JP2003210939A - Method for preventing emission of dioxins and related compound - Google Patents
Method for preventing emission of dioxins and related compoundInfo
- Publication number
- JP2003210939A JP2003210939A JP2002017173A JP2002017173A JP2003210939A JP 2003210939 A JP2003210939 A JP 2003210939A JP 2002017173 A JP2002017173 A JP 2002017173A JP 2002017173 A JP2002017173 A JP 2002017173A JP 2003210939 A JP2003210939 A JP 2003210939A
- Authority
- JP
- Japan
- Prior art keywords
- dioxins
- amount
- dioxin
- activated carbon
- exhaust gas
- 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.)
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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃棄物焼却炉等の
焼却炉や、鉄鋼製造電炉、金属回収炉等の加熱炉などか
らのダイオキシン類の放出を防止する方法に係り、特
に、准連続式又は機械バッチ式都市ごみ焼却炉のよう
に、短期間、例えば１日のうちに炉の起動（立ち上げ）
と停止（立ち下げ）とを行う炉施設において、ダイオキ
シン類の放出を確実に防止する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the release of dioxins from incinerators such as waste incinerators and heating furnaces such as electric steelmaking electric furnaces and metal recovery furnaces, and more particularly, quasi-continuous Start-up (start-up) of a furnace in a short period of time, for example, in one day, such as a manual or mechanical batch-type municipal solid waste incinerator
The present invention relates to a method for surely preventing the release of dioxins in a furnace facility that performs shutdown (shutdown).
【０００２】[0002]
【従来の技術】ごみ焼却炉等の焼却炉においては、燃焼
中にクロロフェノール、クロロベンゼン等の塩素化芳香
族化合物や塩素化アルキル化合物等のダイオキシン類前
駆体が発生する。これらのダイオキシン類前駆体は、飛
灰が共存するとその触媒作用でダイオキシン類（ポリ塩
化ジベンゾダイオキシン及びポリ塩化ジベンゾフラン、
コプラナーＰＣＢ）となり、煤塵や排ガス中に存在する
ようになる。2. Description of the Related Art In an incinerator such as a refuse incinerator, dioxin precursors such as chlorinated aromatic compounds such as chlorophenol and chlorobenzene and chlorinated alkyl compounds are generated during combustion. These dioxin precursors are dioxins (polychlorinated dibenzodioxins and polychlorinated dibenzofuran,
It becomes a coplanar PCB) and becomes present in soot and exhaust gas.
【０００３】ダイオキシン類の放出量を低減するため
に、炉の燃焼改善、バグフィルターや触媒塔の設置等の
改造等が行われている。In order to reduce the emission of dioxins, the combustion of the furnace has been improved, and the bag filter and the catalyst tower have been remodeled.
【０００４】しかしながら、ダイオキシン類の主な生成
場所は、一般に燃焼炉のあとのガスの処理工程であるた
め、炉の燃焼改善だけでは排ガス中のダイオキシン類を
十分に低減できない。また、装置改造は、イニシャルコ
ストが高く、設置に期間を要し、必要とするスペースも
大きい上に、導入に当たっては炉の運転を長期間停止し
なければならないなどの欠点がある。However, since the main production site of dioxins is generally the gas treatment step after the combustion furnace, it is not possible to sufficiently reduce the dioxins in the exhaust gas only by improving the combustion of the furnace. Further, the device modification has the drawbacks that the initial cost is high, the installation requires a long period of time, the required space is large, and the furnace operation must be stopped for a long time before introduction.
【０００５】簡便にダイオキシン類の放出量を低減する
方法として、ダイオキシン類低減薬剤を排ガスに添加す
る方法がある。ダイオキシン類低減薬剤として用いられ
る主な薬剤は、ダイオキシン吸着能を有する活性炭を主
成分とした薬剤、或いは、ダイオキシン類前駆体固定能
を有するアルカリ炭酸水素塩や炭酸塩を主成分とした薬
剤であり、場合によってはこれらの成分に消石灰等の酸
性ガス除去剤、リン酸塩やキレート剤等の重金属固定剤
が併用される。As a method for easily reducing the amount of dioxins released, there is a method of adding a dioxins reducing agent to exhaust gas. The main agents used as dioxins reducing agents are agents that have activated carbon that has the ability to adsorb dioxin as the main ingredient, or agents that have alkali carbonate or carbonate that has the ability to fix dioxin precursors as the main ingredient. Depending on the case, an acid gas removing agent such as slaked lime and a heavy metal fixing agent such as a phosphate or a chelating agent are used together with these components.
【０００６】このような薬剤添加によるダイオキシン類
の放出防止法として、本出願人は先に重曹（炭酸水素ナ
トリウム）等のアルカリと活性炭とを焼却炉排ガスに添
加する方法を提案した（特開２０００−３５４７３
５）。この方法では、重曹を６０〜８０重量％、活性炭
を２０〜４０重量％混合した薬剤を排ガスに対して１０
０〜６００ｍｇ／Ｎｍ３となるように添加するのが好ま
しいとされている。As a method for preventing the release of dioxins by adding such chemicals, the present applicant has previously proposed a method of adding an alkali such as sodium bicarbonate (sodium hydrogen carbonate) and activated carbon to incinerator exhaust gas (Japanese Patent Laid-Open No. 2000-2000). -35473
5). According to this method, a chemical agent containing 60 to 80% by weight of baking soda and 20 to 40% by weight of activated carbon is added to the exhaust gas in an amount of 10%.
It is said that it is preferable to add it so as to be 0 to 600 mg / Nm 3 .
【０００７】従来、これらのダイオキシン類低減薬剤
は、定量吹き込み方式にて、即ち排ガスに対して一定の
添加割合にて添加されているが、消石灰と活性炭の混合
物を排ガスに吹き込む方法にあっては、排ガス中のＨＣ
ｌ濃度によって注入量を制御する場合もある。Conventionally, these dioxins-reducing agents have been added in a fixed-quantity blowing method, that is, at a constant addition ratio to the exhaust gas, but in the method of blowing a mixture of slaked lime and activated carbon into the exhaust gas. , HC in exhaust gas
The injection amount may be controlled depending on the l concentration.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上記特
開２０００−３５４７３５に記載されるような薬剤添加
法は、比較的規模の大きな全連続式焼却炉では良好な結
果が得られているが、中小型焼却炉では十分なダイオキ
シン類の放出防止効果が得られない場合があった。特
に、短期間、例えば１日のうちで立ち上げ（起動）と立
ち下げ（停止）を行う准連続炉や機械バッチ炉に対して
は、十分に満足のいく効果が得られていない。However, the chemical addition method as described in JP-A-2000-354735 gives good results in a relatively large-scale, all-continuous incinerator, but In some cases, a small incinerator could not provide sufficient dioxins emission prevention effect. In particular, a sufficiently satisfactory effect has not been obtained for a quasi-continuous furnace or a mechanical batch furnace that starts (starts) and stops (stops) within a short period of time, for example, one day.
【０００９】また、准連続炉、機械バッチ炉等のよう
に、短期間のうちに起動と停止を行う焼却炉では、この
起動運転時と停止運転時にダイオキシン類及びダイオキ
シン類前駆体濃度が増加する。そして、このことが従来
のダイオキシン類低減薬剤の定量吹き込み方式では、停
止運転及び起動運転後の定常運転時のダイオキシン類発
生量を増大させる原因となる。即ち、ダイオキシン類低
減薬剤の定量吹き込み方式では、停止時及び起動時にダ
イオキシン類前駆体発生量に対してダイオキシン類低減
薬剤が不足する。そして、ダイオキシン類低減薬剤によ
り処理しきれなかったダイオキシン類前駆体は、停止時
及び起動時に煙突から排出されるばかりでなく煙道や排
ガス処理装置等に蓄積され、定常運転時にダイオキシン
類として排出されるようになり、定常運転時の排ガス中
のダイオキシン類濃度を高める結果となる。Further, in incinerators such as a quasi-continuous furnace and a mechanical batch furnace which start and stop in a short period of time, the concentrations of dioxins and dioxin precursors increase during the start-up operation and the stop operation. . Then, in the conventional fixed amount blowing method for dioxins-reducing agents, this causes an increase in the amount of dioxins generated during steady operation after stop operation and start operation. That is, in the fixed amount blowing method of the dioxin-reducing agent, the dioxin-reducing agent is insufficient with respect to the amount of dioxin precursors generated at the time of stopping and starting. The dioxin precursor that could not be completely treated by the dioxin reducing agent is not only discharged from the chimney at the time of stop and start, but also accumulated in the flue and exhaust gas treatment equipment, etc., and discharged as dioxin during steady operation. As a result, the concentration of dioxins in the exhaust gas during normal operation is increased.
【００１０】なお、前記の通り、消石灰と活性炭の混合
物の添加量を排ガスのＨＣｌ濃度に応じて制御する場合
があるが、焼却炉や加熱炉においてＨＣｌ濃度とダイオ
キシン類濃度との相関は低く変動も激しいので、起動時
及び停止時のダイオキシン類発生量の増加には対応し得
ない。As described above, the addition amount of the mixture of slaked lime and activated carbon may be controlled depending on the HCl concentration of the exhaust gas, but in the incinerator and the heating furnace, the correlation between the HCl concentration and the dioxin concentration is low and fluctuates. Since it is severe, it cannot cope with the increase in the amount of dioxins generated at the time of starting and stopping.
【００１１】本発明は上記従来の問題点を解決し、廃棄
物焼却炉等の焼却炉、特に、准連続炉や機械バッチ炉の
ように、短期間のうちに炉の起動（立ち上げ）と停止
（立ち下げ）とを行う炉施設において、ダイオキシン類
の放出を安定かつ確実に防止する方法を提供することを
目的とする。The present invention solves the above-mentioned conventional problems, and incinerators such as waste incinerators, in particular, quasi-continuous furnaces and mechanical batch furnaces, can be started (started) in a short period of time. It is an object of the present invention to provide a method for stably and reliably preventing the release of dioxins in a reactor facility that is shut down (shut down).
【００１２】[0012]
【課題を解決するための手段】請求項１のダイオキシン
類の放出防止方法は、短期間の間に起動と停止とを行う
焼却炉の排ガスに対して、粉末活性炭を５０〜３００ｍ
ｇ／Ｎｍ３、重曹を６００ｍｇ〜３０００ｍｇ／Ｎｍ３
となるように添加することを特徴とする。本発明におい
て、短期間とは１〜３日程度をさす。According to a first aspect of the present invention, there is provided a method for preventing the release of dioxins, wherein 50 to 300 m of powdered activated carbon is added to exhaust gas of an incinerator which is started and stopped in a short period of time.
g / Nm 3, the baking soda 600mg~3000mg / Nm 3
Is added so that In the present invention, the short term refers to about 1 to 3 days.
【００１３】請求項２のダイオキシン類の放出防止方法
は、排ガス中のクロロフェノール類濃度が３〜３０μｇ
／Ｎｍ３となるような焼却炉の排ガスに対して、粉末活
性炭を５０〜３００ｍｇ／Ｎｍ３、重曹を６００ｍｇ〜
３０００ｍｇ／Ｎｍ３となるように添加することを特徴
とする。In the method for preventing the release of dioxins according to claim 2, the concentration of chlorophenols in the exhaust gas is 3 to 30 μg.
Against incinerator exhaust gas such that / Nm 3, the powdered activated carbon 50 to 300 mg / Nm 3, baking soda 600mg~
It is characterized in that it is added so as to be 3000 mg / Nm 3 .
【００１４】発明者らは、重曹が焼却炉排ガス中のダイ
オキシン類の生成抑制に有効であることを確認したが、
重曹の添加量は、適用排ガス中のダイオキシン類前駆体
（例えばクロロフェノール類）の濃度に応じて制御する
ことが効果的であることを確認した。特に、１日のうち
で起動と停止を行う准連続炉（１日の運転時間は１６時
間）や機械バッチ炉（１日の運転時間は８時間）では、
排ガス中のダイオキシン類前駆体濃度は、平均３０μｇ
／Ｎｍ３程度と、全連続炉の排ガス中のダイオキシン類
前駆体濃度の平均２〜３μｇ／Ｎｍ３に対して１０倍程
度高濃度であり、この高濃度のダイオキシン類前駆体に
応じて、重曹の添加量は少なくとも６００ｍｇ／Ｎｍ３
は必要である。重曹の添加量を多くすると、ＨＣｌ等の
酸性ガスを重曹以外のアルカリ剤を用いずに除去するこ
とができるが、３０００ｍｇ／Ｎｍ３を超えて添加して
もこの除去効果は変わらない。従って、重曹の添加量は
６００〜３０００ｍｇ／Ｎｍ３とする。The inventors have confirmed that baking soda is effective in suppressing the formation of dioxins in exhaust gas from incinerators.
It was confirmed that it is effective to control the addition amount of baking soda according to the concentration of the dioxin precursor (eg, chlorophenols) in the applied exhaust gas. Especially in quasi-continuous furnaces (starting time is 16 hours) and mechanical batch furnaces (starting time is 8 hours) that start and stop within a day,
Dioxin precursor concentration in exhaust gas is 30 μg on average
/ Nm 3 , which is about 10 times higher than the average concentration of dioxins precursors in the exhaust gas of all continuous furnaces of 2 to 3 μg / Nm 3 , and baking soda can be added depending on the concentration of dioxins precursor. Is added at least 600 mg / Nm 3
Is necessary. When the amount of baking soda added is increased, acidic gases such as HCl can be removed without using an alkaline agent other than baking soda, but even if added in excess of 3000 mg / Nm 3 , this removal effect does not change. Therefore, the addition amount of baking soda is 600 to 3000 mg / Nm 3 .
【００１５】また、粉末活性炭は、燃焼により生成して
排ガス中に既に存在するガス状のダイオキシン類の吸着
除去を行うが、十分な接触効率を得るためには排ガスに
対して５０ｍｇ／Ｎｍ３以上の添加が必要である。一
方、活性炭はダイオキシン類生成触媒としても働くた
め、過剰添加により逆にダイオキシン類の増加を招くこ
とになる。従って、粉末活性炭は３００ｍｇ／Ｎｍ３以
下での添加が好ましい。Further, the powdered activated carbon adsorbs and removes the gaseous dioxins already produced in the exhaust gas by combustion, but in order to obtain sufficient contact efficiency, 50 mg / Nm 3 or more with respect to the exhaust gas. Is required. On the other hand, since activated carbon also functions as a dioxin-producing catalyst, excessive addition thereof causes an increase in dioxin. Therefore, it is preferable to add the powdered activated carbon at 300 mg / Nm 3 or less.
