JP2010279930A - Exhaust gas treatment method - Google Patents
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本発明はゴミ焼却場等において一般廃棄物、産業廃棄物等の廃棄物を焼却した際や、火力発電所において石炭を燃焼させた際等に生じる排煙中等に含まれる有害な酸性ガス類や、重金属類を同時に確実かつ安全に効率良く処理することのできる排煙処理方法に関する。 The present invention relates to harmful acid gases contained in flue gas generated when incineration of wastes such as general waste and industrial waste in a garbage incineration plant, or when coal is burned in a thermal power plant. The present invention also relates to a method for treating flue gas capable of treating heavy metals at the same time reliably, safely and efficiently.
近年のゴミの多様化に伴い、一般廃棄物、産業廃棄物中には多種多様のプラスチック類、金属類、生ゴミ類が含まれており、また化石燃料である石炭中にも種々の重金属が含まれている。このため、廃棄物を焼却したり石炭を燃焼した際に発生する排煙中には煤塵とともに、塩化水素ガス等の酸性ガス類やダイオキシン類が含まれている虞がある。また沸点の低い水銀、鉛、カドミウム、銅、クロム、亜鉛、セレン、ホウ素、ヒ素等の有害な重金属類はガス化して排煙中に含有され、排煙温度が低下する集塵工程で固化して煤塵中に移行して排煙から分離される。このため、酸性ガスやダイオキシン類が含まれている排煙や、重金属類が含有されている煤塵をそのまま廃棄すると、重大な公害問題を生じる虞がある。 With the recent diversification of garbage, general and industrial waste contains a wide variety of plastics, metals, and garbage, and various heavy metals are also present in fossil fuel coal. include. For this reason, there is a possibility that the exhaust gas generated when incinerating waste or burning coal contains acid gases such as hydrogen chloride gas and dioxins along with soot and dust. In addition, harmful heavy metals such as mercury, lead, cadmium, copper, chromium, zinc, selenium, boron and arsenic, which have a low boiling point, are gasified and contained in the flue gas, and solidify in the dust collection process where the flue gas temperature decreases. It moves into the dust and is separated from the flue gas. For this reason, if the flue gas containing acid gas or dioxins or the soot containing heavy metals is discarded as it is, there is a risk of causing serious pollution problems.
従来より、排煙中の塩化水素ガスに対しては、排煙に水酸化カルシウム、酸化カルシウム、炭酸カルシウム等のアルカリ化合物を添加して中和除去する方法が採用されている。一方、重金属類に対しては、排煙から分離した煤塵に重金属固定化剤を添加し、重金属類の煤塵中からの溶出を防止する処理が行われている。従来、重金属固定化剤としては、鉛やカドミウム等の重金属に対する固定化能の高いジチオカルバミン酸系重金属固定化剤が広く用いられているが、ジチオカルバミン酸系重金属固定化剤は、単独ではヒ素、クロム（ＶＩ）、セレン、ホウ素等に対する固定化能に乏しいという問題があり、しかも処理後の煤塵が酸性下に晒されると固定化した水銀等の重金属類が煤塵中から溶出する虞があった。また排煙中に塩化水素ガスが含まれている場合、ジチオカルバミン酸系重金属捕集剤は、これらのガスを処理できないばかりか、酸性物質が存在すると高温の排煙中で分解して多量の有害ガス（二硫化炭素、硫化水素）が発生し、極めて危険であるなど安全性に大きな問題があり、排煙中の有害ガスと重金属類とを同時に処理するために用いるには問題があった。 Conventionally, a method of neutralizing and removing hydrogen chloride gas in flue gas by adding an alkali compound such as calcium hydroxide, calcium oxide, calcium carbonate to the flue gas has been adopted. On the other hand, for heavy metals, a heavy metal fixing agent is added to the dust separated from the flue gas to prevent the heavy metals from being eluted from the dust. Conventionally, as a heavy metal immobilizing agent, a dithiocarbamic acid heavy metal immobilizing agent having a high immobilizing ability for heavy metals such as lead and cadmium has been widely used, but dithiocarbamic acid heavy metal immobilizing agents are arsenic, chromium alone. There is a problem that (VI), the ability to fix selenium, boron and the like is poor, and when the treated dust is exposed to acid, there is a possibility that the immobilized heavy metals such as mercury may be eluted from the dust. In addition, if the flue gas contains hydrogen chloride gas, the dithiocarbamate heavy metal scavenger not only can not treat these gases, but also decomposes in the high temperature flue gas in the presence of acidic substances, causing a large amount of harmful substances. Gases (carbon disulfide, hydrogen sulfide) are generated and there are serious safety problems such as being extremely dangerous, and there is a problem in using harmful gases in heavy smoke and heavy metals at the same time.
