JP4524493B2 - Fly ash treatment method - Google Patents
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- JP4524493B2 JP4524493B2 JP2005072210A JP2005072210A JP4524493B2 JP 4524493 B2 JP4524493 B2 JP 4524493B2 JP 2005072210 A JP2005072210 A JP 2005072210A JP 2005072210 A JP2005072210 A JP 2005072210A JP 4524493 B2 JP4524493 B2 JP 4524493B2
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Description
本発明は、飛灰の処理方法に関し、特に、一般ゴミをガス化溶融炉で溶融した際に発生する溶融飛灰や、一般ゴミを焼却した際に発生する焼却灰および焼却飛灰をさらに灰溶融炉で溶融した際に発生する溶融飛灰の処理方法に関する。 The present invention relates to a method for treating fly ash, and in particular, ash further includes molten fly ash generated when general garbage is melted in a gasification melting furnace, incineration ash generated when incinerating general garbage, and incineration fly ash. The present invention relates to a method for treating molten fly ash generated when melted in a melting furnace.
従来、焼却炉や溶融炉などの高温処理炉からの飛灰の処理方法として、高温処理炉からの飛灰に鉱酸を含む水を加えてpH3以下に調整しながら浸出を行った後、濾過することにより、鉛精錬原料として使用可能な残渣と亜鉛分の多い濾液とを得る工程と、この濾液にアルカリ剤を添加してpH3〜5に調整することにより生成する珪素主体の晶出物を濾過分離して、精製された濾液を得る工程と、この濾液にアルカリ剤を添加して亜鉛や銅を主体とする重金属の水酸化物を沈澱させるとともに、さらに硫化剤を添加して水酸化物にならなかった残りの重金属分を硫化物として沈殿させ、これらの澱物を濾別して、亜鉛製錬原料として使用可能な亜鉛系殿物と実質上重金属を含まない濾液とを得る工程とからなる、高温処理炉からの重金属含有飛灰の湿式処理方法が提案されている(例えば、特許文献1参照)。 Conventionally, as a method for treating fly ash from a high-temperature treatment furnace such as an incinerator or melting furnace, leaching is carried out while adjusting the pH to 3 or less by adding water containing mineral acid to the fly ash from the high-temperature treatment furnace, followed by filtration. To obtain a residue that can be used as a lead refining raw material and a filtrate containing a large amount of zinc, and by adding an alkali agent to the filtrate and adjusting the pH to 3 to 5, a silicon-based crystallization product is produced. A step of obtaining a purified filtrate by filtration and separation, and adding an alkali agent to the filtrate to precipitate heavy metal hydroxides mainly composed of zinc and copper, and further adding a sulfiding agent to the hydroxides The remaining heavy metal components that did not become precipitates are precipitated as sulfides, and these starches are separated by filtration to obtain a zinc-based material that can be used as a zinc smelting raw material and a filtrate that is substantially free of heavy metals. Including heavy metals from high-temperature processing furnaces Wet processing method fly ash have been proposed (e.g., refer to Patent Document 1).
しかし、特許文献1の方法では、溶融飛灰をpH1〜2で浸出した後にpH3〜5まで中和することにより得られた珪素を主とするスラリーは、珪素のゲル化によって濾過性が非常に悪く、工業的に巨大な濾過機を必要とするという問題がある。また、珪素がゲル化する際に液を含んでいるので、液中に浸出した重金属分の多くがゲルに分配されてしまうという問題もある。さらに、ゲル化した珪素の残渣は高水分であるため、その処理が困難である。
However, in the method of Patent Document 1, the slurry mainly composed of silicon obtained by leaching molten fly ash at pH 1 to 2 and then neutralizing to
このように、特許文献1の方法を工業的に利用するには問題があるため、現在、特別管理一般廃棄物である溶融飛灰は、キレート剤などで溶出防止処理をした後に最終処分場に投棄されている。しかし、既存の最終処分場の残余スペースが逼迫し、新規最終処分場の建設が困難であることから、溶融飛灰を安全な且つ安定した状態で減容化する処理が望まれている。 Thus, since there is a problem in industrially using the method of Patent Document 1, the molten fly ash, which is a specially managed general waste, is currently disposed of in a final disposal site after being subjected to an elution prevention treatment with a chelating agent or the like. Abandoned. However, since the remaining space of the existing final disposal site is tight and it is difficult to construct a new final disposal site, a process for reducing the volume of molten fly ash in a safe and stable state is desired.
