic acid or a salt thereof, homopiperazine-N, N′-biscarbodithioic acid or a salt thereof. The heavy metal immobilization treatment agent according to the above (1),
（３）ホモピペラジンカルボジチオ酸系化合物が、ホモピペラジン−Ｎ−カルボジチオ酸のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、ホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸のアルカリ金属、アルカリ土類金属塩、アンモニウム塩より選ばれた１種又は２種以上である上記（１）又は（２）記載の重金属固定化処理剤、 (3) Homopiperazine carbodithioic acid compounds are homopiperazine-N-carbodithioic acid alkali metal salts, alkaline earth metal salts, ammonium salts, homopiperazine-N, N′-biscarbodithioic acid alkali metals, alkalis The heavy metal fixing treatment agent according to the above (1) or (2), which is one or more selected from earth metal salts and ammonium salts,
（４）ホモピペラジンカルボジチオ酸系化合物が、ホモピペラジン−Ｎ−カルボジチオ酸ナトリウム及び／又はホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸ナトリウムである上記（３）記載の重金属固定化処理剤、 (4) The heavy metal fixing treatment agent according to (3), wherein the homopiperazine carbodithioic acid compound is sodium homopiperazine-N-carbodithioate and / or sodium homopiperazine-N, N′-biscarbodithioate,
（５）ホモピペラジンカルボジチオ酸系化合物が、ホモピペラジン−Ｎ−カルボジチオ酸カリウム及び／又はホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムである上記（３）記載の重金属固定化処理剤、 (5) The heavy metal fixing agent according to (3), wherein the homopiperazine carbodithioic acid compound is potassium homopiperazine-N-carbodithioate and / or potassium homopiperazine-N, N′-biscarbodithioate,
（６）上記（１）〜（５）のいずれかに記載の重金属固定化処理剤を固体状物質に添加し、固体状物質中の重金属を不溶化することを特徴とする固体状物質中の重金属固定化方法、 (6) A heavy metal in a solid substance, characterized in that the heavy metal immobilizing agent according to any one of (1) to (5) above is added to a solid substance to insolubilize the heavy metal in the solid substance. Immobilization method,
（７）固体状物質が飛灰、鉱滓、土壌、汚泥のいずれかである上記（６）記載の固体状物質中の重金属固定化方法、 (7) The heavy metal immobilization method in the solid substance according to (6) above, wherein the solid substance is any one of fly ash, mine, soil, and sludge,
（８）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種以上である上記（６）又は（７）記載の固体状物質中の重金属固定化方法、
を要旨とする。
(8) The heavy metal immobilization method in the solid substance according to the above (6) or (7), wherein the heavy metal is one or more selected from the group consisting of lead, mercury, chromium, cadmium, zinc and copper,
Is the gist.
本発明の重金属固定化処理剤は、飛灰に添加した場合でも従来のものに比べ、二硫化炭素発生の虞が少ない。本発明の重金属固定化処理剤を用いて処理した固体状物質は、処理後の環境変化によっても固定化した重金属が溶出することがなく、長期間に亘って安定した重金属固定化能が発揮され、本発明の重金属固定化処理方法によれば、重金属を含む固体状物質を安全かつ確実に処理することができる。 Even when the heavy metal immobilization treatment agent of the present invention is added to fly ash, there is less risk of carbon disulfide generation than conventional ones. The solid substance treated with the heavy metal immobilization treatment agent of the present invention does not elute the immobilized heavy metal due to environmental changes after treatment, and exhibits stable heavy metal immobilization ability over a long period of time. According to the heavy metal immobilization treatment method of the present invention, a solid substance containing heavy metal can be treated safely and reliably.