排煙中の塩化水素等の酸性ガスに対しては、消石灰を添加して中和する方法が採用されているが、この方法は重金属類に対しては有効ではないため、消石灰と、セメント類、硫酸塩、水酸化アルミニウム、塩化鉄、キレート剤、水ガラス、リン酸塩等の有害金属安定化剤とを排ガス誘導管内に噴霧して排ガスを処理し、排ガス中の酸性ガスと、重金属特に鉛の溶出を防止する方法（特許文献１）、消石灰と、多孔質二酸化ケイ素等の粉体状の多孔質吸着剤を主成分とする排ガス処理剤を排ガス処理工程で吹き込んで、排ガス中の塩化水素等の酸性ガスを中和するとともに、重金属類を安定化する方法（特許文献２）等が提案されている。 For acid gases such as hydrogen chloride in flue gas, a method of neutralizing by adding slaked lime is adopted, but this method is not effective for heavy metals, so slaked lime and cement The exhaust gas is treated by spraying harmful metal stabilizers such as sulfate, aluminum hydroxide, iron chloride, chelating agent, water glass and phosphate into the exhaust gas induction pipe. Method for preventing lead elution (Patent Document 1), exhaust gas treatment agent mainly composed of powdered porous adsorbent such as slaked lime and porous silicon dioxide is blown in the exhaust gas treatment step, and chlorination in exhaust gas A method of neutralizing acidic gases such as hydrogen and stabilizing heavy metals (Patent Document 2) has been proposed.
しかしながら特許文献１記載の方法は、重金属類の中でも鉛の溶出防止効果には優れているが、他の重金属類に対する安定化効果は十分とは言い難い。特に排煙中に含まれるカドミウム、水銀、セレン、クロム（ＶＩ）、砒素、アンチモン等の重金属類はオキソ陰イオンやその塩となっていることがあるが、引用文献１記載の方法はオキソ陰イオンやその塩に対する安定化効果は不十分であった。また引用文献２記載の方法は、高価な多孔質吸着剤を使用するため処理剤コストが高くつくとともに、排煙中の酸性ガス、重金属成分の処理効果も十分とは言い難く、特にオキソ陰イオンやその塩に対する固定化能は不十分であった。また、消石灰と塩化水素ガスとの反応は固体−気体反応であるため反応効率が悪く、排煙中の塩化水素ガスを所定の排出基準値以下まで処理するためには、必要量以上に過剰の消石灰を添加している。このため、排煙から煤塵中に移行した金属は通常、殆どが水不溶性の水酸化物となっており、これらは比較的容易に安全な処理が可能である。しかしながら、排煙中の塩化水素ガス濃度は常に一定ではないため、酸性ガス量に対して消石灰量が過剰となることがあり、その結果、金属捕集剤の添加量が不十分となると煤塵中の金属水酸化物が溶出し易くなる。このような問題を解決するには、予め多量の金属捕集剤等を添加すれば良いが、必要量以上に多量の金属捕集剤を使用することとなり、無駄なコストがかかるという問題がある。煤塵中の金属を確実に固定化するに必要な金属捕集剤を添加するためには、１３号溶出試験を行って煤塵から溶出液中に溶出した金属濃度を原子吸光法等によって測定し、溶出した金属濃度に応じて金属捕集剤添加量を増減させる方法が考えられるが、溶出試験により煤塵からの溶出金属濃度を求めるには長時間が必要となり、刻々変化する酸性ガス濃度、金属濃度に応じた必要最小限度の消石灰、金属捕集剤を添加して効率良く確実に排煙を処理することは困難であった。 However, although the method described in Patent Document 1 is excellent in the effect of preventing lead elution among heavy metals, it is difficult to say that the stabilizing effect on other heavy metals is sufficient. In particular, heavy metals such as cadmium, mercury, selenium, chromium (VI), arsenic, and antimony contained in the flue gas may be oxo anions or salts thereof. The stabilizing effect on ions and their salts was insufficient. Further, the method described in the cited reference 2 uses an expensive porous adsorbent, so that the cost of the treatment agent is high, and it is difficult to say that the treatment effect of the acidic gas and heavy metal component in the flue gas is sufficient. And its immobilization ability for salts was insufficient. Moreover, since the reaction between slaked lime and hydrogen chloride gas is a solid-gas reaction, the reaction efficiency is poor, and in order to treat the hydrogen chloride gas in the flue gas to a predetermined emission standard value or less, an excessive amount more than necessary is required. Slaked