JP4501029B2 - Immobilization of heavy metals in fly ash - Google Patents
Immobilization of heavy metals in fly ash Download PDFInfo
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- JP4501029B2 JP4501029B2 JP2004293235A JP2004293235A JP4501029B2 JP 4501029 B2 JP4501029 B2 JP 4501029B2 JP 2004293235 A JP2004293235 A JP 2004293235A JP 2004293235 A JP2004293235 A JP 2004293235A JP 4501029 B2 JP4501029 B2 JP 4501029B2
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Description
本発明は、焼却炉から発生する飛灰においてその中の重金属の溶出を防ぐために重金属を固定化する方法に関する。より詳しくは、焼却飛灰は、埋め立て処分前に溶融、薬剤処分、セメント固化、溶媒抽出のうちいずれかの処理を施すことが義務付けられているが、本発明は薬剤処理の分野での改善に関する。 The present invention relates to a method for immobilizing heavy metals to prevent elution of heavy metals therein in fly ash generated from an incinerator. More specifically, incineration fly ash is obliged to be subjected to any one of melting, chemical disposal, cement solidification, and solvent extraction prior to landfill disposal, but the present invention relates to improvements in the field of chemical treatment. .
薬剤処理法で用いる薬剤は次の３つに大別される；
Ａ）ｐＨ調整剤またはそれに凝集沈殿効果を付与したもの
Ｂ）キレート剤
Ｃ）その他の薬剤
Ａ）はＢ）やＣ）に比べ単価が安いが、対象となる飛灰のアルカリ度が大きい場合にはその添加量を多くする必要がある。
The drugs used in the drug treatment method are roughly divided into the following three types:
A) A pH adjuster or a substance with a coagulation precipitation effect B) Chelating agent C) Other agents A) is cheaper than B) and C), but the target fly ash has a high alkalinity. It is necessary to increase the amount of addition.
いずれの薬剤についても、被処理飛灰量が大量であるため処理コストが大きく、そのコストの低減が課題となっている。 For any chemical, the amount of fly ash to be processed is large, so the processing cost is high, and the reduction of the cost has been an issue.
現在、重金属溶出防止のための薬剤処理としては、キレート剤を用いる処理が主流であるが、仮に、将来、金属類枯渇のため飛灰処分場内で重金属を再利用することが必要になった場合、加熱処理あるいは強酸処理によりキレート結合を破壊し重金属を回収する必要が生じて来る。いずれの場合も硫黄系のガスが発生することは避けられず、排ガス処理は当然のことながら必要である。 Currently, chelating agents are mainly used as chemical treatments to prevent elution of heavy metals, but if it becomes necessary to reuse heavy metals in the fly ash disposal site in the future due to metal depletion However, it is necessary to recover the heavy metal by breaking the chelate bond by heat treatment or strong acid treatment. In either case, the generation of sulfur-based gas is inevitable, and it is a matter of course that exhaust gas treatment is necessary.
薬剤処理した飛灰は、通常、管理型処分場に埋め立てられるが、この型の処分場は地下へ浸出液が流れ出さないよう遮水されており、浸出水は集められ凝沈等の処理の後放流される。自然界で移動性の小さい重金属類に対し、入口で薬剤処理、さらに出口で凝沈処理といういわゆる“２重処理”を施すことはリスクに対するコスト負担が過剰であり、国費の効果的な利用とは言えない。 Chemically treated fly ash is usually landfilled in a controlled disposal site, but this type of disposal site is shielded against seepage from the leachate to the basement, and the leachate is collected and treated after coagulation. It is released. Applying the so-called “double treatment” of chemical treatment at the entrance and coagulation treatment at the exit to heavy metals that have low mobility in nature is an excessive cost burden for risk, and the effective use of national expenses I can not say.
これらの実状からすると、キレート薬剤による強固な固化処理は現在および将来にわたり国民負担の増大を招くものである。 From these facts, the solidified treatment with chelating agents will increase the burden on the public now and in the future.
そこで、本発明は、ごみ焼却炉における安価な飛灰処理方法を提供することを目的とする。 Then, an object of this invention is to provide the cheap fly ash processing method in a garbage incinerator.