【００１６】以上のことから、請求項１，２のダイオキ
シン類の放出防止方法では、短期間、例えば１日の間に
起動と停止とを行う、ダイオキシン類前駆体濃度の高い
焼却炉排ガス又は、クロロフェノール類濃度が３〜３０
μｇ／Ｎｍ３というようなダイオキシン類前駆体濃度の
高い焼却炉排ガスに対して、粉末活性炭５０〜３００ｍ
ｇ／Ｎｍ３と重曹６００〜３０００ｍｇ／Ｎｍ３とを添
加する。From the above, in the method for preventing the release of dioxins according to claims 1 and 2, incinerator exhaust gas having a high dioxin precursor concentration, which is started and stopped for a short period of time, for example, one day, or Chlorophenol concentration is 3 to 30
50 to 300 m of activated carbon powder for incinerator exhaust gas with a high concentration of dioxins precursor such as μg / Nm 3.
g / Nm 3 and baking soda 600-3000 mg / Nm 3 are added.
【００１７】なお、ここで、クロロフェノール類とは、
モノクロロフェノール、ジクロロフェノール、トリクロ
ロフェノール、テトラクロロフェノール、ペンタクロロ
フェノール、ヘキサクロロフェノール等を指す。Here, the chlorophenols are
It refers to monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, pentachlorophenol, hexachlorophenol, and the like.
【００１８】請求項３のダイオキシン類の放出防止方法
は、炉の排ガスにダイオキシン類低減薬剤を添加してダ
イオキシン類の放出を防止する方法において、該炉の起
動運転時及び停止運転時に、定常運転時よりも多量にダ
イオキシン類低減薬剤を添加することを特徴とする。The method for preventing the release of dioxins according to claim 3 is a method for preventing the release of dioxins by adding a dioxins reducing agent to the exhaust gas of a furnace, wherein the steady operation is performed during the start-up operation and the stop operation of the furnace. It is characterized in that a dioxin-reducing agent is added in a larger amount than the time.
【００１９】このように、ダイオキシン類発生量の多い
炉の起動運転時及び停止運転時において、定常運転時よ
りも多量のダイオキシン類低減薬剤を添加することによ
り、起動運転時及び停止運転時のダイオキシン類前駆体
発生量を低減することができ、これにより、定常運転時
のダイオキシン類発生量を目標値以下に抑えることがで
きる。As described above, during start-up operation and stop operation of a furnace that generates a large amount of dioxins, by adding a larger amount of the dioxin-reducing agent than during steady operation, the dioxin during start-up operation and stop operation It is possible to reduce the amount of precursors generated, and thereby to suppress the amount of dioxins generated during steady operation below the target value.
【００２０】この場合、定常運転時のダイオキシン類前
駆体の発生量は、当該定常運転時の直前の起動運転時と
その直前の停止運転時のダイオキシン類低減薬剤の添加
量に相関する。このため、請求項４の方法では、起動運
転時及び該起動運転の直前の停止運転時のダイオキシン
類低減薬剤の添加量と、該起動運転後の定常運転時のダ
イオキシン類前駆体の発生量との関係を求め、この関係
に基いて起動運転時及び停止運転時のダイオキシン類低
減薬剤の添加量を決定する。In this case, the amount of the dioxin precursors generated during the steady operation correlates with the amount of the dioxin-reducing agent added during the start operation immediately before the steady operation and the stop operation immediately before that. Therefore, in the method according to claim 4, the amount of the dioxin-reducing agent added during the start-up operation and the stop operation immediately before the start-up operation and the amount of the dioxin precursors generated during the steady-state operation after the start-up operation Is calculated, and the addition amount of the dioxin-reducing agent during start-up operation and stop operation is determined based on this relationship.
【００２１】[0021]
【発明の実施の形態】以下に、本発明のダイオキシン類
の放出防止方法の実施の形態を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for preventing the release of dioxins of the present invention will be described in detail below.
【００２２】請求項１，２の方法においては、１日の間
に起動と停止とを行うために、ダイオキシン類前駆体濃
度の高い焼却炉排ガス、又はクロロフェノール類濃度が
３〜３０μｇ／Ｎｍ３というようなダイオキシン類前駆
体濃度の高い焼却炉排ガスに対して、粉末活性炭５０〜
３００ｍｇ／Ｎｍ３好ましくは８０〜１２０ｍｇ／Ｎｍ
３と重曹６００〜３０００ｍｇ／Ｎｍ３好ましくは７０
０〜８００ｍｇ／Ｎｍ ３とを添加する。In the method of claims 1 and 2, during one day
In order to start and stop the
Incinerator exhaust gas with high degree or chlorophenol concentration
3-30 μg / NmThreePrecursor of dioxins such as
Powder activated carbon 50 ~ for incinerator exhaust gas with high body concentration
300 mg / NmThreePreferably 80-120 mg / Nm
ThreeAnd baking soda 600-3000 mg / NmThreePreferably 70
0-800mg / Nm ThreeAnd are added.
【００２３】粉末活性炭と重曹の添加量は上記範囲内で
あれば良いが、添加量が少ないと十分な効果が得られ
ず、逆に多いと煤塵負荷が増加する上に、薬剤コストの
増加を招くことから、粉末活性炭と重曹との合計で６５
０〜２０００ｍｇ／Ｎｍ３程度となるように添加するこ
とが好ましい。また、粉末活性炭と重曹との合計添加量
の８〜２０重量％が粉末活性炭となるように添加するこ
とがダイオキシン類の生成防止効果の面で好ましい。The amount of powdered activated carbon and baking soda added may be within the above range, but if the amount of addition is small, a sufficient effect cannot be obtained, and conversely, if the amount is large, the dust load increases and the drug cost also increases. In total, the total amount of activated carbon powder and baking soda is 65
It is preferable to add it so as to be about 0 to 2000 mg / Nm 3 . Further, it is preferable to add 8 to 20% by weight of the total amount of the powdered activated carbon and baking soda to form the powdered activated carbon from the viewpoint of the effect of preventing the formation of dioxins.
【００２４】粉末活性炭と重曹は、これらを予め混合し
て添加しても良く、また、別々に添加しても良いが、予
め混合しておくことにより、活性炭の発火の危険性を低
減することができる上に、添加設備を簡素化することが
でき、好ましい。The powdered activated carbon and the baking soda may be added by mixing them in advance, or may be added separately, but by mixing them in advance, the risk of ignition of the activated carbon is reduced. In addition to being able to do so, the addition equipment can be simplified, which is preferable.
【００２５】粉末活性炭と重曹とを予め混合する場合、
混合割合は、粉末活性炭を８〜２０重量％、重曹を９２
〜８０重量％となるような割合で混合することが、ダイ
オキシン類の生成防止効果の面で好ましい。When powdered activated carbon and baking soda are premixed,
The mixing ratio is 8 to 20% by weight of powdered activated carbon and 92% of baking soda.
It is preferable to mix them in such a proportion that the content becomes ˜80 wt%, from the viewpoint of the effect of preventing the formation of dioxins.
【００２６】請求項１，２において、粉末活性炭として
は、平均粒径が５０μｍ以下、例えば平均粒径が１０〜
３０μｍ程度の粉末活性炭が好ましい。In Claims 1 and 2, the powdered activated carbon has an average particle size of 50 μm or less, for example, an average particle size of 10 to 10.
Powdered activated carbon of about 30 μm is preferable.
【００２７】また、このような粉末活性炭との均一混合
性及び排ガスとの接触効率並びに取り扱い性の面から、
重曹は平均粒径５〜１５μ程度であることが好ましい。
このとき、任意の粒径の活性炭と重曹を、噴霧直前にそ
れぞれ１０〜３０μｍ、５〜１５μｍとなるように粉砕
しても良い。From the viewpoints of such uniform mixing with powdered activated carbon, contact efficiency with exhaust gas, and handleability,
The baking soda preferably has an average particle size of about 5 to 15 μm.
At this time, activated carbon and baking soda having arbitrary particle sizes may be pulverized immediately before spraying so as to have a particle size of 10 to 30 μm and 5 to 15 μm, respectively.
【００２８】なお、粉末活性炭は、ダイオキシン類生成
の触媒作用を抑制するために、アルカリを添着して用い
ても良い。The powdered activated carbon may be used with an alkali impregnated in order to suppress the catalytic action of dioxins generation.
【００２９】この場合、アルカリとしては、アミン化合
物、アンモニア、アンモニウム塩、アルカリ金属化合物
等の１種又は２種以上を用いることができる。このう
ち、アミン化合物としては、トリメチルアミン等のアル
キルアミン、トリエタノールアミン、モノエタノールア
ミン等のアルカノールアミンなどのほか、これらのアミ
ン化合物の塩酸塩、硫酸塩、炭酸塩等のアミン塩が挙げ
られる。アンモニウム塩としては、重炭酸アンモニウ
ム、硫酸アンモニウム、リン酸水素二アンモニウム等が
挙げられる。アルカリ金属化合物としては、ケイ酸ナト
リウム、ケイ酸カリウム等のアルカリ金属のケイ酸塩、
水酸化ナトリウム、水酸化カリウム等のアルカリ金属水
酸化物、炭酸塩等が挙げられ、これらのアルカリの添着
量は、好ましくは粉末活性炭に対して３０重量％以下、
特に好ましくは０．５〜１０重量％程度である。In this case, as the alkali, one or more of amine compounds, ammonia, ammonium salts, alkali metal compounds and the like can be used. Among these, examples of the amine compound include alkylamines such as trimethylamine, alkanolamines such as triethanolamine and monoethanolamine, and amine salts such as hydrochlorides, sulfates and carbonates of these amine compounds. Examples of the ammonium salt include ammonium bicarbonate, ammonium sulfate, diammonium hydrogen phosphate and the like. As the alkali metal compound, silicates of alkali metals such as sodium silicate and potassium silicate,
Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates, and the like, and the amount of these alkalis impregnated is preferably 30% by weight or less based on the powdered activated carbon.
Particularly preferably, it is about 0.5 to 10% by weight.
【００３０】粉末活性炭及び重曹の添加箇所は排ガスの
冷却工程の何れの箇所でも良いが、好ましくは、集塵機
手前の１５０〜４００℃の温度領域の部分に添加するの
が望ましい。The powdered activated carbon and baking soda may be added at any place in the exhaust gas cooling step, but it is preferable to add them to the temperature region of 150 to 400 ° C. before the dust collector.
【００３１】即ち、排ガスの冷却工程におけるダイオキ
シン類の合成は、温度約２００〜４００℃の領域で行わ
れるとされているが、実際の施設においては、集塵機内
部での合成が主であり、焼却炉から排出された高温度の
状態から冷却されて集塵機に流入するまでの間は滞留時
間が短いため、合成量は非常に少ない。従って、冷却さ
れた４００℃以下の条件で粉末活性炭及び重曹を注入す
れば、重曹により大部分のダイオキシン類の合成を防止
することができる。また、同時に粉末活性炭により、既
に焼却炉で生成した少量のダイオキシン類を吸着し、こ
れを集塵機で分離することにより、効率的にダイオキシ
ン類の除去を行える。That is, the synthesis of dioxins in the exhaust gas cooling process is said to be carried out in the temperature range of about 200 to 400 ° C. However, in actual facilities, the synthesis is mainly performed inside the dust collector and is incinerated. The amount of synthesis is very small because the residence time is short from the high temperature state discharged from the furnace until it is cooled and flows into the dust collector. Therefore, if powdered activated carbon and baking soda are injected under the cooled condition of 400 ° C. or less, the synthesis of most dioxins can be prevented by the baking soda. At the same time, powdered activated carbon adsorbs a small amount of dioxins already produced in the incinerator and separates them with a dust collector, so that dioxins can be efficiently removed.
【００３２】請求項３の方法では、廃棄物焼却炉等の焼
却炉や、鉄鋼製造電炉、金属回収炉等の加熱炉のような
ダイオキシン類が発生する炉施設において、炉の起動運
転時及び停止運転時において、ダイオキシン類低減薬剤
の添加量を定常運転時のダイオキシン類低減薬剤添加量
よりも多くする。この起動運転時及び停止運転時のダイ
オキシン類低減薬剤添加量は、適用対象の炉施設の運転
状況、ダイオキシン類の発生状況によっても異なるが、
通常の炉施設にあっては、定常運転時のダイオキシン類
低減薬剤添加量の１．３〜３倍程度の範囲で決定するこ
とが好ましい。According to the method of claim 3, in the incinerator such as a waste incinerator, in a furnace facility where dioxins are generated such as a heating furnace such as a steel manufacturing electric furnace, a metal recovery furnace, etc., at the time of starting and stopping the furnace. The amount of the dioxin-reducing agent added during operation is made larger than the amount of the dioxin-reducing agent added during steady operation. The amount of dioxin-reducing chemicals added during start-up and stop-operations will vary depending on the operating conditions of the target furnace facility and the dioxin generation.
In a normal furnace facility, it is preferable to determine the amount within a range of about 1.3 to 3 times the amount of the dioxin-reducing agent added during steady operation.
【００３３】前述の如く、定常運転時のダイオキシン類
前駆体の発生量は、当該定常運転時の直前の起動運転時
と更にその直前の停止運転時のダイオキシン類低減薬剤
の添加量に相関することから、請求項３の方法において
は、請求項４の方法に従って、起動運転時及び該起動運
転の直前の停止運転時のダイオキシン類低減薬剤の添加
量と、該起動運転後の定常運転時のダイオキシン類前駆
体の発生量との関係を求め、この関係に基いて起動運転
時及び停止運転時のダイオキシン類低減薬剤の添加量を
決定することが好ましい。As described above, the amount of dioxin precursors generated during steady operation should be correlated with the amount of dioxin-reducing agent added during the start operation immediately before the steady operation and the stop operation immediately before that. Therefore, according to the method of claim 3, according to the method of claim 4, the amount of the dioxin-reducing agent added during the start-up operation and the stop operation immediately before the start-up operation, and the dioxin during the steady-state operation after the start-up operation. It is preferable to determine the relationship with the amount of the precursors to be generated, and to determine the addition amount of the dioxin-reducing agent during start-up operation and stop operation based on this relationship.
【００３４】即ち、例えば、１日のうちに起動と停止と
を行う准連続炉や機械バッチ炉では、当日の起動運転時
と前日の停止運転時のダイオキシン類低減薬剤添加量と
当日の定常運転時のダイオキシン類前駆体の発生量との
関係を求め、別途求めておいたダイオキシン類前駆体発
生量とダイオキシン類発生量との関係から、ダイオキシ
ン類発生量が目標値以下となるダイオキシン類前駆体発
生量に抑えることができるように、起動運転時と停止運
転時のダイオキシン類低減薬剤の添加量を決定すれば良
い。That is, for example, in a quasi-continuous furnace or a mechanical batch furnace that starts and stops within one day, the amount of dioxin-reducing chemicals added during the start operation on the day and the stop operation on the previous day and the steady operation on the day. The relationship between the amount of dioxin precursors generated at that time and the relationship between the amount of dioxin precursors generated and the amount of dioxin precursors that was separately calculated, and the dioxin precursors that are below the target value The amount of the dioxin-reducing agent added during the start-up operation and the stop operation may be determined so that the generation amount can be suppressed.