lime is added. For this reason, most of the metals that have migrated from the flue gas into the dust are usually water-insoluble hydroxides, which can be treated with relative ease and safety. However, since the concentration of hydrogen chloride gas in the flue gas is not always constant, the amount of slaked lime may be excessive with respect to the amount of acid gas. As a result, if the amount of metal scavenger added is insufficient, It becomes easy to elute the metal hydroxide. In order to solve such a problem, it is sufficient to add a large amount of a metal scavenger or the like in advance, but there is a problem that a large amount of the metal scavenger is used more than necessary, resulting in unnecessary costs. . In order to add a metal scavenger necessary for securely immobilizing the metal in the dust, the concentration of metal eluted from the dust in the eluate is measured by an atomic absorption method or the like by performing No. 13 dissolution test. A method to increase or decrease the amount of metal scavenger added according to the dissolved metal concentration can be considered, but it takes a long time to determine the dissolved metal concentration from soot dust by the dissolution test, and the acid gas concentration and metal concentration that change every moment are required. It was difficult to efficiently and surely treat the flue gas by adding the necessary minimum amount of slaked lime and metal scavenger.
本発明は上記従来技術の課題に鑑みなされたもので、排煙中に含まれる塩化水素ガス等の酸性ガス類や重金属類を効率よく確実に無害化して排煙を安全に処理することができる排煙処理方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and can efficiently and reliably detoxify acidic gases such as hydrogen chloride gas and heavy metals contained in the flue gas, and safely treat the flue gas. An object is to provide a method for treating flue gas.
即ち本発明は、
（１）焼却施設において排出される排煙を２００℃以下に冷却した後、集塵機出口の塩化水素ガス濃度及び集塵機から分離した煤塵の溶出試験における溶出液のｐＨを所定時間毎に測定しながら、塩化水素ガス濃度が１００ｐｐｍ以下となる量の消石灰及び、溶出試験における溶出液のｐＨが１０．５〜１２．０となる量の、硫酸アルミニウム及び／又は硫酸第一鉄を主成分として含む煤塵処理剤を煙道内に導入して排煙と接触させることを特徴とする排煙処理方法、
（２）排煙から分離した煤塵に、水とともに重金属固定化剤を添加して混練する上記（１）の排煙処理方法、
（３）重金属固定化剤がジチオカルバミン酸型重金属固定化剤である上記（２）の排煙処理方法、
を要旨とするものである。
That is, the present invention
(1) After cooling the flue gas discharged at the incineration facility to 200 ° C. or lower, while measuring the hydrogen chloride gas concentration at the outlet of the dust collector and the pH of the eluate in the elution test of the dust separated from the dust collector, Dust treatment containing slaked lime with a hydrogen chloride gas concentration of 100 ppm or less and aluminum sulfate and / or ferrous sulfate in the amount of pH 10.5 to 12.0 in the elution test as a main component A smoke treatment method characterized by introducing an agent into the flue and bringing it into contact with the smoke,
(2) The smoke treatment method according to (1), wherein a heavy metal fixing agent is added together with water to the dust separated from the smoke, and kneaded.