本発明の重金属固定化処理剤は、ホモピペラジンを例えば水等の溶媒に溶解させ、これに二硫化炭素を添加して反応させる等の方法により行うことができる。本発明の重金属固定化処理剤における官能基であるカルボジチオ基は、酸型（カルボジチオ酸型）であっても塩型（カルボジチオ酸塩型）であっても良い。塩型のカルボジチオ基を有する重金属固定化処理剤は、ホモピペラジンと二硫化炭素との反応終了後、アルカリ金属の水酸化物や炭酸塩、アルカリ土類金属の水酸化物や炭酸塩、或いはアンモニア、アミン等のアルカリで処理するか、ホモピペラジンと二硫化炭素との反応を、これらのアルカリの存在下で行うことにより得ることができる。上記アルカリ金属の水酸化物や炭酸塩としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等が用いられ、アルカリ土類金属の水酸化物や炭酸塩としては、例えば水酸化カルシウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム等が用いられる。またアミンとしては例えば、アゼチジン、ピロリジン、ピペリジン、ピペラジン、ホモピペラジン、ピロール、ピリジン、アンモニア、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、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン等が用いられる。本発明の重金属固定化処理剤は、官能基としてカルボジチオ酸のナトリウム塩、カリウム塩を有するものが好ましい。 The heavy metal immobilization treatment agent of the present invention can be carried out by a method such as dissolving homopiperazine in a solvent such as water and adding carbon disulfide thereto for reaction. The carbodithio group, which is a functional group in the heavy metal immobilization treatment agent of the present invention, may be acid type (carbodithioic acid type) or salt type (carbodithioate type). The heavy metal immobilizing agent having a salt-type carbodithio group can be used after completion of the reaction of homopiperazine and carbon disulfide, after alkali metal hydroxide or carbonate, alkaline earth metal hydroxide or carbonate, or ammonia. It can be obtained by treating with an alkali such as an amine, or by reacting homopiperazine and carbon disulfide in the presence of these alkalis. Examples of the alkali metal hydroxide and carbonate include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Examples of the alkaline earth metal hydroxide and carbonate include calcium hydroxide. Magnesium hydroxide, calcium carbonate, magnesium carbonate and the like are used. Examples of the amine include azetidine, pyrrolidine, piperidine, piperazine, homopiperazine, pyrrole, pyridine, ammonia, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. The heavy metal immobilizing agent of the present invention preferably has a carbodithioic acid sodium salt or potassium salt as a functional group.
ホモピペラジンは、二硫化炭素との反応によってカルボジチオ基が導入され得る窒素原子を２個有しているが、本発明の重金属固定化処理剤はカルボジチオ基を１個のみ有するものであっても、２個有するものであっても良い。またカルボジチオ基を２個有する場合、２個のカルボジチオ基がともに酸型のものであっても、ともに塩型のものであっても良く、また１個が酸型のカルボジチオ基、他の１個が塩型のカルボジチオ基であっても良い。本発明の重金属固定化処理剤は、カルボジチオ基の種類（酸型や塩型、塩の種類等）の異なる化合物や、カルボジチオ基の数が異なる化合物の混合物であっても良い。また１個のカルボジチオ基を有する場合、残る窒素原子にカルボジチオ基以外の官能基が結合した化合物であっても良い。 Homopiperazine has two nitrogen atoms into which a carbodithio group can be introduced by reaction with carbon disulfide, but the heavy metal immobilizing agent of the present invention has only one carbodithio group, You may have two. In the case of having two carbodithio groups, both of the two carbodithio groups may be of the acid type or of the salt type, and one is an acid type carbodithio group and the other one. May be a salt-type carbodithio group. The heavy metal immobilization treatment agent of the present invention may be a compound having different types of carbodithio groups (acid type, salt type, salt type, etc.) or a mixture of compounds having different numbers of carbodithio groups. Moreover, when it has one carbodithio group, the compound which functional groups other than the carbodithio group couple | bonded with the remaining nitrogen atom may be sufficient.