【００３５】この場合、濃度の測定対象となるダイオキ
シン類前駆体としては、トリクロロフェノール等のクロ
ロフェノール類やクロロベンゼン類が挙げられるが、特
にトリクロロフェノールが好ましい。これらのダイオキ
シン類前駆体は、ダイオキシン類に比べて濃度測定が容
易であり、しかもダイオキシン類濃度と相関するため、
ダイオキシン類濃度の指標として有効である。In this case, examples of the dioxin precursor whose concentration is to be measured include chlorophenols such as trichlorophenol and chlorobenzenes, with trichlorophenol being particularly preferred. These dioxin precursors are easier to measure the concentration than dioxins, and since they correlate with the dioxin concentration,
It is effective as an index for the concentration of dioxins.
【００３６】なお、請求項３，４の方法において、原則
として、炉の起動運転時は、炉施設の誘引ファン（誘引
送風機又はブロワ）の運転開始から炉内温度が設定温度
に達するまでの期間を指し、停止運転時とは、一般的に
は最後の被処理物投入（例えば、ごみ焼却炉であれば、
最後のごみ投入）から誘引ファンを停止するまでの期間
を指す。ただし、これらの期間の始点及び終点はこの期
間よりも若干前後にずれても良い。特に、起動時につい
ては、ダイオキシン類低減薬剤の定量注入で試運転を行
い、起動運転を行った場合に、排ガス中のダイオキシン
類前躯体濃度が十分に下がるまでの時間を予め求めてお
き、誘引ファンの運転開始からこの時間までを「起動運
転時」としてダイオキシン類低減薬剤の添加量を増やす
ようにすることが好ましい。また、停止運転時について
も同様に、ダイオキシン類低減薬剤の定量注入で試運転
を行い、排ガス中のダイオキシン類前躯体濃度が上昇し
始める時間を予め求めておき、この時間から誘引ファン
の運転停止までを「停止運転時」としてダイオキシン類
低減薬剤の添加量を増やすようにすることが好ましい。In the method of claims 3 and 4, in principle, during the start-up operation of the furnace, the period from the start of operation of the induction fan (induction blower or blower) of the furnace facility until the temperature in the furnace reaches the set temperature. In general, the term “stopped operation” means that the last material to be processed is charged (for example, in the case of a refuse incinerator,
It refers to the period from when the last garbage is thrown in) until the attraction fan is stopped. However, the start point and the end point of these periods may be slightly shifted before and after this period. Especially, at the time of start-up, a trial run is performed by quantitative injection of dioxins-reducing agents, and when the start-up run is performed, the time until the concentration of dioxin precursors in exhaust gas is sufficiently reduced is obtained in advance, and the induction fan It is preferable to increase the amount of the dioxin-reducing agent added from the start of the operation up to this time as the “start-up operation”. Also during stop operation, similarly, test operation is performed by quantitative injection of dioxins reducing agent, the time when the concentration of dioxin precursor in the exhaust gas begins to rise is obtained in advance, and from this time until the operation of the induction fan is stopped. It is preferable to increase the amount of the dioxin-reducing agent to be added as "at the time of stop operation".
【００３７】請求項３，４の方法において、炉施設に添
加するダイオキシン類低減薬剤は、ダイオキシン類の生
成を防止し得る薬剤、或いはダイオキシン類を吸着除去
できる薬剤等であり、例えば、活性炭、ゼオライト、シ
リカゲル、ケイソウ土、活性白土、酸性白土、カオリ
ン、ベントナイト、アロフェン、アパタイト等の有機又
は無機の吸着剤（特に活性炭、ゼオライトが好まし
い）；上記吸着剤、例えば活性炭もしくはゼオライトと
消石灰の混合物；ナトリウム、カリウム、カルシウム及
びマグネシウムよりなる群から選ばれる１種又は２種以
上の炭酸塩及び／又は炭酸水素塩；ナトリウム、カリウ
ム、カルシウム及びマグネシウムよりなる群から選ばれ
る１種又は２種以上の炭酸塩及び／又は炭酸水素塩と、
有機もしくは無機吸着剤、例えば活性炭もしくはゼオラ
イトとの混合物；ナトリウム、カリウム、カルシウム及
びマグネシウムよりなる群から選ばれる１種又は２種以
上の炭酸塩及び／又は炭酸水素塩と、有機もしくは無機
吸着剤、例えば活性炭もしくはゼオライトと、重金属固
定剤との混合物；活性炭もしくはゼオライトと消石灰及
び重金属固定剤との混合物等を用いることができる。In the methods of claims 3 and 4, the dioxin-reducing agent added to the furnace facility is a agent capable of preventing the formation of dioxins, or an agent capable of adsorbing and removing dioxins, such as activated carbon or zeolite. , Silica gel, diatomaceous earth, activated clay, acid clay, kaolin, bentonite, allophane, apatite and other organic or inorganic adsorbents (especially activated carbon and zeolite are preferred); the above adsorbents, such as activated carbon or a mixture of zeolite and slaked lime; sodium , One or more carbonates and / or hydrogencarbonates selected from the group consisting of, potassium, calcium and magnesium; and one or more carbonates selected from the group consisting of sodium, potassium, calcium and magnesium. And / or hydrogen carbonate,
Organic or inorganic adsorbents such as a mixture with activated carbon or zeolite; one or more carbonates and / or hydrogen carbonates selected from the group consisting of sodium, potassium, calcium and magnesium, and organic or inorganic adsorbents, For example, a mixture of activated carbon or zeolite and a heavy metal fixing agent; a mixture of activated carbon or zeolite and slaked lime and a heavy metal fixing agent, etc. can be used.
【００３８】これらのダイオキシン類低減薬剤の添加箇
所は、ダイオキシン類低減薬剤の種類に応じて当該添加
箇所の温度やダイオキシン類の生成場所等を考慮して決
定される。例えば、粉末活性炭であれば、集塵機手前に
添加するのが好ましく、アルカリ炭酸塩／炭酸水素塩で
あれば、約２００〜８００℃の範囲で適用可能であるた
め、ボイラから集塵機の手前で注入するのが好ましい。The locations where these dioxin-reducing agents are added are determined in consideration of the temperature of the locations where the dioxin-reducing agents are added, the location where the dioxins are generated, etc., depending on the type of the dioxin-reducing agent. For example, in the case of powdered activated carbon, it is preferable to add it in front of the dust collector, and in the case of alkali carbonate / hydrogen carbonate, it can be applied in the range of about 200 to 800 ° C. Therefore, it is injected from the boiler before the dust collector. Is preferred.
【００３９】請求項３，４のダイオキシン類の放出防止
方法は、短期間の間に起動、停止を行う准連続炉、機械
バッチ炉等への適用に好適であるが、全連続炉におい
て、定期点検や修理のために運転を停止した後、運転を
再開する場合などにも適用可能である。The method for preventing the release of dioxins according to claims 3 and 4 is suitable for application to a quasi-continuous furnace, a machine batch furnace, etc., which starts and stops in a short period of time. It can also be applied when restarting operation after stopping operation for inspection or repair.
【００４０】請求項３，４の方法は、特に、請求項１，
２の方法と組み合わせて実施することが好ましく、短期
間の間に起動、停止を行う准連続炉、機械バッチ炉等に
おいて、請求項１，２の粉末活性炭及び重曹添加量で定
常運転を行い、請求項３，４の方法に従って、起動運転
時及び停止運転時の粉末活性炭及び重曹の添加量を定常
運転時よりも増加することが好ましい。The methods of claims 3 and 4 are particularly applicable to claims 1 and 2.
It is preferable to carry out in combination with the method of 2, and in a quasi-continuous furnace, a machine batch furnace, etc. that start and stop in a short period of time, carry out a steady operation with the powdered activated carbon and the amount of sodium bicarbonate added according to claims 1 and 2. According to the methods of claims 3 and 4, it is preferable to increase the amount of powdered activated carbon and sodium bicarbonate added during the start-up operation and the stop operation as compared with the steady-state operation.
【００４１】[0041]
【実施例】以下に、実施例及び比較例を挙げて本発明を
より具体的に説明する。EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples.
【００４２】実施例１
処理能力２．５ｔ／ｈｒで、１日の運転時間が８時間
の、図１に示すようなストーカ炉１、ガス冷却室２、空
気予熱器３、電気集塵機４、誘引送風機５及び煙突６か
らなる都市ごみ焼却炉において、定常運転時に、粉末活
性炭の配合割合を１／９とした重曹（平均粒径１０μ
ｍ）／粉末活性炭（平均粒径２０μｍ）混合薬剤を電気
集塵機４の手前のＡの箇所から排ガスに対して９００ｍ
ｇ／Ｎｍ３（即ち、粉末活性炭添加量１００ｍｇ／Ｎｍ
３，重曹添加量８００ｍｇ／Ｎｍ３）の割合で添加し、
煙突６のダイオキシン類濃度を測定したところ、２．５
ｎｇ−ＴＥＱ／Ｎｍ３となった。Example 1 A stoker furnace 1, a gas cooling chamber 2, an air preheater 3, an electrostatic precipitator 4, and an induction device having a processing capacity of 2.5 t / hr and an operating time of 8 hours a day as shown in FIG. In a municipal solid waste incinerator consisting of a blower 5 and a chimney 6, during normal operation, baking soda with a mixing ratio of activated carbon powder of 1/9 (average particle size 10 μm
m) / powdered activated carbon (average particle size 20 μm) mixed chemical from the location A in front of the electrostatic precipitator 4 to the exhaust gas to 900 m
g / Nm 3 (that is, powder activated carbon addition amount 100 mg / Nm
3 , the addition amount of baking soda 800 mg / Nm 3 ),
When the concentration of dioxins in the chimney 6 was measured, it was 2.5
It became ng-TEQ / Nm 3 .
【００４３】なお、薬剤添加前の電気集塵機入口部分の
排ガス中のクロロフェノール濃度は、９．２μｇ／Ｎｍ
３であった。The concentration of chlorophenol in the exhaust gas at the inlet of the electrostatic precipitator before the chemical addition was 9.2 μg / Nm.
It was 3 .
【００４４】比較例１
実施例１において、薬剤を全く添加しないこと以外は同
様にして運転を行い、同様にクロロフェノール濃度とダ
イオキシン類濃度を測定し、結果を表１に示した。Comparative Example 1 The same operation as in Example 1 was carried out except that no chemicals were added, the chlorophenol concentration and dioxins concentration were measured in the same manner, and the results are shown in Table 1.
【００４５】比較例２〜４
実施例１において、粉末活性炭及び重曹の添加量を表１
に示す量としたこと以外は同様にして運転を行い、同様
にクロロフェノール濃度とダイオキシン類濃度を測定
し、結果を表１に示した。Comparative Examples 2 to 4 In Example 1, the addition amounts of powdered activated carbon and baking soda are shown in Table 1.
The operation was performed in the same manner except that the amounts shown in Table 1 were used, and the chlorophenol concentration and dioxins concentration were measured in the same manner, and the results are shown in Table 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】表１より明らかなように、粉末活性炭１０
０ｍｇ／Ｎｍ３及び重曹８００ｍｇ／Ｎｍ３を添加した
実施例１では、薬剤無添加の比較例１に比べて、ダイオ
キシン類濃度を約１／２に低減することができた。As is clear from Table 1, the powdered activated carbon 10
In Example 1 was added to 0 mg / Nm 3 and sodium bicarbonate 800 mg / Nm 3, as compared with Comparative Example 1 of no drug addition, it was possible to reduce the dioxin concentration to about 1/2.
【００４８】これに対して、粉末活性炭の混合比を１／
３として合計３００ｍｇ／Ｎｍ３添加した比較例２で
は、ダイオキシン類濃度は６．５ｎｇ−ＴＥＱ／Ｎｍ３
と薬剤無添加の場合よりも多くなった。また、粉末活性
炭の添加量を４００ｍｇ／Ｎｍ ３又は３０ｍｇ／Ｎｍ３
とした比較例３，４でも十分なダイオキシン類濃度の低
減効果は得られなかった。これは、粉末活性炭の添加量
が少な過ぎると既に存在するダイオキシン類の吸着除去
を十分に行えず、逆に活性炭がダイオキシン類前躯体か
らダイオキシン類を生成する触媒として働くため多過ぎ
るとダイオキシン類の生成を助長するためと考えられ
る。On the other hand, the mixing ratio of powdered activated carbon is 1 /
3 as a total of 300 mg / NmThreeIn Comparative Example 2 added
Has a dioxin concentration of 6.5 ng-TEQ / NmThree
And it was more than when no drug was added. Also powder activity
The amount of charcoal added is 400 mg / Nm ThreeOr 30 mg / NmThree
Even in Comparative Examples 3 and 4, the concentration of dioxins is sufficiently low.
No reduction effect was obtained. This is the amount of powdered activated carbon added
If too little is present, adsorption removal of existing dioxins
On the contrary, if the activated carbon is a precursor of dioxins
Too much to act as a catalyst to generate dioxins
Is thought to promote the formation of dioxins.
It
【００４９】比較例５
都市ごみ焼却炉において、粉末活性炭の添加量を１００
ｍｇ／Ｎｍ３、重曹の添加量を４００ｍｇ／Ｎｍ３と
し、合計５００ｍｇ／Ｎｍ３の一定量注入で、図２に示
すタイムスケジュールで１日の炉の起動運転、定常運転
及び停止運転を行い、このときの電気集塵機出口の排ガ
ス中のトリクロロフェノール濃度の変化及び電気集塵機
の温度の変化を図２に示した。COMPARATIVE EXAMPLE 5 In the municipal waste incinerator, the amount of powdered activated carbon added was 100.
mg / Nm 3 , the addition amount of baking soda was 400 mg / Nm 3, and a fixed amount of 500 mg / Nm 3 was injected in a fixed amount, the start-up operation, the steady operation, and the shutdown operation of the furnace for one day were performed according to the time schedule shown in FIG. The change in the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator and the change in the temperature of the electrostatic precipitator at this time are shown in FIG.