本発明は、湿式による酸性排ガス処理にアルカリ剤を使うことで、炭酸塩等を含むアルカリ液を製造し、これを中性飛灰の重金属固定剤として使用するというものである。炭酸塩等を含むアルカリ液を飛灰と混合することで、飛灰中の重金属類が不溶性の炭酸塩等となり、また溶液はｐＨ緩衝性が高く、飛灰を適正なｐＨにすることが容易である。 The present invention uses an alkali agent for wet acidic exhaust gas treatment to produce an alkali liquid containing carbonate and the like, and uses this as a heavy metal fixing agent for neutral fly ash. By mixing alkaline liquid containing carbonate etc. with fly ash, heavy metals in fly ash become insoluble carbonate, etc., and the solution has high pH buffering property, making it easy to adjust fly ash to an appropriate pH. It is.
すなわち、本発明の第１のものは、第１反応槽（１）に蓄えた水にＨＣｌおよびＣＯ ２ 含有ガスを吹き込み、ついで、第１反応槽（１）の液の一部を第２反応槽（２）へ送り、同槽（２）内の液にＮａＯＨまたはＫＯＨの溶液を加えて、第２反応槽（２）の液のｐＨを９〜１２．５に調整し、その後この液を第１反応槽（１）に戻して、ＨＣｌおよびＣＯ２よりなる酸性成分を含むガスを、ＮａＯＨまたはＫＯＨの溶液で洗浄し、これらの操作を連続して行うことにより得られたＮａ２ＣＯ３ およびＮａＣｌ、またはＫ ２ ＣＯ ３ およびＫＣｌを含む第１反応槽（１）内の塩含有液を、重金属含有飛灰と混合することを特徴とする、飛灰中重金属の固定化方法に関する。ＨＣｌ、ＣＯ ２ よりなる酸性成分を含むガスを、ＮａＯＨ、ＫＯＨのアルカリ溶液で洗浄した後、同液のｐＨを９〜１２．５、好ましくは１０．５〜１１．５に調整する。
That is, according to the first aspect of the present invention , HCl and CO 2 -containing gas is blown into the water stored in the first reaction tank (1), and then a part of the liquid in the first reaction tank (1) is subjected to the second reaction. It is sent to the tank (2), and a solution of NaOH or KOH is added to the liquid in the tank (2) to adjust the pH of the liquid in the second reaction tank (2) to 9 to 12.5. back to the first reaction vessel (1), a gas containing an acidic component consisting of HCl and CO 2, and washed with a solution of NaOH or KOH, Na 2 CO 3 obtained by continuously performing these operations And a salt-containing liquid in the first reaction vessel (1) containing NaCl, or K 2 CO 3 and KCl, and a heavy metal-containing fly ash, and a method for immobilizing heavy metals in fly ash. After the gas containing an acidic component composed of HCl and CO 2 is washed with an alkaline solution of NaOH and KOH, the pH of the solution is adjusted to 9 to 12.5, preferably 10.5 to 11.5.
本発明の第２のものは、第１反応槽（１）に蓄えた水にＨＣｌおよびＣＯ ２ 含有ガスを吹き込み、ついで、第１反応槽（１）の液の一部を第２反応槽（２）へ送り、同槽（２）内の液にＮａＯＨまたはＫＯＨの溶液を加えて、第２反応槽（２）の液のｐＨを９〜１２．５に調整し、その後この液を第１反応槽（１）に戻して、ＨＣｌおよびＣＯ２よりなる酸性成分を含むガスを、ＮａＯＨまたはＫＯＨの溶液で洗浄し、これらの操作を連続して行うことにより得られたＮａ２ＣＯ３ およびＮａＣｌ、またはＫ ２ ＣＯ ３ およびＫＣｌを含む塩含有液からなることを特徴とする、飛灰中重金属の固定化薬剤に関する。ＨＣｌ、ＣＯ ２ よりなる酸性成分を含むガスを、ＮａＯＨ、ＫＯＨのアルカリ溶液で洗浄した後、同液のｐＨを９〜１２．５、好ましくは１０．５〜１１．５に調整する。
In the second aspect of the present invention , HCl and CO 2 -containing gas is blown into the water stored in the first reaction tank (1), and then a part of the liquid in the first reaction tank (1) is second reaction tank ( 2), and a solution of NaOH or KOH is added to the liquid in the tank (2) to adjust the pH of the liquid in the second reaction tank (2) to 9 to 12.5. Returning to the reaction vessel (1), the gas containing an acidic component composed of HCl and CO 2 was washed with a solution of NaOH or KOH, and Na 2 CO 3 and NaCl obtained by continuously performing these operations. or it characterized by comprising a salt-containing solution containing K 2 CO 3 and KCl, relates immobilization agents of heavy metals in fly ash. After the gas containing an acidic component composed of HCl and CO 2 is washed with an alkaline solution of NaOH and KOH, the pH of the solution is adjusted to 9 to 12.5, preferably 10.5 to 11.5.