したがって、本発明は、このような従来の問題点に鑑み、工業的に簡単且つ安価に利用することができるとともに、溶融飛灰の安全な且つ安定した状態の減容化と再資源化を図ることができる、飛灰の処理方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention can be used industrially easily and inexpensively, and at the same time, it is possible to reduce the volume and recycle the molten fly ash in a safe and stable state. An object is to provide a method for treating fly ash.
本発明者らは、上記課題を解決するために鋭意研究した結果、重金属を含有する飛灰を水洗した後に固液分離して大部分のナトリウム、カリウムなどの塩化物が除かれた水洗残渣に、硫酸などの鉱酸を含む水を加えてpH3〜4に調整し、反応温度60℃以上、好ましくは80℃以上で2時間以上、好ましくは3時間以上反応させて浸出を行って珪素のゲル化を抑え、得られた浸出液に石灰などのアルカリ剤を添加してpH7以上に中和することにより、工業的に簡単且つ安価に利用することができるとともに、溶融飛灰の安全な且つ安定した状態の減容化と再資源化を図ることができる、飛灰の処理方法を提供することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have obtained a water washing residue from which most of chlorides such as sodium and potassium have been removed by solid-liquid separation after washing heavy ash containing heavy metals. Then, water containing a mineral acid such as sulfuric acid is added to adjust the pH to 3 to 4, and the reaction temperature is 60 ° C. or higher, preferably 80 ° C. or higher for 2 hours or longer, preferably 3 hours or longer to perform leaching to obtain a silicon gel. By adding an alkaline agent such as lime to the obtained leachate and neutralizing it to pH 7 or higher, it can be used industrially easily and inexpensively, and the molten fly ash is safe and stable. The present inventors have found that it is possible to provide a fly ash treatment method capable of reducing the volume and recycling of the state, and have completed the present invention.
すなわち、本発明による溶融飛灰の処理方法は、重金属を含有する飛灰を水洗する水洗工程と、この水洗工程後に固液分離して得られた水洗残渣に、鉱酸を含む水を加えてpH3〜4に調整し、反応温度60℃以上、好ましくは80℃以上で2時間以上、好ましくは3時間以上反応させて浸出を行う浸出工程と、この浸出工程後に固液分離して得られた浸出液にアルカリ剤を添加してpH7以上に中和する中和工程とを備えたことを特徴とする。この飛灰の処理方法において、飛灰が亜鉛を含有する場合には、中和工程後に固液分離して得られた残渣を、亜鉛が濃縮された残渣として回収するのが好ましい。また、浸出工程後に固液分離して得られた残渣からのHg、Cd、Pb、Cr、Asなどの溶出を防止して最終処分するために、浸出工程後に固液分離して得られた残渣に中和剤を添加して混練してもよい。さらに、中和工程後に固液分離して得られた液を水洗工程で使用してもよい。 That is, the method for treating molten fly ash according to the present invention includes a water washing step of washing fly ash containing heavy metals, and a water washing residue obtained by solid-liquid separation after the water washing step, by adding water containing a mineral acid. The pH was adjusted to 3 to 4, and the reaction temperature was 60 ° C. or higher, preferably 80 ° C. or higher for 2 hours or longer, preferably 3 hours or longer for leaching, and solid-liquid separation was performed after the leaching step. And a neutralization step of adding an alkaline agent to the leachate to neutralize to pH 7 or higher. In this fly ash treatment method, when fly ash contains zinc, it is preferable to recover the residue obtained by solid-liquid separation after the neutralization step as a residue concentrated in zinc. In addition, in order to prevent elution of Hg, Cd, Pb, Cr, As and the like from the residue obtained by solid-liquid separation after the leaching step and to dispose of the residue, the residue obtained by solid-liquid separation after the leaching step A neutralizing agent may be added to and kneaded. Furthermore, a liquid obtained by solid-liquid separation after the neutralization step may be used in the water washing step.
本発明によれば、工業的に簡単且つ安価に利用することができるとともに、溶融飛灰の安全な且つ安定した状態の減容化と再資源化を図ることができる、飛灰の処理方法を提供することができる。 According to the present invention, there is provided a fly ash treatment method that can be used industrially easily and inexpensively, and that can achieve safe and stable volume reduction and recycling of molten fly ash. Can be provided.
以下、添付図面を参照して、本発明による飛灰の処理方法の実施の形態について説明する。 Hereinafter, embodiments of a fly ash treatment method according to the present invention will be described with reference to the accompanying drawings.