【００５０】また、定常運転時の電気集塵機出口の排ガ
ス中のダイオキシン類濃度を調べ、結果を表２に示し
た。電気集塵機入口の排ガスのクロロフェノール濃度は
４８５０μｇ／Ｎｍ３であった。また、定常運転時の電
気集塵機出口の排ガス中のトリクロロフェノール濃度
（平均値）を調べ、結果を図４に示した。Further, the concentration of dioxins in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in Table 2. The concentration of chlorophenol in the exhaust gas at the entrance of the electrostatic precipitator was 4850 μg / Nm 3 . Moreover, the trichlorophenol concentration (average value) in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５１】実施例２
比較例５において、起動運転時及び停止運転時の薬剤注
入量を粉末活性炭２００ｍｇ／Ｎｍ３、重曹８００ｍｇ
／Ｎｍ３の合計１０００ｍｇ／Ｎｍ３としたこと以外は
同様にして図３に示すタイムスケジュールで運転を行
い、電気集塵機出口の排ガスのトリクロロフェノール濃
度の変化を調べ、結果を図３に示した。Example 2 In Comparative Example 5, the amount of the chemicals injected during the start-up operation and the stop operation was 200 mg of powdered activated carbon / Nm 3 and 800 mg of baking soda.
/ Nm 3 except that the total was 1000 mg / Nm 3 , the same operation was performed according to the time schedule shown in FIG. 3, and the change in the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator was examined, and the results are shown in FIG.
【００５２】また、定常運転時の電気集塵機出口の排ガ
スのダイオキシン類濃度を調べ、結果を表２に示した。
また、定常運転時の電気集塵機出口の排ガス中のトリク
ロロフェノール濃度（平均値）を調べ、結果を図４に示
した。The concentration of dioxins in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in Table 2.
Moreover, the trichlorophenol concentration (average value) in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５３】[0053]
【表２】 [Table 2]
【００５４】図２，３及び表２より、薬剤の一定量注入
では、起動運転時及び停止運転時に定常運転時よりもト
リクロロフェノール濃度が増加し、定常運転時のダイオ
キシン類濃度も増加するが、起動運転時及び停止運転時
の薬剤注入量を、定常運転時の薬剤注入量よりも増加さ
せることにより、起動運転時及び停止運転時の排ガス中
のトリクロロフェノール濃度を低減することができ、こ
の結果、定常運転時のダイオキシン類発生量を低減する
ことができることがわかる。From FIGS. 2 and 3 and Table 2, in the constant amount injection of the drug, the trichlorophenol concentration during the start-up operation and the stop operation increased more than that during the steady operation, and the dioxin concentration during the steady operation also increased. By increasing the drug injection amount during start-up operation and stop operation over the drug injection amount during steady-state operation, it is possible to reduce the trichlorophenol concentration in the exhaust gas during start-up operation and stop operation. It is understood that the amount of dioxins generated during steady operation can be reduced.
【００５５】比較例６
実施例２において、起動運転時及び停止運転時に薬剤の
注入を行わなかったこと以外は同様にして運転を行い、
定常運転時の電気集塵機出口のトリクロロフェノール濃
度（平均値）を調べ、結果を図４に示した。Comparative Example 6 The same operation as in Example 2 was carried out except that no drug was injected during the start-up operation and the stop operation,
The trichlorophenol concentration (average value) at the exit of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５６】図４より、前日の停止運転時及び当日の起
動運転時の薬剤添加量と当日の定常運転時のトリクロロ
フェノール濃度とには相関があることがわかる。It can be seen from FIG. 4 that there is a correlation between the amount of chemicals added during the stop operation on the previous day and during the start operation on the day and the trichlorophenol concentration during the steady operation on the day.
【００５７】なお、この都市ごみ焼却炉において、電気
集塵機出口の排ガス中のトリクロロフェノール濃度とダ
イオキシン類発生量との関係を調べたところ、図５に示
す如く、両者に相関関係があることが認められた。In this municipal solid waste incinerator, the relationship between the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator and the amount of dioxins generated was examined. As shown in FIG. 5, there was a correlation between the two. Was given.
【００５８】実施例３
図５より、電気集塵機出口排ガスのダイオキシン類濃度
を１ｎｇ−ＴＥＱ／Ｎｍ３以下とするためには、電気集
塵機出口のトリクロロフェノールは約７μｇ／Ｎｍ３以
下とすれば良いことがわかる。一方で、図４より、定常
運転時５００ｍｇ／Ｎｍ３の薬剤注入量としている場
合、定常運転時の電気集塵機出口のトリクロロフェノー
ル濃度を７μｇ／Ｎｍ３以下とするためには、停止運転
時及び起動運転時の薬剤注入量を７５０ｍｇ／Ｎｍ３以
上とすれば良いことがわかる。Example 3 From FIG. 5, in order to reduce the concentration of dioxins in the exhaust gas from the outlet of the electrostatic precipitator to 1 ng-TEQ / Nm 3 or less, the amount of trichlorophenol at the outlet of the electrostatic precipitator should be about 7 μg / Nm 3 or less. I understand. On the other hand, from FIG. 4, when the chemical injection amount is 500 mg / Nm 3 at the time of steady operation, in order to keep the concentration of trichlorophenol at the outlet of the electrostatic precipitator at 7 μg / Nm 3 or less at the time of steady operation, at the time of stop operation and start-up. It is understood that the drug injection amount during operation should be 750 mg / Nm 3 or more.
【００５９】そこで、実施例２において、停止運転時及
び起動運転時の薬剤添加量を７５０ｍｇ／Ｎｍ３とした
こと以外は同様にして運転を行ったところ、ダイオキシ
ン発生量を１ｎｇ−ＴＥＱ／Ｎｍ３以下に抑えることが
できることが確認された。Therefore, in Example 2, when the operation was performed in the same manner except that the chemical addition amount during the stop operation and the start operation was 750 mg / Nm 3 , the dioxin generation amount was 1 ng-TEQ / Nm 3. It was confirmed that it can be suppressed to the following.
【００６０】[0060]
【発明の効果】以上詳述した通り、本発明のダイオキシ
ン類の放出防止方法によれば、廃棄物焼却炉等の焼却
炉、特に、准連続炉や機械バッチ炉のように、１日のう
ちに炉の起動（立ち上げ）と停止（立ち下げ）とを行
う、ダイオキシン類前駆体発生量の多い炉施設におい
て、ダイオキシン類の放出を安定かつ確実に防止するこ
とができる。As described in detail above, according to the method for preventing the release of dioxins of the present invention, an incinerator such as a waste incinerator, particularly a quasi-continuous furnace or a mechanical batch furnace, can be used within one day. It is possible to reliably and reliably prevent the release of dioxins in a reactor facility in which a large amount of dioxin precursor is generated, in which the furnace is started (started up) and stopped (stopped).
【図１】実施例１において処理した都市ごみ焼却炉の構
成を示す系統図である。FIG. 1 is a system diagram showing a configuration of an municipal solid waste incinerator treated in Example 1.
【図２】比較例５における都市ごみ焼却炉の電気集塵機
の温度と排ガス中のトリクロロフェノール濃度の経時変
化を示すグラフである。FIG. 2 is a graph showing the changes over time in the temperature of the electric dust collector of the municipal solid waste incinerator and the concentration of trichlorophenol in the exhaust gas in Comparative Example 5.
【図３】実施例２における排ガス中のトリクロロフェノ
ール濃度の経時変化と薬剤添加量を示すグラフである。FIG. 3 is a graph showing changes over time in the concentration of trichlorophenol in exhaust gas and the amount of chemicals added in Example 2.
【図４】実施例２及び比較例５，６における、前日の停
止運転時と当日の起動運転時の薬剤添加量と、定常運転
時の排ガス中のトリクロロフェノール濃度との関係を示
すグラフである。FIG. 4 is a graph showing the relationship between the amount of chemicals added during the stop operation on the previous day and the start operation on the same day and the trichlorophenol concentration in the exhaust gas during the steady operation in Example 2 and Comparative Examples 5 and 6. .
【図５】都市ごみ焼却炉の排ガス中のトリクロロフェノ
ール濃度とダイオキシン類濃度との関係を示すグラフで
ある。FIG. 5 is a graph showing the relationship between the concentration of trichlorophenol and the concentration of dioxins in the exhaust gas of the municipal solid waste incinerator.
１ ストーカ炉 ２ ガス冷却室 ３ 空気予熱器 ４ 電気集塵機 ５ 誘引送風機 ６ 煙突 1 stoker furnace 2 gas cooling room 3 Air preheater 4 Electric dust collector 5 induction blower 6 chimney
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１５年１月１４日（２００３．１．１
４）[Submission date] January 14, 2003 (2003.1.1
4)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】[0012]
【課題を解決するための手段】請求項１のダイオキシン
類の放出防止方法は、短期間の間に起動と停止とを行う
焼却炉の排ガスに対して、粉末活性炭が５０〜３００ｍ
ｇ／Ｎｍ３ で、重曹が６００ｍｇ〜３０００ｍｇ／Ｎｍ
３ で、粉末活性炭と重曹との合計添加量の８〜２０重量
％が粉末活性炭となるように添加することを特徴とす
る。本発明において、短期間とは１〜３日程度をさす。According to the method for preventing the release of dioxins according to claim 1, the activated carbon powder is 50 to 300 m against exhaust gas of an incinerator which is started and stopped in a short period of time.
in g / Nm 3, baking soda is 600mg~3000mg / Nm
3 , 8 to 20 weight of the total addition amount of powdered activated carbon and baking soda
% Is added so as to be powdered activated carbon . In the present invention, the short term refers to about 1 to 3 days.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】請求項２のダイオキシン類の放出防止方法
は、排ガス中のクロロフェノール類濃度が３〜３０μｇ
／Ｎｍ３となるような焼却炉の排ガスに対して、粉末活
性炭が５０〜３００ｍｇ／Ｎｍ３ で、重曹が６００ｍｇ
〜３０００ｍｇ／Ｎｍ３ で、粉末活性炭と重曹との合計
添加量の８〜２０重量％が粉末活性炭となるように添加
することを特徴とする。In the method for preventing the release of dioxins according to claim 2, the concentration of chlorophenols in the exhaust gas is 3 to 30 μg.
/ Relative Nm 3 become such incinerator exhaust gas, powdered activated carbon at 50 to 300 mg / Nm 3, baking soda 600mg
~ 3000 mg / Nm 3 , total of powdered activated carbon and baking soda
It is characterized in that 8 to 20% by weight of the added amount is added so as to become powdered activated carbon .
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１６】以上のことから、請求項１，２のダイオキ
シン類の放出防止方法では、短期間、例えば１日の間に
起動と停止とを行う、ダイオキシン類前駆体濃度の高い
焼却炉排ガス又は、クロロフェノール類濃度が３〜３０
μｇ／Ｎｍ３というようなダイオキシン類前駆体濃度の
高い焼却炉排ガスに対して、粉末活性炭５０〜３００ｍ
ｇ／Ｎｍ３と重曹６００〜３０００ｍｇ／Ｎｍ３とを、
粉末活性炭と重曹との合計添加量の８〜２０重量％が粉
末活性炭となるように添加する。From the above, in the method for preventing the release of dioxins according to claims 1 and 2, incinerator exhaust gas having a high dioxin precursor concentration, which is started and stopped for a short period of time, for example, one day, or Chlorophenol concentration is 3 to 30
50 to 300 m of activated carbon powder for incinerator exhaust gas with a high concentration of dioxins precursor such as μg / Nm 3.
g / Nm 3 and baking soda 600 to 3000 mg / Nm 3 ,
8-20% by weight of the total amount of powdered activated carbon and baking soda added is powder.
Add so that it becomes powdered activated carbon .
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１８】請求項３のダイオキシン類の放出防止方法
は、炉の排ガスにダイオキシン類低減薬剤を添加してダ
イオキシン類の放出を防止する方法において、該炉の起
動運転時及び停止運転時に、定常運転時のダイオキシン
類低減薬剤添加量の１．３〜３倍のダイオキシン類低減
薬剤を添加することを特徴とする。The method for preventing the release of dioxins according to claim 3 is a method for preventing the release of dioxins by adding a dioxins reducing agent to the exhaust gas of a furnace, wherein the steady operation is performed during the start-up operation and the stop operation of the furnace. Dioxin of time
It is characterized in that a dioxin-reducing agent is added in an amount 1.3 to 3 times as much as the amount of the group-reducing agent added .
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Name of item to be corrected] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２２】請求項１，２の方法においては、１日の間
に起動と停止とを行うために、ダイオキシン類前駆体濃
度の高い焼却炉排ガス、又はクロロフェノール類濃度が
３〜３０μｇ／Ｎｍ３というようなダイオキシン類前駆
体濃度の高い焼却炉排ガスに対して、粉末活性炭５０〜
３００ｍｇ／Ｎｍ３好ましくは８０〜１２０ｍｇ／Ｎｍ
３と重曹６００〜３０００ｍｇ／Ｎｍ３好ましくは７０
０〜８００ｍｇ／Ｎｍ ３とを、粉末活性炭と重曹との合
計添加量の８〜２０重量％が粉末活性炭となるように添
加する。In the method of claims 1 and 2, during one day
In order to start and stop the
Incinerator exhaust gas with high degree or chlorophenol concentration
3-30 μg / NmThreePrecursor of dioxins such as
Powder activated carbon 50 ~ for incinerator exhaust gas with high body concentration
300 mg / NmThreePreferably 80-120 mg / Nm
ThreeAnd baking soda 600-3000 mg / NmThreePreferably 70
0-800mg / Nm ThreeAnd, Powdered activated carbon and baking soda
8 to 20% by weight of the total amount added is powdered activated carbonAttendant
Add
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Name of item to be corrected] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３２】請求項３の方法では、廃棄物焼却炉等の焼
却炉や、鉄鋼製造電炉、金属回収炉等の加熱炉のような
ダイオキシン類が発生する炉施設において、炉の起動運
転時及び停止運転時において、ダイオキシン類低減薬剤
の添加量を定常運転時のダイオキシン類低減薬剤添加量
よりも多くする。この起動運転時及び停止運転時のダイ
オキシン類低減薬剤添加量は、適用対象の炉施設の運転
状況、ダイオキシン類の発生状況によっても異なるが、
定常運転時のダイオキシン類低減薬剤添加量の１．３〜
３倍の範囲で決定する。 According to the method of claim 3, in the incinerator such as a waste incinerator, in a furnace facility where dioxins are generated such as a heating furnace such as a steel manufacturing electric furnace, a metal recovery furnace, etc., at the time of starting and stopping the furnace. The amount of the dioxin-reducing agent added during operation is made larger than the amount of the dioxin-reducing agent added during steady operation. The amount of dioxin-reducing chemicals added during start-up and stop-operations will vary depending on the operating conditions of the target furnace facility and the dioxin generation .
1.3 of dioxins reducing agent amount during steady operation
That determine at three times the range.