本発明において、上記酸性成分は、ＨＣｌ、ＣＯ ２ である。アルカリはＮａＯＨ、ＫＯＨである。酸性成分を含むガスをアルカリ溶液で洗浄した結果、中和によりこの液中にＮａ２ＣＯ３，Ｋ２ＣＯ３，ＮａＣｌ，ＫＣｌの塩が生成する。ｐＨを９〜１２．５、好ましくは１０．５〜１１．５に調整するには、ＮａＯＨ，ＫＯＨのアルカリの添加量を調整する。
In the present invention, the acidic component is HCl, CO 2 . The alkali is NaOH or KOH . As a result of washing the gas containing an acidic component with an alkaline solution, a salt of Na 2 CO 3 , K 2 CO 3 , NaCl,
こうして得られたＮａ２ＣＯ３，Ｋ２ＣＯ３，ＮａＣｌ，ＫＣｌの塩を含む液を飛灰中重金属の固定化薬剤として、重金属含有飛灰と混合する。 The liquid containing the salt of Na 2 CO 3 , K 2 CO 3 , NaCl, and K 2 Cl thus obtained is mixed with heavy metal-containing fly ash as a heavy metal immobilizing agent in the fly ash.
飛灰は水分を含む灰またはスラリー灰であってもよい。固定化薬剤と重金属含有飛灰の混合は撹拌下または混練下に行うのが好ましい。固定化薬剤と重金属含有飛灰の混合物に水酸化アルミニウム、ポリ塩化アルミニウム、Ｆｅ（ＯＨ）３、ＦｅＣｌ３、Ｆｅ２（ＳＯ４）３の凝集沈殿作用のある薬剤を単独であるいは組み合わせで加えることが好ましい。 The fly ash may be ash containing water or slurry ash. Mixing of the immobilization agent and heavy metal-containing fly ash is preferably performed with stirring or kneading. Adding a single agent or a combination of agents having an aggregating action of aluminum hydroxide, polyaluminum chloride, Fe (OH) 3 , FeCl 3 , Fe 2 (SO 4 ) 3 to the mixture of the immobilizing agent and heavy metal-containing fly ash Is preferred.
湿式洗煙塔のアルカリ水は循環して使用することが好ましい。循環水のｐＨを９〜１２．５、好ましくは１０．５〜１１．５に調整する。循環ラインヘは一部新しいアルカリ剤を供給し、供給分の循環水を抜き出す。抜き出した液を混練機等の飛灰混合機に送り、ここで重金属含有飛灰と十分に混合する。 It is preferable to circulate and use the alkaline water of the wet smoke-washing tower. The pH of the circulating water is adjusted to 9 to 12.5, preferably 10.5 to 11.5. Part of the circulation line is supplied with fresh alkaline agent, and the circulating water for the supply is extracted. The extracted liquid is sent to a fly ash mixer such as a kneader, where it is thoroughly mixed with the heavy metal-containing fly ash.