(3) The flue gas treatment method according to (2), wherein the heavy metal immobilizing agent is a dithiocarbamic acid type heavy metal immobilizing agent,
Is a summary.
本発明の排煙処理方法は、酸性ガスとしての塩化水素ガス濃度を集塵機出口において測定し、当該塩素ガス濃度が１００ｐｐｍ以下となる量の消石灰を添加するようにしたため、排煙中の塩素ガス等の酸性ガスを効果的に除去できる。また集塵機で分離された煤塵の溶出試験における溶出液のｐＨを測定し、硫酸アルミニウム及び／又は硫酸鉄を主成分として含む煤塵処理剤をｐＨが１０．５〜１２．０となる量添加して、排煙を処理する方法を採用したため、排煙から分離した煤塵中の消石灰含有量が多い場合であっても、重金属類を確実に処理するに必要な量の煤塵処理剤を添加することができ、必要以上に過剰な処理剤の添加を抑えることができる。しかも、従来の金属捕集剤では固定化が困難であった鉛、カドミウム、水銀、セレン、クロム（ＶＩ）、砒素、ホウ素、アンチモン等がオキソ陰イオンやその塩の形態で含まれていても、これらを確実に不溶化処理することができる。また煤塵の溶出試験における溶出液のｐＨを測定して煤塵処理剤の添加量を増減するようにしたため、原子吸光法等によって煤塵からの溶出金属濃度を測定する方法に比べ、金属濃度等が変化した場合でも迅速に対応でき、最適量の煤塵処理剤を添加することができるため、効率良く確実かつ安全に排煙の処理を行うことができる。また、排煙から分離した煤塵に水とともにジチオカルバミン酸型重金属固定化剤を添加して処理すると、煤塵中の重金属類をより効果的に固定化できるとともに、排煙から分離した煤塵中の酸性物質は消石灰によって中和されているため、ジチオカルバミン酸型重金属固定化剤が分解されて有害ガスが発生する虞もなく、効果的に重金属類を処理できる。 In the flue gas treatment method of the present invention, the concentration of hydrogen chloride gas as an acid gas is measured at the dust collector outlet, and slaked lime is added in such an amount that the chlorine gas concentration becomes 100 ppm or less. The acidic gas can be effectively removed. Further, the pH of the eluate in the elution test of the soot separated by the dust collector is measured, and the soot treating agent containing aluminum sulfate and / or iron sulfate as a main component is added in an amount so that the pH becomes 10.5 to 12.0. Because the method of treating flue gas is adopted, even if the slaked lime content in the dust separated from the flue gas is high, it is possible to add the amount of dust treatment agent necessary to reliably treat heavy metals It is possible to suppress the addition of an excessive amount of processing agent more than necessary. In addition, lead, cadmium, mercury, selenium, chromium (VI), arsenic, boron, antimony, etc., which were difficult to fix with conventional metal scavengers, may be contained in the form of oxoanions or their salts. These can be reliably insolubilized. In addition, since the pH of the eluate in the dust dissolution test was measured to increase or decrease the amount of dust treatment agent added, the metal concentration, etc. changed compared to the method of measuring the concentration of metal eluted from the dust by atomic absorption spectrometry, etc. In this case, it is possible to respond quickly and to add an optimal amount of the dust treatment agent, so that it is possible to efficiently and reliably and safely process the flue gas. In addition, by adding a dithiocarbamic acid type heavy metal immobilizing agent together with water to the dust separated from the flue gas, the heavy metals in the dust can be more effectively fixed, and the acidic substances in the dust separated from the flue gas Since it is neutralized by slaked lime, there is no risk that the dithiocarbamic acid type heavy metal fixing agent is decomposed to generate harmful gas, and heavy metals can be treated effectively.