【手続補正書】[Procedure amendment]
【提出日】平成１５年３月２８日（２００３．３．２
８）[Submission date] March 28, 2003 (2003.3.2)
8)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 ダイオキシン類の放出防止方法Title: Method for preventing the release of dioxins
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、廃棄物焼却炉等の
焼却炉や、鉄鋼製造電炉、金属回収炉等の加熱炉などか
らのダイオキシン類の放出を防止する方法に係り、特
に、准連続式又は機械バッチ式都市ごみ焼却炉のよう
に、短期間、例えば１日のうちに炉の起動（立ち上げ）
と停止（立ち下げ）とを行う炉施設において、ダイオキ
シン類の放出を確実に防止する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the release of dioxins from incinerators such as waste incinerators and heating furnaces such as electric steelmaking electric furnaces and metal recovery furnaces, and more particularly, quasi-continuous Start-up (start-up) of a furnace in a short period of time, for example, in one day, such as a manual or mechanical batch-type municipal solid waste incinerator
The present invention relates to a method for surely preventing the release of dioxins in a furnace facility that performs shutdown (shutdown).
【０００２】[0002]
【従来の技術】ごみ焼却炉等の焼却炉においては、燃焼
中にクロロフェノール、クロロベンゼン等の塩素化芳香
族化合物や塩素化アルキル化合物等のダイオキシン類前
駆体が発生する。これらのダイオキシン類前駆体は、飛
灰が共存するとその触媒作用でダイオキシン類（ポリ塩
化ジベンゾダイオキシン及びポリ塩化ジベンゾフラン、
コプラナーＰＣＢ）となり、煤塵や排ガス中に存在する
ようになる。2. Description of the Related Art In an incinerator such as a refuse incinerator, dioxin precursors such as chlorinated aromatic compounds such as chlorophenol and chlorobenzene and chlorinated alkyl compounds are generated during combustion. These dioxin precursors are dioxins (polychlorinated dibenzodioxins and polychlorinated dibenzofuran,
It becomes a coplanar PCB) and becomes present in soot and exhaust gas.
【０００３】ダイオキシン類の放出量を低減するため
に、炉の燃焼改善、バグフィルターや触媒塔の設置等の
改造等が行われている。In order to reduce the emission of dioxins, the combustion of the furnace has been improved, and the bag filter and the catalyst tower have been remodeled.
【０００４】しかしながら、ダイオキシン類の主な生成
場所は、一般に燃焼炉のあとのガスの処理工程であるた
め、炉の燃焼改善だけでは排ガス中のダイオキシン類を
十分に低減できない。また、装置改造は、イニシャルコ
ストが高く、設置に期間を要し、必要とするスペースも
大きい上に、導入に当たっては炉の運転を長期間停止し
なければならないなどの欠点がある。However, since the main production site of dioxins is generally the gas treatment step after the combustion furnace, it is not possible to sufficiently reduce the dioxins in the exhaust gas only by improving the combustion of the furnace. Further, the device modification has the drawbacks that the initial cost is high, the installation requires a long period of time, the required space is large, and the furnace operation must be stopped for a long time before introduction.
【０００５】簡便にダイオキシン類の放出量を低減する
方法として、ダイオキシン類低減薬剤を排ガスに添加す
る方法がある。ダイオキシン類低減薬剤として用いられ
る主な薬剤は、ダイオキシン吸着能を有する活性炭を主
成分とした薬剤、或いは、ダイオキシン類前駆体固定能
を有するアルカリ炭酸水素塩や炭酸塩を主成分とした薬
剤であり、場合によってはこれらの成分に消石灰等の酸
性ガス除去剤、リン酸塩やキレート剤等の重金属固定剤
が併用される。As a method for easily reducing the amount of dioxins released, there is a method of adding a dioxins reducing agent to exhaust gas. The main agents used as dioxins reducing agents are agents that have activated carbon that has the ability to adsorb dioxin as the main ingredient, or agents that have alkali carbonate or carbonate that has the ability to fix dioxin precursors as the main ingredient. Depending on the case, an acid gas removing agent such as slaked lime and a heavy metal fixing agent such as a phosphate or a chelating agent are used together with these components.
【０００６】このような薬剤添加によるダイオキシン類
の放出防止法として、本出願人は先に重曹（炭酸水素ナ
トリウム）等のアルカリと活性炭とを焼却炉排ガスに添
加する方法を提案した（特開２０００−３５４７３
５）。この方法では、重曹を６０〜８０重量％、活性炭
を２０〜４０重量％混合した薬剤を排ガスに対して１０
０〜６００ｍｇ／Ｎｍ３となるように添加するのが好ま
しいとされている。As a method for preventing the release of dioxins by adding such chemicals, the present applicant has previously proposed a method of adding an alkali such as sodium bicarbonate (sodium hydrogen carbonate) and activated carbon to incinerator exhaust gas (Japanese Patent Laid-Open No. 2000-2000). -35473
5). According to this method, a chemical agent containing 60 to 80% by weight of baking soda and 20 to 40% by weight of activated carbon is added to the exhaust gas in an amount of 10%.
It is said that it is preferable to add it so as to be 0 to 600 mg / Nm 3 .
【０００７】従来、これらのダイオキシン類低減薬剤
は、定量吹き込み方式にて、即ち排ガスに対して一定の
添加割合にて添加されているが、消石灰と活性炭の混合
物を排ガスに吹き込む方法にあっては、排ガス中のＨＣ
ｌ濃度によって注入量を制御する場合もある。Conventionally, these dioxins-reducing agents have been added in a fixed-quantity blowing method, that is, at a constant addition ratio to the exhaust gas, but in the method of blowing a mixture of slaked lime and activated carbon into the exhaust gas. , HC in exhaust gas
The injection amount may be controlled depending on the l concentration.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上記特
開２０００−３５４７３５に記載されるような薬剤添加
法は、比較的規模の大きな全連続式焼却炉では良好な結
果が得られているが、中小型焼却炉では十分なダイオキ
シン類の放出防止効果が得られない場合があった。特
に、短期間、例えば１日のうちで立ち上げ（起動）と立
ち下げ（停止）を行う准連続炉や機械バッチ炉に対して
は、十分に満足のいく効果が得られていない。However, the chemical addition method as described in JP-A-2000-354735 gives good results in a relatively large-scale, all-continuous incinerator, but In some cases, a small incinerator could not provide sufficient dioxins emission prevention effect. In particular, a sufficiently satisfactory effect has not been obtained for a quasi-continuous furnace or a mechanical batch furnace that starts (starts) and stops (stops) within a short period of time, for example, one day.
【０００９】また、准連続炉、機械バッチ炉等のよう
に、短期間のうちに起動と停止を行う焼却炉では、この
起動運転時と停止運転時にダイオキシン類及びダイオキ
シン類前駆体濃度が増加する。そして、このことが従来
のダイオキシン類低減薬剤の定量吹き込み方式では、停
止運転及び起動運転後の定常運転時のダイオキシン類発
生量を増大させる原因となる。即ち、ダイオキシン類低
減薬剤の定量吹き込み方式では、停止時及び起動時にダ
イオキシン類前駆体発生量に対してダイオキシン類低減
薬剤が不足する。そして、ダイオキシン類低減薬剤によ
り処理しきれなかったダイオキシン類前駆体は、停止時
及び起動時に煙突から排出されるばかりでなく煙道や排
ガス処理装置等に蓄積され、定常運転時にダイオキシン
類として排出されるようになり、定常運転時の排ガス中
のダイオキシン類濃度を高める結果となる。Further, in incinerators such as a quasi-continuous furnace and a mechanical batch furnace which start and stop in a short period of time, the concentrations of dioxins and dioxin precursors increase during the start-up operation and the stop operation. . Then, in the conventional fixed amount blowing method for dioxins-reducing agents, this causes an increase in the amount of dioxins generated during steady operation after stop operation and start operation. That is, in the fixed amount blowing method of the dioxin-reducing agent, the dioxin-reducing agent is insufficient with respect to the amount of dioxin precursors generated at the time of stopping and starting. The dioxin precursor that could not be completely treated by the dioxin reducing agent is not only discharged from the chimney at the time of stop and start, but also accumulated in the flue and exhaust gas treatment equipment, etc., and discharged as dioxin during steady operation. As a result, the concentration of dioxins in the exhaust gas during normal operation is increased.
【００１０】なお、前記の通り、消石灰と活性炭の混合
物の添加量を排ガスのＨＣｌ濃度に応じて制御する場合
があるが、焼却炉や加熱炉においてＨＣｌ濃度とダイオ
キシン類濃度との相関は低く変動も激しいので、起動時
及び停止時のダイオキシン類発生量の増加には対応し得
ない。As described above, the addition amount of the mixture of slaked lime and activated carbon may be controlled depending on the HCl concentration of the exhaust gas, but in the incinerator and the heating furnace, the correlation between the HCl concentration and the dioxin concentration is low and fluctuates. Since it is severe, it cannot cope with the increase in the amount of dioxins generated at the time of starting and stopping.
【００１１】本発明は上記従来の問題点を解決し、廃棄
物焼却炉等の焼却炉、特に、准連続炉や機械バッチ炉の
ように、短期間のうちに炉の起動（立ち上げ）と停止
（立ち下げ）とを行う炉施設において、ダイオキシン類
の放出を安定かつ確実に防止する方法を提供することを
目的とする。The present invention solves the above-mentioned conventional problems, and incinerators such as waste incinerators, in particular, quasi-continuous furnaces and mechanical batch furnaces, can be started (started) in a short period of time. It is an object of the present invention to provide a method for stably and reliably preventing the release of dioxins in a reactor facility that is shut down (shut down).
【００１２】[0012]
【課題を解決するための手段】請求項１のダイオキシン
類の放出防止方法は、短期間の間に起動と停止とを行う
焼却炉の排ガスに対して、粉末活性炭が５０〜３００ｍ
ｇ／Ｎｍ３で、重曹が６００ｍｇ〜３０００ｍｇ／Ｎｍ
３で、粉末活性炭と重曹との合計添加量の８〜２０重量
％が粉末活性炭となるように添加することを特徴とす
る。本発明において、短期間とは１〜３日程度をさす。According to the method for preventing the release of dioxins according to claim 1, the activated carbon powder is 50 to 300 m against exhaust gas of an incinerator which is started and stopped in a short period of time.
g / Nm 3 , baking soda 600 mg to 3000 mg / Nm
In item 3, 8 to 20% by weight of the total amount of the powdered activated carbon and baking soda is added so that the powdered activated carbon is added. In the present invention, the short term refers to about 1 to 3 days.
【００１３】請求項２のダイオキシン類の放出防止方法
は、排ガス中のクロロフェノール類濃度が３〜３０μｇ
／Ｎｍ３となるような焼却炉の排ガスに対して、粉末活
性炭が５０〜３００ｍｇ／Ｎｍ３で、重曹が６００ｍｇ
〜３０００ｍｇ／Ｎｍ３で、粉末活性炭と重曹との合計
添加量の８〜２０重量％が粉末活性炭となるように添加
することを特徴とする。In the method for preventing the release of dioxins according to claim 2, the concentration of chlorophenols in the exhaust gas is 3 to 30 μg.
/ Relative Nm 3 become such incinerator exhaust gas, powdered activated carbon at 50 to 300 mg / Nm 3, baking soda 600mg
˜3000 mg / Nm 3 , and 8 to 20% by weight of the total addition amount of the powdered activated carbon and baking soda is added so as to be the powdered activated carbon.
【００１４】発明者らは、重曹が焼却炉排ガス中のダイ
オキシン類の生成抑制に有効であることを確認したが、
重曹の添加量は、適用排ガス中のダイオキシン類前駆体
（例えばクロロフェノール類）の濃度に応じて制御する
ことが効果的であることを確認した。特に、１日のうち
で起動と停止を行う准連続炉（１日の運転時間は１６時
間）や機械バッチ炉（１日の運転時間は８時間）では、
排ガス中のダイオキシン類前駆体濃度は、平均３０μｇ
／Ｎｍ３程度と、全連続炉の排ガス中のダイオキシン類
前駆体濃度の平均２〜３μｇ／Ｎｍ３に対して１０倍程
度高濃度であり、この高濃度のダイオキシン類前駆体に
応じて、重曹の添加量は少なくとも６００ｍｇ／Ｎｍ３
は必要である。重曹の添加量を多くすると、ＨＣｌ等の
酸性ガスを重曹以外のアルカリ剤を用いずに除去するこ
とができるが、３０００ｍｇ／Ｎｍ３を超えて添加して
もこの除去効果は変わらない。従って、重曹の添加量は
６００〜３０００ｍｇ／Ｎｍ３とする。The inventors have confirmed that baking soda is effective in suppressing the formation of dioxins in exhaust gas from incinerators.
It was confirmed that it is effective to control the addition amount of baking soda according to the concentration of the dioxin precursor (eg, chlorophenols) in the applied exhaust gas. Especially in quasi-continuous furnaces (starting time is 16 hours) and mechanical batch furnaces (starting time is 8 hours) that start and stop within a day,
Dioxin precursor concentration in exhaust gas is 30 μg on average
/ Nm 3 , which is about 10 times higher than the average concentration of dioxins precursors in the exhaust gas of all continuous furnaces of 2 to 3 μg / Nm 3 , and baking soda can be added depending on the concentration of dioxins precursor. Is added at least 600 mg / Nm 3
Is necessary. When the amount of baking soda added is increased, acidic gases such as HCl can be removed without using an alkaline agent other than baking soda, but even if added in excess of 3000 mg / Nm 3 , this removal effect does not change. Therefore, the addition amount of baking soda is 600 to 3000 mg / Nm 3 .
【００１５】また、粉末活性炭は、燃焼により生成して
排ガス中に既に存在するガス状のダイオキシン類の吸着
除去を行うが、十分な接触効率を得るためには排ガスに
対して５０ｍｇ／Ｎｍ３以上の添加が必要である。一
方、活性炭はダイオキシン類生成触媒としても働くた
め、過剰添加により逆にダイオキシン類の増加を招くこ
とになる。従って、粉末活性炭は３００ｍｇ／Ｎｍ３以
下での添加が好ましい。Further, the powdered activated carbon adsorbs and removes the gaseous dioxins already produced in the exhaust gas by combustion, but in order to obtain sufficient contact efficiency, 50 mg / Nm 3 or more with respect to the exhaust gas. Is required. On the other hand, since activated carbon also functions as a dioxin-producing catalyst, excessive addition thereof causes an increase in dioxin. Therefore, it is preferable to add the powdered activated carbon at 300 mg / Nm 3 or less.