本発明は、湿式による酸性排ガス処理にアルカリ剤を使うことで、炭酸塩等を含むアルカリ液を製造し、これを中性飛灰の重金属固定化薬剤として使用するというもので、具体的には、第１反応槽（１）に蓄えた水にＨＣｌおよびＣＯ ２ 含有ガスを吹き込み、ついで、第１反応槽（１）の液の一部を第２反応槽（２）へ送り、同槽（２）内の液にＮａＯＨまたはＫＯＨの溶液を加えて、第２反応槽（２）の液のｐＨを９〜１２．５に調整し、その後この液を第１反応槽（１）に戻して、ＨＣｌおよびＣＯ２よりなる酸性成分を含むガスを、ＮａＯＨまたはＫＯＨの溶液で洗浄し、これらの操作を連続して行うことにより得られたＮａ２ＣＯ３ およびＮａＣｌ、またはＫ ２ ＣＯ ３ およびＫＣｌを含む塩含有液を固定化薬剤として、重金属含有飛灰と混合するもので、本発明により、酸性排ガス水を飛灰固定化剤として利用することで、優れたコストパファーマンスを示す飛灰中重金属の薬剤固定化が可能となる。本発明によるプロセスは大幅なコスト削減だけでなく、排ガス中のＣＯ２排出低減にも貢献することが出来る。
The present invention uses an alkali agent for wet acidic exhaust gas treatment to produce an alkaline liquid containing carbonate and the like, and uses this as a heavy metal fixing agent for neutral fly ash. Then, HCl and CO 2 containing gas is blown into the water stored in the first reaction tank (1), and then a part of the liquid in the first reaction tank (1) is sent to the second reaction tank (2). 2) A solution of NaOH or KOH is added to the liquid in the tank to adjust the pH of the liquid in the second reaction tank (2) to 9 to 12.5, and then the liquid is returned to the first reaction tank (1). , a gas containing an acidic component consisting of HCl and CO 2, and washed with a solution of NaOH or KOH, Na 2 CO 3 and NaCl obtained by continuously performing these operations or K 2 CO 3 and KCl, as the immobilized drug salt-containing solution containing heavy metals Intended to be mixed with Yuhihai, the present invention, by utilizing an acidic gas water as fly ash fixing agent, it is possible to drug immobilization of fly ash show an excellent cost puffer performance heavy metals. The process according to the present invention can contribute not only to significant cost reduction but also to CO 2 emission reduction in exhaust gas.
つぎに、本発明を具体的に説明するために、本発明の実施例をいくつか挙げる。 Next, in order to explain the present invention specifically, some examples of the present invention will be given.
ａ）図１に示す装置を用いて、酸性ガス処理塔の擬似循環液を作製した。すなわち、第１反応槽（１）に蓄えた水にＨＣｌおよびＣＯ２含有ガスを吹き込んだ。これにより第１反応槽（１）の液のｐＨは徐々に低下した。第１反応槽（１）の液の一部を第２反応槽（２）へ送り、同槽（２）内の液を撹拌しながらここにＮａＯＨを加えた。第２反応槽（２）の液のｐＨを９、１１または１２．５になるようにし、その後この液を第１反応槽（１）に戻した。これらの操作を連続して行った。一定時間経過後、装置の運転を停止し、第１反応槽（１）内の液を酸性ガス処理塔の擬似循環液とした。
a) Using the apparatus shown in FIG. 1, a simulated circulating liquid for an acid gas treatment tower was prepared. That is, HCl and CO 2 -containing gas was blown into the water stored in the first reaction tank (1). Thereby, pH of the liquid of the 1st reaction tank (1) fell gradually . Part of the liquid in the first reaction tank (1) was sent to the second reaction tank (2), and NaOH was added thereto while stirring the liquid in the tank (2). The pH of the liquid in the second reaction tank (2) was adjusted to 9, 11, or 12.5, and then this liquid was returned to the first reaction tank (1). These operations were performed continuously. After a certain period of time, the operation of the apparatus was stopped, and the liquid in the first reaction tank (1) was used as a simulated circulation liquid for the acid gas treatment tower.
ｂ）こうして作成した擬似循環液を３０ｗｔ％ずつ２種類の飛灰（Ａ）（Ｂ）に添加し、均一になるよう混練した。得られた混練物について、環境庁告示第１３号による溶出試験を行い、溶出液のｐＨとＰｂ濃度を測定した。この測定結果を表１に示す。
表１から明らかなように、すべての試験で飛灰中Ｐｂの固定効果が認められた。模擬循環液のｐＨが９の場合、飛灰Ｂに対するＰｂ固定化効果がやや小さかった。模擬循環液のｐＨが１２．５の場合は、逆に飛灰Ａに対するＰｂ固定化効果がやや小さかった。擬似循環液のｐＨが１１の場合は、飛灰（Ａ）（Ｂ）ともにＰｂ固定化効果が高く、この近辺のｐＨで擬似循環液を使用することにより、より多様な飛灰に対応できると考えられる。 As is clear from Table 1, the effect of fixing Pb in fly ash was observed in all tests. When the simulated circulating fluid had a pH of 9, the Pb immobilization effect on fly ash B was slightly small. On the contrary, when the simulated circulating fluid had a pH of 12.5, the Pb immobilization effect on the fly ash A was slightly small. When the simulated circulating fluid has a pH of 11, both fly ash (A) and (B) have a high Pb immobilization effect. By using the simulated circulating fluid at a pH near this, Conceivable.
１：第１反応槽
２：第２反応槽
1: First reaction tank
2: Second reaction tank
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