図1に示すように、まず、重金属を含有する溶融飛灰を水洗して固液分離することにより大分のNa、K、Clなどの塩化物を除去し、水洗水を排水処理する。 As shown in FIG. 1, first, molten fly ash containing heavy metal is washed with water and subjected to solid-liquid separation to remove a large amount of chlorides such as Na, K, and Cl, and the washing water is subjected to drainage treatment.
次に、得られた水洗残渣に、硫酸などの鉱酸を含む水を加えて、pH3〜4、反応温度60℃以上、好ましくは80℃以上に調整しながら2時間以上、好ましくは3時間以上反応させる。この浸出により、珪素のゲル化を抑えて濾過性の良い浸出残渣を得ることができるとともに、浸出液中に珪素を溶解させることなく、溶融飛灰中に含まれる亜鉛を主とする重金属を浸出液に移行させることができる。なお、反応時間を2時間以上とするのは、一旦溶解した珪素を析出させるためであり、反応温度が高い方が珪素の析出に有利である。 Next, water containing a mineral acid such as sulfuric acid is added to the obtained water washing residue to adjust the pH to 3 to 4 and the reaction temperature to 60 ° C. or higher, preferably 80 ° C. or higher, preferably 2 hours or longer, preferably 3 hours or longer. React. By this leaching, it is possible to obtain a leaching residue having good filterability by suppressing the gelation of silicon, and to dissolve the heavy metal mainly composed of zinc contained in the molten fly ash into the leaching solution without dissolving the silicon in the leaching solution. Can be migrated. The reason for setting the reaction time to 2 hours or longer is to precipitate silicon once dissolved, and a higher reaction temperature is advantageous for silicon precipitation.
得られた浸出残渣は、石灰などのアルカリ剤を混練して安定化させた後に、最終処分場に埋め立てるのに適した状態にして埋立て処分とすることができる。このように溶融飛灰を水洗して浸出することにより、溶融飛灰を減容することができ、最終処分場への負荷を少なくすることができる。また、埋立て処分の基準を満たすことができるので、高価なキレート剤を使用する必要がなくなる。なお、浸出残渣には重金属の一部が残存しているので、溶融炉などにより乾式処理することによって、重金属を再度飛灰として回収することもできる。 The obtained leaching residue is stabilized by kneading an alkaline agent such as lime, and then made into a state suitable for being landfilled in a final disposal site and can be used as landfill disposal. Thus, the molten fly ash is washed with water and leached, so that the volume of the molten fly ash can be reduced and the load on the final disposal site can be reduced. Further, since the standard for landfill disposal can be satisfied, there is no need to use an expensive chelating agent. In addition, since a part of heavy metal remains in the leaching residue, the heavy metal can be recovered as fly ash again by performing a dry treatment using a melting furnace or the like.
次に、得られた浸出液を石灰などのアルカリ剤でpH7以上に中和して、重金属の水酸化物や酸化物を沈澱として回収する。このとき、浸出液中に珪素が溶解していると、中和によりゲル化して濾過性の極めて悪い残渣が得られるが、本発明による飛灰の処理方法の実施の形態では、浸出液中に珪素が溶解していないので、ゲル化しない濾過性の良い残渣が得られる。また、浸出液をpH7以上に中和することにより、飛灰中に含まれる亜鉛を主とする重金属を中和残渣中に高品位で回収し、非鉄製錬原料として使用することができる。また、二段階で中和と濾過を行えば、ZnおよびCuとCdおよびMgとをある程度分別回収することもできる。一方、中和后液は重金属を除去した液であり、工業的には、排水量を削減するために水洗工程で再利用するのが望ましい。 Next, the obtained leachate is neutralized with an alkaline agent such as lime to a pH of 7 or more to recover heavy metal hydroxides and oxides as precipitates. At this time, if silicon is dissolved in the leachate, it is gelled by neutralization to obtain a residue with extremely poor filterability. In the embodiment of the fly ash treatment method according to the present invention, silicon is contained in the leachate. Since it is not dissolved, a filterable residue that does not gel is obtained. Further, by neutralizing the leachate to pH 7 or higher, heavy metals mainly composed of zinc contained in fly ash can be recovered in a neutralized residue with high quality and used as a non-ferrous smelting raw material. In addition, if neutralization and filtration are performed in two stages, Zn and Cu and Cd and Mg can be separated and recovered to some extent. On the other hand, the neutralized solution is a solution from which heavy metals have been removed, and industrially, it is desirable to reuse it in the washing step in order to reduce the amount of drainage.