【００１６】以上のことから、請求項１，２のダイオキ
シン類の放出防止方法では、短期間、例えば１日の間に
起動と停止とを行う、ダイオキシン類前駆体濃度の高い
焼却炉排ガス又は、クロロフェノール類濃度が３〜３０
μｇ／Ｎｍ３というようなダイオキシン類前駆体濃度の
高い焼却炉排ガスに対して、粉末活性炭５０〜３００ｍ
ｇ／Ｎｍ３と重曹６００〜３０００ｍｇ／Ｎｍ３とを、
粉末活性炭と重曹との合計添加量の８〜２０重量％が粉
末活性炭となるように添加する。From the above, in the method for preventing the release of dioxins according to claims 1 and 2, incinerator exhaust gas having a high dioxin precursor concentration, which is started and stopped for a short period of time, for example, one day, or Chlorophenol concentration is 3 to 30
50 to 300 m of activated carbon powder for incinerator exhaust gas with a high concentration of dioxins precursor such as μg / Nm 3.
g / Nm 3 and baking soda 600 to 3000 mg / Nm 3 ,
8 to 20% by weight of the total amount of powdered activated carbon and baking soda is added so as to be powdered activated carbon.
【００１７】なお、ここで、クロロフェノール類とは、
モノクロロフェノール、ジクロロフェノール、トリクロ
ロフェノール、テトラクロロフェノール、ペンタクロロ
フェノール、ヘキサクロロフェノール等を指す。Here, the chlorophenols are
It refers to monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, pentachlorophenol, hexachlorophenol, and the like.
【００１８】請求項３のダイオキシン類の放出防止方法
は、炉の排ガスにダイオキシン類低減薬剤を添加してダ
イオキシン類の放出を防止する方法において、該炉の起
動運転時及び停止運転時に、定常運転時のダイオキシン
類低減薬剤添加量の１．３〜３倍のダイオキシン類低減
薬剤を添加する方法であって、該起動運転時及び該起動
運転の直前の停止運転時のダイオキシン類低減薬剤の添
加量と、該起動運転後の定常運転時のダイオキシン類前
駆体の発生量との関係を求め、この関係に基いて起動運
転時及び停止運転時のダイオキシン類低減薬剤添加量を
決定することを特徴とする。The method for preventing the release of dioxins according to claim 3 is a method for preventing the release of dioxins by adding a dioxins reducing agent to the exhaust gas of a furnace, wherein the steady operation is performed during the start-up operation and the stop operation of the furnace. A method for adding a dioxin-reducing agent in an amount 1.3 to 3 times as much as the amount of dioxin-reducing agent added during the start-up operation and the start-up.
Immediately before operation Addition of dioxin-reducing agents during operation
Before addition of dioxins during steady operation after the start-up operation
Obtain the relationship with the amount of the generated body, and based on this relationship, start operation
The amount of dioxin-reducing chemicals added during turning and stopping operation
It is characterized by making a decision .
【００１９】このように、ダイオキシン類発生量の多い
炉の起動運転時及び停止運転時において、定常運転時よ
りも多量のダイオキシン類低減薬剤を添加することによ
り、起動運転時及び停止運転時のダイオキシン類前駆体
発生量を低減することができ、これにより、定常運転時
のダイオキシン類発生量を目標値以下に抑えることがで
きる。As described above, during start-up operation and stop operation of a furnace that generates a large amount of dioxins, by adding a larger amount of the dioxin-reducing agent than during steady operation, the dioxin during start-up operation and stop operation It is possible to reduce the amount of precursors generated, and thereby to suppress the amount of dioxins generated during steady operation below the target value.
【００２０】この場合、定常運転時のダイオキシン類前
駆体の発生量は、当該定常運転時の直前の起動運転時と
その直前の停止運転時のダイオキシン類低減薬剤の添加
量に相関する。このため、請求項３の方法では、起動運
転時及び該起動運転の直前の停止運転時のダイオキシン
類低減薬剤の添加量と、該起動運転後の定常運転時のダ
イオキシン類前駆体の発生量との関係を求め、この関係
に基いて起動運転時及び停止運転時のダイオキシン類低
減薬剤の添加量を決定する。In this case, the amount of the dioxin precursors generated during the steady operation correlates with the amount of the dioxin-reducing agent added during the start operation immediately before the steady operation and the stop operation immediately before that. Therefore, according to the method of claim 3, the amount of the dioxin-reducing agent added during the start-up operation and the stop operation immediately before the start-up operation, and the amount of the dioxin precursors generated during the steady-state operation after the start-up operation. Is calculated, and the addition amount of the dioxin-reducing agent during start-up operation and stop operation is determined based on this relationship.
【００２１】[0021]
【発明の実施の形態】以下に、本発明のダイオキシン類
の放出防止方法の実施の形態を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for preventing the release of dioxins of the present invention will be described in detail below.
【００２２】請求項１，２の方法においては、１日の間
に起動と停止とを行うために、ダイオキシン類前駆体濃
度の高い焼却炉排ガス、又はクロロフェノール類濃度が
３〜３０μｇ／Ｎｍ３というようなダイオキシン類前駆
体濃度の高い焼却炉排ガスに対して、粉末活性炭５０〜
３００ｍｇ／Ｎｍ３好ましくは８０〜１２０ｍｇ／Ｎｍ
３と重曹６００〜３０００ｍｇ／Ｎｍ３好ましくは７０
０〜８００ｍｇ／Ｎｍ ３とを、粉末活性炭と重曹との合
計添加量の８〜２０重量％が粉末活性炭となるように添
加する。In the method of claims 1 and 2, during one day
In order to start and stop the
Incinerator exhaust gas with high degree or chlorophenol concentration
3-30 μg / NmThreePrecursor of dioxins such as
Powder activated carbon 50 ~ for incinerator exhaust gas with high body concentration
300 mg / NmThreePreferably 80-120 mg / Nm
ThreeAnd baking soda 600-3000 mg / NmThreePreferably 70
0-800mg / Nm ThreeAnd the powdered activated carbon and baking soda
Add so that 8 to 20% by weight of the total amount added becomes powdered activated carbon.
Add
【００２３】粉末活性炭と重曹の添加量は上記範囲内で
あれば良いが、添加量が少ないと十分な効果が得られ
ず、逆に多いと煤塵負荷が増加する上に、薬剤コストの
増加を招くことから、粉末活性炭と重曹との合計で６５
０〜２０００ｍｇ／Ｎｍ３程度となるように添加するこ
とが好ましい。また、粉末活性炭と重曹との合計添加量
の８〜２０重量％が粉末活性炭となるように添加するこ
とがダイオキシン類の生成防止効果の面で好ましい。The amount of powdered activated carbon and baking soda added may be within the above range, but if the amount of addition is small, a sufficient effect cannot be obtained, and conversely, if the amount is large, the dust load increases and the drug cost also increases. In total, the total amount of activated carbon powder and baking soda is 65
It is preferable to add it so as to be about 0 to 2000 mg / Nm 3 . Further, it is preferable to add 8 to 20% by weight of the total amount of the powdered activated carbon and baking soda to form the powdered activated carbon from the viewpoint of the effect of preventing the formation of dioxins.
【００２４】粉末活性炭と重曹は、これらを予め混合し
て添加しても良く、また、別々に添加しても良いが、予
め混合しておくことにより、活性炭の発火の危険性を低
減することができる上に、添加設備を簡素化することが
でき、好ましい。The powdered activated carbon and the baking soda may be added by mixing them in advance, or may be added separately, but by mixing them in advance, the risk of ignition of the activated carbon is reduced. In addition to being able to do so, the addition equipment can be simplified, which is preferable.
【００２５】粉末活性炭と重曹とを予め混合する場合、
混合割合は、粉末活性炭を８〜２０重量％、重曹を９２
〜８０重量％となるような割合で混合することが、ダイ
オキシン類の生成防止効果の面で好ましい。When powdered activated carbon and baking soda are premixed,
The mixing ratio is 8 to 20% by weight of powdered activated carbon and 92% of baking soda.
It is preferable to mix them in such a proportion that the content becomes ˜80 wt%, from the viewpoint of the effect of preventing the formation of dioxins.
【００２６】請求項１，２において、粉末活性炭として
は、平均粒径が５０μｍ以下、例えば平均粒径が１０〜
３０μｍ程度の粉末活性炭が好ましい。In Claims 1 and 2, the powdered activated carbon has an average particle size of 50 μm or less, for example, an average particle size of 10 to 10.
Powdered activated carbon of about 30 μm is preferable.
【００２７】また、このような粉末活性炭との均一混合
性及び排ガスとの接触効率並びに取り扱い性の面から、
重曹は平均粒径５〜１５μ程度であることが好ましい。
このとき、任意の粒径の活性炭と重曹を、噴霧直前にそ
れぞれ１０〜３０μｍ、５〜１５μｍとなるように粉砕
しても良い。From the viewpoints of such uniform mixing with powdered activated carbon, contact efficiency with exhaust gas, and handleability,
The baking soda preferably has an average particle size of about 5 to 15 μm.
At this time, activated carbon and baking soda having arbitrary particle sizes may be pulverized immediately before spraying so as to have a particle size of 10 to 30 μm and 5 to 15 μm, respectively.
【００２８】なお、粉末活性炭は、ダイオキシン類生成
の触媒作用を抑制するために、アルカリを添着して用い
ても良い。The powdered activated carbon may be used with an alkali impregnated in order to suppress the catalytic action of dioxins generation.
【００２９】この場合、アルカリとしては、アミン化合
物、アンモニア、アンモニウム塩、アルカリ金属化合物
等の１種又は２種以上を用いることができる。このう
ち、アミン化合物としては、トリメチルアミン等のアル
キルアミン、トリエタノールアミン、モノエタノールア
ミン等のアルカノールアミンなどのほか、これらのアミ
ン化合物の塩酸塩、硫酸塩、炭酸塩等のアミン塩が挙げ
られる。アンモニウム塩としては、重炭酸アンモニウ
ム、硫酸アンモニウム、リン酸水素二アンモニウム等が
挙げられる。アルカリ金属化合物としては、ケイ酸ナト
リウム、ケイ酸カリウム等のアルカリ金属のケイ酸塩、
水酸化ナトリウム、水酸化カリウム等のアルカリ金属水
酸化物、炭酸塩等が挙げられ、これらのアルカリの添着
量は、好ましくは粉末活性炭に対して３０重量％以下、
特に好ましくは０．５〜１０重量％程度である。In this case, as the alkali, one or more of amine compounds, ammonia, ammonium salts, alkali metal compounds and the like can be used. Among these, examples of the amine compound include alkylamines such as trimethylamine, alkanolamines such as triethanolamine and monoethanolamine, and amine salts such as hydrochlorides, sulfates and carbonates of these amine compounds. Examples of the ammonium salt include ammonium bicarbonate, ammonium sulfate, diammonium hydrogen phosphate and the like. As the alkali metal compound, silicates of alkali metals such as sodium silicate and potassium silicate,
Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates, and the like, and the amount of these alkalis impregnated is preferably 30% by weight or less based on the powdered activated carbon.
Particularly preferably, it is about 0.5 to 10% by weight.
【００３０】粉末活性炭及び重曹の添加箇所は排ガスの
冷却工程の何れの箇所でも良いが、好ましくは、集塵機
手前の１５０〜４００℃の温度領域の部分に添加するの
が望ましい。The powdered activated carbon and baking soda may be added at any place in the exhaust gas cooling step, but it is preferable to add them to the temperature region of 150 to 400 ° C. before the dust collector.
【００３１】即ち、排ガスの冷却工程におけるダイオキ
シン類の合成は、温度約２００〜４００℃の領域で行わ
れるとされているが、実際の施設においては、集塵機内
部での合成が主であり、焼却炉から排出された高温度の
状態から冷却されて集塵機に流入するまでの間は滞留時
間が短いため、合成量は非常に少ない。従って、冷却さ
れた４００℃以下の条件で粉末活性炭及び重曹を注入す
れば、重曹により大部分のダイオキシン類の合成を防止
することができる。また、同時に粉末活性炭により、既
に焼却炉で生成した少量のダイオキシン類を吸着し、こ
れを集塵機で分離することにより、効率的にダイオキシ
ン類の除去を行える。That is, the synthesis of dioxins in the exhaust gas cooling process is said to be carried out in the temperature range of about 200 to 400 ° C. However, in actual facilities, the synthesis is mainly performed inside the dust collector and is incinerated. The amount of synthesis is very small because the residence time is short from the high temperature state discharged from the furnace until it is cooled and flows into the dust collector. Therefore, if powdered activated carbon and baking soda are injected under the cooled condition of 400 ° C. or less, the synthesis of most dioxins can be prevented by the baking soda. At the same time, powdered activated carbon adsorbs a small amount of dioxins already produced in the incinerator and separates them with a dust collector, so that dioxins can be efficiently removed.
【００３２】請求項３の方法では、廃棄物焼却炉等の焼
却炉や、鉄鋼製造電炉、金属回収炉等の加熱炉のような
ダイオキシン類が発生する炉施設において、炉の起動運
転時及び停止運転時において、ダイオキシン類低減薬剤
の添加量を定常運転時のダイオキシン類低減薬剤添加量
よりも多くする。この起動運転時及び停止運転時のダイ
オキシン類低減薬剤添加量は、適用対象の炉施設の運転
状況、ダイオキシン類の発生状況によっても異なるが、
定常運転時のダイオキシン類低減薬剤添加量の１．３〜
３倍の範囲で決定する。According to the method of claim 3, in the incinerator such as a waste incinerator, in a furnace facility where dioxins are generated such as a heating furnace such as a steel manufacturing electric furnace, a metal recovery furnace, etc., at the time of starting and stopping the furnace. The amount of the dioxin-reducing agent added during operation is made larger than the amount of the dioxin-reducing agent added during steady operation. The amount of dioxin-reducing chemicals added during start-up and stop-operations will vary depending on the operating conditions of the target furnace facility and the dioxin generation.
The amount of dioxin-reducing agents added during steady operation is 1.3-
Determine within a triple range.
【００３３】前述の如く、定常運転時のダイオキシン類
前駆体の発生量は、当該定常運転時の直前の起動運転時
と更にその直前の停止運転時のダイオキシン類低減薬剤
の添加量に相関することから、請求項３の方法において
は、起動運転時及び該起動運転の直前の停止運転時のダ
イオキシン類低減薬剤の添加量と、該起動運転後の定常
運転時のダイオキシン類前駆体の発生量との関係を求
め、この関係に基いて起動運転時及び停止運転時のダイ
オキシン類低減薬剤の添加量を決定する。 As described above, the amount of dioxin precursors generated during steady operation should be correlated with the amount of dioxin-reducing agent added during the start operation immediately before the steady operation and the stop operation immediately before that. from, in the method of claim 3, the amount of shutdown time of dioxins reducing agent immediately before and during the start-up operation start operation, the amount of dioxin precursors in the steady operation after the starting operation the relationship between the determined, that determine the amount of startup operation and shutdown time of dioxins reducing agent based on this relationship.