本発明の重金属固定化処理剤は、固体状物質中の重金属を捕集して不溶化処理することができる。本発明の処理剤により固体状物質の処理を行うには、固体状物質に本発明処理剤を添加すれば良い。本発明重金属固定化処理剤は、粉末等の固体状、水分散液、水溶液等として固体状物質に散布、噴霧する等により添加することができる。また必要によって添加後に混練しても良い。固体状物質中の重金属を固定化する反応には水等の溶媒が必要であるため、焼却灰、煤塵、鉱滓等を処理する場合には、本発明処理剤を水等の溶媒に溶解させて固体状物質に添加し、必要により混練するか、本発明処理剤と水とを固体状物質に添加し、必要により混練する方法が採用される。また活性汚泥や土壌等には一般に水分が含有されているため、本発明処理剤を添加し、必要により混練するだけでも効果があるが、更に水を併用することが好ましい。本発明方法で処理した固体状物質は、必要によってセメント等で固めて埋設する等によって、安全に最終処分することができる。本発明固体状物質の処理方法が処理の対象とする固体状物質としては、焼却灰や煤塵、鉱滓、汚泥、土壌等が挙げられるが、本発明方法は特に飛灰の処理に特に好適である。また重金属として、鉛、水銀、クロム、カドミウム、亜鉛及び銅を含む固体状物質の処理に好適である。 The heavy metal immobilization treatment agent of the present invention can collect heavy metals in a solid substance and insolubilize them. In order to treat the solid substance with the treating agent of the present invention, the treating agent of the present invention may be added to the solid substance. The heavy metal immobilizing agent of the present invention can be added by spraying, spraying, etc. on a solid substance as a solid such as a powder, an aqueous dispersion, an aqueous solution or the like. If necessary, kneading may be performed after the addition. Since a solvent such as water is required for the reaction for immobilizing heavy metals in the solid substance, when treating incineration ash, dust, slag, etc., the treatment agent of the present invention is dissolved in a solvent such as water. A method of adding to the solid substance and kneading if necessary, or adding the treating agent of the present invention and water to the solid substance and kneading if necessary is employed. In addition, since activated sludge, soil, and the like generally contain moisture, it is effective to add the treatment agent of the present invention and knead if necessary, but it is preferable to use water together. The solid substance treated by the method of the present invention can be safely disposed of by, for example, solidifying with a cement or the like if necessary and embedding. Examples of the solid substance to be treated by the method for treating a solid substance of the present invention include incinerated ash, dust, slag, sludge, soil, and the like, but the method of the present invention is particularly suitable for the treatment of fly ash. . Moreover, it is suitable for the treatment of solid substances containing lead, mercury, chromium, cadmium, zinc and copper as heavy metals.
以下、実施例、比較例を挙げて本発明を更に詳細に説明する。尚、実施例、比較例において用いた重金属固定化処理剤は以下の通りである。
重金属固定化処理剤Ａ（本発明品）：ホモピペラジン−Ｎ−カルボジチオ酸ナトリウム。
重金属固定化処理剤Ｂ（本発明品）：ホモピペラジン−Ｎ−カルボジチオ酸カリウム。
重金属固定化処理剤Ｃ（本発明品）：ホモピペラジン−Ｎ−カルボジチオ酸カリウムと、ホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウムとの１：１（モル比）混合物。
重金属固定化処理剤Ｄ（本発明品）：ホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸ナトリウム。
重金属固定化処理剤Ｅ（本発明品）：ホモピペラジン−Ｎ，Ｎ’−ビスカルボジチオ酸カリウム。
重属固定化処理剤Ｆ（従来品）：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。
重金属固定化処理剤Ｇ（従来品）：テトラエチレンペンタミン−Ｎ，Ｎ’，Ｎ’’，Ｎ’’’−ペンタカルボジチオ酸ナトリウム。
重金属固定化処理剤Ｈ（従来品）：ピペラジン−Ｎ、Ｎ’−ビスカルボジチオ酸カリウム。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The heavy metal immobilizing agents used in the examples and comparative examples are as follows.
Heavy metal immobilization treatment agent A (product of the present invention): homopiperazine-sodium N-carbodithioate.
Heavy metal immobilization treatment agent B (product of the present invention): homopiperazine-potassium N-carbodithioate.
Heavy metal immobilization treatment agent C (product of the present invention): A 1: 1 (molar ratio) mixture of homopiperazine-N-carbodithioic acid potassium and homopiperazine-N, N′-biscarbodithioic acid potassium.
Heavy metal immobilization treatment agent D (product of the present invention): homopiperazine-N, N′-biscarbodithioate sodium.
Heavy metal immobilization treatment agent E (product of the present invention): homopiperazine-N, N′-biscarbodithioate potassium.