以下、本発明による飛灰の処理方法の実施例について詳細に説明する。 Hereinafter, embodiments of the fly ash treatment method according to the present invention will be described in detail.
[実施例1]
表1に示す品位の溶融飛灰1、2、3を用意し、それぞれパルプ濃度300g/Lで水洗し、濾別して得られた各々の水洗残渣に、硫酸を含む水を加えて、パルプ濃度100g/Lに調整するとともに、それぞれpH3、pH3.5およびpH4に調整し、80℃で4時間反応させて浸出を行った。得られた各々の浸出残渣の発生率(飛灰の量に対するドライベースの残渣の発生率)を図2に示す。この図から、水洗と浸出によって溶融飛灰が減容化されているのがわかる。なお、浸出残渣の濾過速度は、6kg/cm2の濾過圧でいずれも20L/分/m2程度と良好であった。
[Example 1]
Prepare
[実施例2]
表1に示す品位の溶融飛灰1を用意し、パルプ濃度300g/Lで水洗し、濾別して得られた水洗残渣に、硫酸を含む水を加えて、パルプ濃度100g/Lに調整するとともに、それぞれpH3、pH3.5およびpH4に調整し、80℃で反応させて浸出を行った。各々の浸出液の珪素および亜鉛の濃度と反応時間との関係を図3および図4に示す。これらの図から、pH3およびpH3.5では、珪素は一旦液中に溶解するものの、時間が経過するにつれて析出を完了し、濾過性の良い残渣が得られるのがわかる。また、亜鉛の最終到達濃度は、pHによらず一定であった。これらの珪素の析出挙動と亜鉛の浸出挙動から、反応時間を2時間以上にするのが好ましいことがわかった。
[Example 2]
Prepare molten fly ash 1 of the grade shown in Table 1, wash with water at a pulp concentration of 300 g / L, add water containing sulfuric acid to the water washing residue obtained by filtration, and adjust to a pulp concentration of 100 g / L, The pH was adjusted to
[実施例3]
表2に示す品位の溶融飛灰を用意し、パルプ濃度300g/Lで水洗し、濾別して得られた水洗残渣に、硫酸を含む水を加えて、パルプ濃度100g/L、pH4に調整し、それぞれ60℃と80℃で反応させて浸出を行った。反応温度60℃と80℃における浸出液中の珪素の濃度と反応時間の関係を図5に示す。この図からわかるように、60℃で珪素が沈殿して濾過性の良い残渣が得られるので、反応温度を60℃以上とするのが好ましい。
[Example 3]
Prepare molten fly ash of the grade shown in Table 2, wash with water at a pulp concentration of 300 g / L, add water containing sulfuric acid to the water washing residue obtained by filtration, adjust to a pulp concentration of 100 g / L,
[実施例4]
表1に示す品位の溶融飛灰2を用意し、パルプ濃度300g/Lで水洗し、濾別して得られた水洗残渣に、硫酸を含む水を加えて、パルプ濃度100g/L、pH4に調整し、80℃で反応させて浸出を行った後、得られた浸出液を生石灰でpH8に中和した。得られた中和残渣中のCa、SおよびZnの含有量を表3に示す。この表3からわかるように、この中和により亜鉛を濃縮した残渣を得ることができ、この残渣を亜鉛製錬の原料として使用することができる。
[Example 4]
Prepare molten fly ash 2 of the grade shown in Table 1, wash with water at a pulp concentration of 300 g / L, add water containing sulfuric acid to the water washing residue obtained by filtration, and adjust to a pulp concentration of 100 g / L and
[実施例5]
表1に示す品位の溶融飛灰1、2、3を用意し、それぞれパルプ濃度300g/Lで水洗し、濾別して得られた各々の水洗残渣に、硫酸を含む水を加えて、パルプ濃度100g/L、pH4に調整し、80℃で反応させて浸出を行った後、得られた浸出残渣に様々な比率で生石灰を添加して混練し、混練物からの溶出試験を行った。この溶出試験の結果を表4〜6に示す。これらの表から、いずれの混練物も埋立て基準を満たし、混練物の粉体pHを10程度にするのが好ましいことがわかる。
[Example 5]
Prepare
Claims (5)
The method for treating fly ash according to any one of claims 1 to 4, wherein a liquid obtained by solid-liquid separation after the neutralization step is used in the water washing step.
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