【００３４】即ち、例えば、１日のうちに起動と停止と
を行う准連続炉や機械バッチ炉では、当日の起動運転時
と前日の停止運転時のダイオキシン類低減薬剤添加量と
当日の定常運転時のダイオキシン類前駆体の発生量との
関係を求め、別途求めておいたダイオキシン類前駆体発
生量とダイオキシン類発生量との関係から、ダイオキシ
ン類発生量が目標値以下となるダイオキシン類前駆体発
生量に抑えることができるように、起動運転時と停止運
転時のダイオキシン類低減薬剤の添加量を決定すれば良
い。That is, for example, in a quasi-continuous furnace or a mechanical batch furnace that starts and stops within one day, the amount of dioxin-reducing chemicals added during the start operation on the day and the stop operation on the previous day and the steady operation on the day. The relationship between the amount of dioxin precursors generated at that time and the relationship between the amount of dioxin precursors generated and the amount of dioxin precursors that was separately calculated, and the dioxin precursors that are below the target value The amount of the dioxin-reducing agent added during the start-up operation and the stop operation may be determined so that the generation amount can be suppressed.
【００３５】この場合、濃度の測定対象となるダイオキ
シン類前駆体としては、トリクロロフェノール等のクロ
ロフェノール類やクロロベンゼン類が挙げられるが、特
にトリクロロフェノールが好ましい。これらのダイオキ
シン類前駆体は、ダイオキシン類に比べて濃度測定が容
易であり、しかもダイオキシン類濃度と相関するため、
ダイオキシン類濃度の指標として有効である。In this case, examples of the dioxin precursor whose concentration is to be measured include chlorophenols such as trichlorophenol and chlorobenzenes, with trichlorophenol being particularly preferred. These dioxin precursors are easier to measure the concentration than dioxins, and since they correlate with the dioxin concentration,
It is effective as an index for the concentration of dioxins.
【００３６】なお、請求項３の方法において、原則とし
て、炉の起動運転時は、炉施設の誘引ファン（誘引送風
機又はブロワ）の運転開始から炉内温度が設定温度に達
するまでの期間を指し、停止運転時とは、一般的には最
後の被処理物投入（例えば、ごみ焼却炉であれば、最後
のごみ投入）から誘引ファンを停止するまでの期間を指
す。ただし、これらの期間の始点及び終点はこの期間よ
りも若干前後にずれても良い。特に、起動時について
は、ダイオキシン類低減薬剤の定量注入で試運転を行
い、起動運転を行った場合に、排ガス中のダイオキシン
類前躯体濃度が十分に下がるまでの時間を予め求めてお
き、誘引ファンの運転開始からこの時間までを「起動運
転時」としてダイオキシン類低減薬剤の添加量を増やす
ようにすることが好ましい。また、停止運転時について
も同様に、ダイオキシン類低減薬剤の定量注入で試運転
を行い、排ガス中のダイオキシン類前躯体濃度が上昇し
始める時間を予め求めておき、この時間から誘引ファン
の運転停止までを「停止運転時」としてダイオキシン類
低減薬剤の添加量を増やすようにすることが好ましい。In the method of claim 3 , in principle, during the start-up operation of the furnace, the period from the start of operation of the induction fan (induction blower or blower) of the furnace facility until the temperature inside the furnace reaches the set temperature. The term “during stop operation” generally refers to a period from the last charging of the object to be treated (for example, in the case of a waste incinerator, the last charging of the waste) to the stop of the induction fan. However, the start point and the end point of these periods may be slightly shifted before and after this period. Especially, at the time of start-up, a trial run is performed by quantitative injection of dioxins-reducing agents, and when the start-up run is performed, the time until the concentration of dioxin precursors in exhaust gas is sufficiently reduced is obtained in advance, and the induction fan It is preferable to increase the amount of the dioxin-reducing agent added from the start of the operation up to this time as the “start-up operation”. Also during stop operation, similarly, test operation is performed by quantitative injection of dioxins reducing agent, the time when the concentration of dioxin precursor in the exhaust gas begins to rise is obtained in advance, and from this time until the operation of the induction fan is stopped. It is preferable to increase the amount of the dioxin-reducing agent to be added as "at the time of stop operation".
【００３７】請求項３の方法において、炉施設に添加す
るダイオキシン類低減薬剤は、ダイオキシン類の生成を
防止し得る薬剤、或いはダイオキシン類を吸着除去でき
る薬剤等であり、例えば、活性炭、ゼオライト、シリカ
ゲル、ケイソウ土、活性白土、酸性白土、カオリン、ベ
ントナイト、アロフェン、アパタイト等の有機又は無機
の吸着剤（特に活性炭、ゼオライトが好ましい）；上記
吸着剤、例えば活性炭もしくはゼオライトと消石灰の混
合物；ナトリウム、カリウム、カルシウム及びマグネシ
ウムよりなる群から選ばれる１種又は２種以上の炭酸塩
及び／又は炭酸水素塩；ナトリウム、カリウム、カルシ
ウム及びマグネシウムよりなる群から選ばれる１種又は
２種以上の炭酸塩及び／又は炭酸水素塩と、有機もしく
は無機吸着剤、例えば活性炭もしくはゼオライトとの混
合物；ナトリウム、カリウム、カルシウム及びマグネシ
ウムよりなる群から選ばれる１種又は２種以上の炭酸塩
及び／又は炭酸水素塩と、有機もしくは無機吸着剤、例
えば活性炭もしくはゼオライトと、重金属固定剤との混
合物；活性炭もしくはゼオライトと消石灰及び重金属固
定剤との混合物等を用いることができる。In the method of claim 3 , the dioxin-reducing agent added to the furnace facility is an agent capable of preventing the formation of dioxin, or an agent capable of adsorbing and removing dioxin, such as activated carbon, zeolite or silica gel. Organic or inorganic adsorbents such as diatomaceous earth, activated clay, acid clay, kaolin, bentonite, allophane and apatite (particularly activated carbon and zeolite are preferable); adsorbents such as activated carbon or a mixture of zeolite and slaked lime; sodium and potassium. , One or more carbonates and / or hydrogencarbonates selected from the group consisting of calcium and magnesium; one or more carbonates selected from the group consisting of sodium, potassium, calcium and magnesium, and / or Or bicarbonate and organic or inorganic adsorbents, eg For example, a mixture with activated carbon or zeolite; one or more carbonates and / or hydrogen carbonates selected from the group consisting of sodium, potassium, calcium and magnesium, and an organic or inorganic adsorbent such as activated carbon or zeolite, A mixture with a heavy metal fixing agent; a mixture of activated carbon or zeolite with slaked lime and a heavy metal fixing agent can be used.
【００３８】これらのダイオキシン類低減薬剤の添加箇
所は、ダイオキシン類低減薬剤の種類に応じて当該添加
箇所の温度やダイオキシン類の生成場所等を考慮して決
定される。例えば、粉末活性炭であれば、集塵機手前に
添加するのが好ましく、アルカリ炭酸塩／炭酸水素塩で
あれば、約２００〜８００℃の範囲で適用可能であるた
め、ボイラから集塵機の手前で注入するのが好ましい。The locations where these dioxin-reducing agents are added are determined in consideration of the temperature of the locations where the dioxin-reducing agents are added, the location where the dioxins are generated, etc., depending on the type of the dioxin-reducing agent. For example, in the case of powdered activated carbon, it is preferable to add it in front of the dust collector, and in the case of alkali carbonate / hydrogen carbonate, it can be applied in the range of about 200 to 800 ° C. Therefore, it is injected from the boiler before the dust collector. Is preferred.
【００３９】請求項３のダイオキシン類の放出防止方法
は、短期間の間に起動、停止を行う准連続炉、機械バッ
チ炉等への適用に好適であるが、全連続炉において、定
期点検や修理のために運転を停止した後、運転を再開す
る場合などにも適用可能である。The method for preventing the release of dioxins according to claim 3 is suitable for application to quasi-continuous furnaces, mechanical batch furnaces, etc. that start and stop in a short period of time. It is also applicable to the case of restarting the operation after stopping the operation for repair.
【００４０】請求項３の方法は、特に、請求項１，２の
方法と組み合わせて実施することが好ましく、短期間の
間に起動、停止を行う准連続炉、機械バッチ炉等におい
て、請求項１，２の粉末活性炭及び重曹添加量で定常運
転を行い、請求項３の方法に従って、起動運転時及び停
止運転時の粉末活性炭及び重曹の添加量を定常運転時よ
りも増加することが好ましい。The method of claim 3 is particularly preferably carried out in combination with the method of claims 1 and 2, and a quasi-continuous furnace, a machine batch furnace or the like which starts and stops in a short period of time is used. It is preferable to perform steady operation with the powdered activated carbon and baking soda addition amounts of 1 and 2 and to increase the addition amount of the powdered activated carbon and baking soda during start-up operation and stop operation more than in steady operation according to the method of claim 3 .
【００４１】[0041]
【実施例】以下に、実施例及び比較例を挙げて本発明を
より具体的に説明する。EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples.
【００４２】実施例１
処理能力２．５ｔ／ｈｒで、１日の運転時間が８時間
の、図１に示すようなストーカ炉１、ガス冷却室２、空
気予熱器３、電気集塵機４、誘引送風機５及び煙突６か
らなる都市ごみ焼却炉において、定常運転時に、粉末活
性炭の配合割合を１／９とした重曹（平均粒径１０μ
ｍ）／粉末活性炭（平均粒径２０μｍ）混合薬剤を電気
集塵機４の手前のＡの箇所から排ガスに対して９００ｍ
ｇ／Ｎｍ３（即ち、粉末活性炭添加量１００ｍｇ／Ｎｍ
３，重曹添加量８００ｍｇ／Ｎｍ３）の割合で添加し、
煙突６のダイオキシン類濃度を測定したところ、２．５
ｎｇ−ＴＥＱ／Ｎｍ３となった。Example 1 A stoker furnace 1, a gas cooling chamber 2, an air preheater 3, an electrostatic precipitator 4, and an induction device having a processing capacity of 2.5 t / hr and an operating time of 8 hours a day as shown in FIG. In a municipal solid waste incinerator consisting of a blower 5 and a chimney 6, during normal operation, baking soda with a mixing ratio of activated carbon powder of 1/9 (average particle size 10 μm
m) / powdered activated carbon (average particle size 20 μm) mixed chemical from the location A in front of the electrostatic precipitator 4 to the exhaust gas to 900 m
g / Nm 3 (that is, powder activated carbon addition amount 100 mg / Nm
3 , the addition amount of baking soda 800 mg / Nm 3 ),
When the concentration of dioxins in the chimney 6 was measured, it was 2.5
It became ng-TEQ / Nm 3 .
【００４３】なお、薬剤添加前の電気集塵機入口部分の
排ガス中のクロロフェノール濃度は、９．２μｇ／Ｎｍ
３であった。The concentration of chlorophenol in the exhaust gas at the inlet of the electrostatic precipitator before the chemical addition was 9.2 μg / Nm.
It was 3 .
【００４４】比較例１
実施例１において、薬剤を全く添加しないこと以外は同
様にして運転を行い、同様にクロロフェノール濃度とダ
イオキシン類濃度を測定し、結果を表１に示した。Comparative Example 1 The same operation as in Example 1 was carried out except that no chemicals were added, the chlorophenol concentration and dioxins concentration were measured in the same manner, and the results are shown in Table 1.
【００４５】比較例２〜４
実施例１において、粉末活性炭及び重曹の添加量を表１
に示す量としたこと以外は同様にして運転を行い、同様
にクロロフェノール濃度とダイオキシン類濃度を測定
し、結果を表１に示した。Comparative Examples 2 to 4 In Example 1, the addition amounts of powdered activated carbon and baking soda are shown in Table 1.
The operation was performed in the same manner except that the amounts shown in Table 1 were used, and the chlorophenol concentration and dioxins concentration were measured in the same manner, and the results are shown in Table 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】表１より明らかなように、粉末活性炭１０
０ｍｇ／Ｎｍ３及び重曹８００ｍｇ／Ｎｍ３を添加した
実施例１では、薬剤無添加の比較例１に比べて、ダイオ
キシン類濃度を約１／２に低減することができた。As is clear from Table 1, the powdered activated carbon 10
In Example 1 was added to 0 mg / Nm 3 and sodium bicarbonate 800 mg / Nm 3, as compared with Comparative Example 1 of no drug addition, it was possible to reduce the dioxin concentration to about 1/2.
【００４８】これに対して、粉末活性炭の混合比を１／
３として合計３００ｍｇ／Ｎｍ３添加した比較例２で
は、ダイオキシン類濃度は６．５ｎｇ−ＴＥＱ／Ｎｍ３
と薬剤無添加の場合よりも多くなった。また、粉末活性
炭の添加量を４００ｍｇ／Ｎｍ ３又は３０ｍｇ／Ｎｍ３
とした比較例３，４でも十分なダイオキシン類濃度の低
減効果は得られなかった。これは、粉末活性炭の添加量
が少な過ぎると既に存在するダイオキシン類の吸着除去
を十分に行えず、逆に活性炭がダイオキシン類前躯体か
らダイオキシン類を生成する触媒として働くため多過ぎ
るとダイオキシン類の生成を助長するためと考えられ
る。On the other hand, the mixing ratio of powdered activated carbon is 1 /
3 as a total of 300 mg / NmThreeIn Comparative Example 2 added
Has a dioxin concentration of 6.5 ng-TEQ / NmThree
And it was more than when no drug was added. Also powder activity
The amount of charcoal added is 400 mg / Nm ThreeOr 30 mg / NmThree
Even in Comparative Examples 3 and 4, the concentration of dioxins is sufficiently low.
No reduction effect was obtained. This is the amount of powdered activated carbon added
If too little is present, adsorption removal of existing dioxins
On the contrary, if the activated carbon is a precursor of dioxins
Too much to act as a catalyst to generate dioxins
Is thought to promote the formation of dioxins.
It
【００４９】比較例５
都市ごみ焼却炉において、粉末活性炭の添加量を１００
ｍｇ／Ｎｍ３、重曹の添加量を４００ｍｇ／Ｎｍ３と
し、合計５００ｍｇ／Ｎｍ３の一定量注入で、図２に示
すタイムスケジュールで１日の炉の起動運転、定常運転
及び停止運転を行い、このときの電気集塵機出口の排ガ
ス中のトリクロロフェノール濃度の変化及び電気集塵機
の温度の変化を図２に示した。COMPARATIVE EXAMPLE 5 In the municipal waste incinerator, the amount of powdered activated carbon added was 100.
mg / Nm 3 , the addition amount of baking soda was 400 mg / Nm 3, and a fixed amount of 500 mg / Nm 3 was injected in a fixed amount, the start-up operation, the steady operation, and the shutdown operation of the furnace for one day were performed according to the time schedule shown in FIG. The change in the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator and the change in the temperature of the electrostatic precipitator at this time are shown in FIG.