Heavy metal fixing treatment agent F (conventional product): sodium diethylenetriamine-N, N′-N ″ -triscarbodithioate.
Heavy metal immobilizing agent G (conventional product): tetraethylenepentamine-N, N ′, N ″, N ′ ″-sodium pentacarbodithioate.
Heavy metal immobilization treatment agent H (conventional product): Piperazine-N, N′-potassium biscarbodithioate.
実施例１〜５、比較例１〜３
鉛２５００ｍｇ／ｋｇを含む飛灰１００ｇ当たりに対し、表１に示す重金属固定化剤を水に分散又は溶解させた処理液を、重金属固定化剤の添加量が０．７ｇ（無水物としての量）となるように添加し、１０分間混練した。処理直後の飛灰と、処理後に室温、暗所にて１８０日間放置した後の飛灰を環境庁告示第１３号試験に従い溶出試験を行った。鉛の溶出結果を表１に示す。また、重金属固定化処理剤のアルカリ性飛灰接触時の二硫化炭素の発生の有無を、以下の方法により測定した。
Examples 1-5, Comparative Examples 1-3
With respect to 100 g of fly ash containing 2500 mg / kg of lead, the amount of heavy metal fixing agent added is 0.7 g (an amount as an anhydride) for a processing solution in which the heavy metal fixing agent shown in Table 1 is dispersed or dissolved in water. And kneaded for 10 minutes. The fly ash immediately after the treatment and the fly ash after being left in the dark at room temperature for 180 days after the treatment were subjected to a dissolution test according to the Environmental Agency Notification No. 13 test. The lead elution results are shown in Table 1. Moreover, the presence or absence of generation | occurrence | production of the carbon disulfide at the time of the alkaline fly ash contact of a heavy metal fixed processing agent was measured with the following method.
二硫化炭素発生量測定方法
密栓した５００ｍｌ四つ口フラスコにアルカリ性飛灰を２０．０ｇ仕込み、窒素置換した後、０．４ｇ（固形分）の重金属固定化処理剤と水の合計量が３０．０ｇに調整して均一に溶解し、飛灰に添加した。添加後、６０℃で１５分間攪拌した後、二硫化炭素検知管（株式会社ガステック製）にて二硫化炭素発生量を測定した。
Method for measuring carbon disulfide generation amount After charging 20.0 g of alkaline fly ash into a sealed 500 ml four-necked flask and replacing with nitrogen, the total amount of 0.4 g (solid content) heavy metal immobilizing agent and water was 30. It adjusted to 0g, melt | dissolved uniformly, and added to the fly ash. After the addition, the mixture was stirred at 60 ° C. for 15 minutes, and the amount of carbon disulfide generated was measured with a carbon disulfide detector tube (manufactured by Gastec Corporation).
実施例６〜１０、比較例４〜６
鉛４００ｍｇ／ｋｇを含む鉱滓１００ｇ当たりに対し、表２に示す重金属固定化剤を水に分散又は溶解させた処理液を、重金属固定化剤の添加量が０．７ｇ（無水物としての量）となるように添加し、１０分間混練した。処理直後の鉱滓と、処理後に室温、暗所にて１８０日間放置した後の各々鉱滓５０ｇを純水５００ｍＬ中で常温にて６時間振とうして鉛の溶出試験を行った。結果を表２に示す。
Examples 6-10, Comparative Examples 4-6
With respect to 100 g of iron ore containing 400 mg / kg of lead, a processing solution in which the heavy metal fixing agent shown in Table 2 is dispersed or dissolved in water is added in an amount of 0.7 g of heavy metal fixing agent (an amount as an anhydride). And kneaded for 10 minutes. The lead elution test was performed by shaking the iron slag immediately after the treatment and 50 g of each iron slag after being left in the dark at room temperature for 180 days after the treatment in 500 mL of pure water at room temperature for 6 hours. The results are shown in Table 2.
Claims (8)
The method for immobilizing a heavy metal in a solid substance according to claim 6 or 7, wherein the heavy metal is at least one selected from the group consisting of lead, mercury, chromium, cadmium, zinc and copper.
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