【００５０】また、定常運転時の電気集塵機出口の排ガ
ス中のダイオキシン類濃度を調べ、結果を表２に示し
た。電気集塵機入口の排ガスのクロロフェノール濃度は
４８５０μｇ／Ｎｍ３であった。また、定常運転時の電
気集塵機出口の排ガス中のトリクロロフェノール濃度
（平均値）を調べ、結果を図４に示した。Further, the concentration of dioxins in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in Table 2. The concentration of chlorophenol in the exhaust gas at the entrance of the electrostatic precipitator was 4850 μg / Nm 3 . Moreover, the trichlorophenol concentration (average value) in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５１】実施例２
比較例５において、起動運転時及び停止運転時の薬剤注
入量を粉末活性炭２００ｍｇ／Ｎｍ３、重曹８００ｍｇ
／Ｎｍ３の合計１０００ｍｇ／Ｎｍ３としたこと以外は
同様にして図３に示すタイムスケジュールで運転を行
い、電気集塵機出口の排ガスのトリクロロフェノール濃
度の変化を調べ、結果を図３に示した。Example 2 In Comparative Example 5, the amount of the chemicals injected during the start-up operation and the stop operation was 200 mg of powdered activated carbon / Nm 3 and 800 mg of baking soda.
/ Nm 3 except that the total was 1000 mg / Nm 3 , the same operation was performed according to the time schedule shown in FIG. 3, and the change in the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator was examined, and the results are shown in FIG.
【００５２】また、定常運転時の電気集塵機出口の排ガ
スのダイオキシン類濃度を調べ、結果を表２に示した。
また、定常運転時の電気集塵機出口の排ガス中のトリク
ロロフェノール濃度（平均値）を調べ、結果を図４に示
した。The concentration of dioxins in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in Table 2.
Moreover, the trichlorophenol concentration (average value) in the exhaust gas at the outlet of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５３】[0053]
【表２】 [Table 2]
【００５４】図２，３及び表２より、薬剤の一定量注入
では、起動運転時及び停止運転時に定常運転時よりもト
リクロロフェノール濃度が増加し、定常運転時のダイオ
キシン類濃度も増加するが、起動運転時及び停止運転時
の薬剤注入量を、定常運転時の薬剤注入量よりも増加さ
せることにより、起動運転時及び停止運転時の排ガス中
のトリクロロフェノール濃度を低減することができ、こ
の結果、定常運転時のダイオキシン類発生量を低減する
ことができることがわかる。From FIGS. 2 and 3 and Table 2, in the constant amount injection of the drug, the trichlorophenol concentration during the start-up operation and the stop operation increased more than that during the steady operation, and the dioxin concentration during the steady operation also increased. By increasing the drug injection amount during start-up operation and stop operation over the drug injection amount during steady-state operation, it is possible to reduce the trichlorophenol concentration in the exhaust gas during start-up operation and stop operation. It is understood that the amount of dioxins generated during steady operation can be reduced.
【００５５】比較例６
実施例２において、起動運転時及び停止運転時に薬剤の
注入を行わなかったこと以外は同様にして運転を行い、
定常運転時の電気集塵機出口のトリクロロフェノール濃
度（平均値）を調べ、結果を図４に示した。Comparative Example 6 The same operation as in Example 2 was carried out except that no drug was injected during the start-up operation and the stop operation,
The trichlorophenol concentration (average value) at the exit of the electrostatic precipitator during steady operation was examined, and the results are shown in FIG.
【００５６】図４より、前日の停止運転時及び当日の起
動運転時の薬剤添加量と当日の定常運転時のトリクロロ
フェノール濃度とには相関があることがわかる。It can be seen from FIG. 4 that there is a correlation between the amount of chemicals added during the stop operation on the previous day and during the start operation on the day and the trichlorophenol concentration during the steady operation on the day.
【００５７】なお、この都市ごみ焼却炉において、電気
集塵機出口の排ガス中のトリクロロフェノール濃度とダ
イオキシン類発生量との関係を調べたところ、図５に示
す如く、両者に相関関係があることが認められた。In this municipal solid waste incinerator, the relationship between the concentration of trichlorophenol in the exhaust gas at the outlet of the electrostatic precipitator and the amount of dioxins generated was examined. As shown in FIG. 5, there was a correlation between the two. Was given.
【００５８】実施例３
図５より、電気集塵機出口排ガスのダイオキシン類濃度
を１ｎｇ−ＴＥＱ／Ｎｍ３以下とするためには、電気集
塵機出口のトリクロロフェノールは約７μｇ／Ｎｍ３以
下とすれば良いことがわかる。一方で、図４より、定常
運転時５００ｍｇ／Ｎｍ３の薬剤注入量としている場
合、定常運転時の電気集塵機出口のトリクロロフェノー
ル濃度を７μｇ／Ｎｍ３以下とするためには、停止運転
時及び起動運転時の薬剤注入量を７５０ｍｇ／Ｎｍ３以
上とすれば良いことがわかる。Example 3 From FIG. 5, in order to reduce the concentration of dioxins in the exhaust gas from the outlet of the electrostatic precipitator to 1 ng-TEQ / Nm 3 or less, the amount of trichlorophenol at the outlet of the electrostatic precipitator should be about 7 μg / Nm 3 or less. I understand. On the other hand, from FIG. 4, when the chemical injection amount is 500 mg / Nm 3 at the time of steady operation, in order to keep the concentration of trichlorophenol at the outlet of the electrostatic precipitator at 7 μg / Nm 3 or less at the time of steady operation, at the time of stop operation and start-up. It is understood that the drug injection amount during operation should be 750 mg / Nm 3 or more.
【００５９】そこで、実施例２において、停止運転時及
び起動運転時の薬剤添加量を７５０ｍｇ／Ｎｍ３とした
こと以外は同様にして運転を行ったところ、ダイオキシ
ン発生量を１ｎｇ−ＴＥＱ／Ｎｍ３以下に抑えることが
できることが確認された。Therefore, in Example 2, when the operation was performed in the same manner except that the chemical addition amount during the stop operation and the start operation was 750 mg / Nm 3 , the dioxin generation amount was 1 ng-TEQ / Nm 3. It was confirmed that it can be suppressed to the following.
【００６０】[0060]
【発明の効果】以上詳述した通り、本発明のダイオキシ
ン類の放出防止方法によれば、廃棄物焼却炉等の焼却
炉、特に、准連続炉や機械バッチ炉のように、１日のう
ちに炉の起動（立ち上げ）と停止（立ち下げ）とを行
う、ダイオキシン類前駆体発生量の多い炉施設におい
て、ダイオキシン類の放出を安定かつ確実に防止するこ
とができる。As described in detail above, according to the method for preventing the release of dioxins of the present invention, an incinerator such as a waste incinerator, particularly a quasi-continuous furnace or a mechanical batch furnace, can be used within one day. It is possible to reliably and reliably prevent the release of dioxins in a reactor facility in which a large amount of dioxin precursor is generated, in which the furnace is started (started up) and stopped (stopped).
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例１において処理した都市ごみ焼却炉の構
成を示す系統図である。FIG. 1 is a system diagram showing a configuration of an municipal solid waste incinerator treated in Example 1.
【図２】比較例５における都市ごみ焼却炉の電気集塵機
の温度と排ガス中のトリクロロフェノール濃度の経時変
化を示すグラフである。FIG. 2 is a graph showing the changes over time in the temperature of the electric dust collector of the municipal solid waste incinerator and the concentration of trichlorophenol in the exhaust gas in Comparative Example 5.
【図３】実施例２における排ガス中のトリクロロフェノ
ール濃度の経時変化と薬剤添加量を示すグラフである。FIG. 3 is a graph showing changes over time in the concentration of trichlorophenol in exhaust gas and the amount of chemicals added in Example 2.
【図４】実施例２及び比較例５，６における、前日の停
止運転時と当日の起動運転時の薬剤添加量と、定常運転
時の排ガス中のトリクロロフェノール濃度との関係を示
すグラフである。FIG. 4 is a graph showing the relationship between the amount of chemicals added during the stop operation on the previous day and the start operation on the same day and the trichlorophenol concentration in the exhaust gas during the steady operation in Example 2 and Comparative Examples 5 and 6. .
【図５】都市ごみ焼却炉の排ガス中のトリクロロフェノ
ール濃度とダイオキシン類濃度との関係を示すグラフで
ある。FIG. 5 is a graph showing the relationship between the concentration of trichlorophenol and the concentration of dioxins in the exhaust gas of the municipal solid waste incinerator.
【符号の説明】 １ ストーカ炉 ２ ガス冷却室 ３ 空気予熱器 ４ 電気集塵機 ５ 誘引送風機 ６ 煙突[Explanation of symbols] 1 stoker furnace 2 gas cooling room 3 Air preheater 4 Electric dust collector 5 induction blower 6 chimney
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ２３Ｊ 15/00 Ｂ０１Ｄ 53/34 ＺＡＢ // Ｃ０７Ｄ 319/24 Ｆ２３Ｊ 15/00 Ｊ (72)発明者 宮田 博司 東京都新宿区西新宿三丁目４番７号 栗田 工業株式会社内 Ｆターム(参考） 3K065 AA24 AB01 AC01 BA01 HA01 3K070 DA05 DA38 DA83 4D002 AA19 AA21 AC04 BA03 BA04 CA01 CA11 DA02 DA16 DA41 GA01 GA03 GB02 GB06 GB08 4H006 AA05 AC26 FC52 FE13 FE73 FE75 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) F23J 15/00 B01D 53/34 ZAB // C07D 319/24 F23J 15/00 J (72) Inventor Hiroshi Miyata 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurata Industry Co., Ltd. F-term (reference) 3K065 AA24 AB01 AC01 BA01 HA01 3K070 DA05 DA38 DA83 4D002 AA19 AA21 AC04 BA03 BA04 CA01 CA11 DA02 DA16 DA41 GA01 GA03 GB02 GB06 GB08 4H006 AA05 AC26 FC52 FE13 FE73 FE75
Claims (4)
排ガスに対して、粉末活性炭を５０〜３００ｍｇ／Ｎｍ
３、重曹を６００ｍｇ〜３０００ｍｇ／Ｎｍ ３となるよ
うに添加することを特徴とするダイオキシン類の放出防
止方法。1. An incinerator that starts and stops within a short period of time
50-300 mg / Nm of powdered activated carbon with respect to exhaust gas
Three, Baking soda 600mg-3000mg / Nm ThreeWill be
Release of dioxins characterized by adding
How to stop.
〜３０μｇ／Ｎｍ３となるような焼却炉の排ガスに対し
て、粉末活性炭を５０〜３００ｍｇ／Ｎｍ３、重曹を６
００ｍｇ〜３０００ｍｇ／Ｎｍ３となるように添加する
ことを特徴とするダイオキシン類の放出防止方法。2. The concentration of chlorophenols in the exhaust gas is 3
50 to 300 mg / Nm 3 of powdered activated carbon and 6 parts of baking soda against the exhaust gas of the incinerator such that the amount becomes to 30 μg / Nm 3 .
A method for preventing the release of dioxins, which is characterized in that it is added in an amount of 00 mg to 3000 mg / Nm 3 .
添加してダイオキシン類の放出を防止する方法におい
て、 該炉の起動運転時及び停止運転時に、定常運転時よりも
多量にダイオキシン類低減薬剤を添加することを特徴と
するダイオキシン類の放出防止方法。3. A method for preventing the release of dioxins by adding a dioxins reducing agent to the exhaust gas of a furnace, comprising a greater amount of the dioxins reducing agent during start-up and shutdown of the furnace than during steady operation. A method for preventing the release of dioxins, which is characterized by being added.
起動運転の直前の停止運転時のダイオキシン類低減薬剤
の添加量と、該起動運転後の定常運転時のダイオキシン
類前駆体の発生量との関係を求め、この関係に基いて起
動運転時及び停止運転時のダイオキシン類低減薬剤添加
量を決定することを特徴とするダイオキシン類の放出防
止方法。4. The amount of dioxin-reducing agent added during the start-up operation and during stop operation immediately before the start-up operation, and the amount of dioxin precursors generated during steady-state operation after the start-up operation according to claim 3. The method for preventing the release of dioxins according to claim 1, wherein the amount of dioxin-reducing agent added during start-up operation and stop operation is determined based on this relationship.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002017173A JP3449371B2 (en) | 2002-01-25 | 2002-01-25 | Prevention method of dioxins release |
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| Publication Number | Publication Date |
|---|---|
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| JP3449371B2 JP3449371B2 (en) | 2003-09-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH119960A (en) * | 1997-06-24 | 1999-01-19 | Kurita Water Ind Ltd | Material for preventing emission of dioxin |
| JPH11101424A (en) * | 1997-09-30 | 1999-04-13 | Plantec:Kk | Non-continuous combustion waste incineration facility and method of reducing dioxin in same |
| JPH11128679A (en) * | 1997-10-31 | 1999-05-18 | Plantec:Kk | Device for reducing dioxines of discontinuous combustion refuse incineration plant and reducing method therefor |
| JP2000354735A (en) * | 1999-06-15 | 2000-12-26 | Kurita Water Ind Ltd | Agent and method for controlling dioxin generation |
| JP2001232151A (en) * | 2000-02-24 | 2001-08-28 | Kurita Water Ind Ltd | Dioxin treating method in wet smoke gas cleaning tower |
-
2002
- 2002-01-25 JP JP2002017173A patent/JP3449371B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH119960A (en) * | 1997-06-24 | 1999-01-19 | Kurita Water Ind Ltd | Material for preventing emission of dioxin |
| JPH11101424A (en) * | 1997-09-30 | 1999-04-13 | Plantec:Kk | Non-continuous combustion waste incineration facility and method of reducing dioxin in same |
| JPH11128679A (en) * | 1997-10-31 | 1999-05-18 | Plantec:Kk | Device for reducing dioxines of discontinuous combustion refuse incineration plant and reducing method therefor |
| JP2000354735A (en) * | 1999-06-15 | 2000-12-26 | Kurita Water Ind Ltd | Agent and method for controlling dioxin generation |
| JP2001232151A (en) * | 2000-02-24 | 2001-08-28 | Kurita Water Ind Ltd | Dioxin treating method in wet smoke gas cleaning tower |
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