本発明の排煙処理方法において、消石灰としては、市販の微粉末状の物を用いることができるが、更に多孔質状のものがより好ましい。消石灰は、集塵機出口の塩化水素ガス濃度を測定しながら、当該箇所の塩化水素ガス濃度が１００ｐｐｍ以下となる量を添加する。消石灰による塩化水素ガスの中和反応は、固体−気体反応であり反応効率が悪いため、集塵機出口の塩化水素ガス濃度を１００ｐｐｍ以下とするのに必要な量に対して等量の消石灰を添加したのでは、１００ｐｐｍ以下にすることは困難である。集塵機出口の塩化水素ガス濃度を確実に１００ｐｐｍ以下となるようにするためには、消石灰添加前の塩化水素ガス濃度（初期濃度当量）の２〜４倍等量の消石灰を添加することが好ましく、２．５〜３．０倍等量添加することがより好ましい。集塵機出口の塩化水素ガス濃度はＪＩＳ Ｋ０１０７に準じて連続または３０秒〜５分間隔で測定するが、連続測定することが好ましい。 In the smoke treatment method of the present invention, as the slaked lime, a commercially available fine powder can be used, but a porous one is more preferable. The slaked lime is added in such an amount that the hydrogen chloride gas concentration at the location becomes 100 ppm or less while measuring the hydrogen chloride gas concentration at the outlet of the dust collector. Since the neutralization reaction of hydrogen chloride gas with slaked lime is a solid-gas reaction and the reaction efficiency is poor, an equal amount of slaked lime was added to the amount necessary to make the hydrogen chloride gas concentration at the dust collector outlet 100 ppm or less. Therefore, it is difficult to make it 100 ppm or less. In order to ensure that the hydrogen chloride gas concentration at the dust collector outlet is 100 ppm or less, it is preferable to add slaked lime in an amount equivalent to 2 to 4 times the hydrogen chloride gas concentration (initial concentration equivalent) before slaked lime addition, It is more preferable to add an equivalent amount of 2.5 to 3.0 times. The concentration of hydrogen chloride gas at the outlet of the dust collector is measured continuously or at intervals of 30 seconds to 5 minutes in accordance with JIS K0107.
本発明方法において煤塵処理剤として用いる（ａ）硫酸第一鉄、および（ｂ）硫酸アルミニウムは、無水塩、含水塩のいずれも用いることができ、２種以上の塩を組み合わせて用いることができるが、含水塩がより好ましい。煤塵処理剤が確実に水に溶解しないと煤塵からの溶出液のｐＨを１２．０以下とすることが困難である。このため水に溶けにくい硫酸第一鉄や硫酸アルミニウムの無水物よりも、水溶性の高い含水塩が好ましく、含水量の多いものほど好ましい。また含水塩は自身の融点以上である、１５０〜２００℃の煙道中で一度溶解し、水分が蒸発しその際に自身はより多孔質となり、煙道中の重金属類を良く吸着するとともに、水中で良く溶解し易くなる。そこで（ａ）硫酸第一鉄含水塩粉末として、生産量や価格面から硫酸第一鉄含水塩の１水塩〜７水塩が好ましく、１水塩〜３水塩の粉末がより好ましい。また、（ｂ）硫酸アルミニウムの６水塩〜１８水塩が用いられるが、中でも硫酸アルミニウム８水塩〜１６水塩が好ましい。煤塵処理剤として用いる（ａ）硫酸第一鉄、（ｂ）硫酸アルミニウムはいずれか一方を用いても、両者を併用してもよいが、両者を重量比で（ａ）：（ｂ）＝３０〜８０：２０〜７０の割合となるように添加することが好ましく、特に４０〜７０：３０〜６０の割合となるように添加することが好ましい。 In the method of the present invention, (a) ferrous sulfate and (b) aluminum sulfate used as the dust treatment agent can be used in any of anhydrous salts and hydrated salts, and can be used in combination of two or more kinds of salts. However, a hydrate salt is more preferable. If the dust treatment agent does not dissolve in water reliably, it is difficult to adjust the pH of the eluate from the dust to 12.0 or less. For this reason, hydrated salts with high water solubility are preferred over ferrous sulfate and aluminum sulfate anhydrides, which are less soluble in water, and those with a higher water content are more preferred. In addition, the hydrated salt is once dissolved in the flue at 150 to 200 ° C., which is higher than its melting point, and the water evaporates to become more porous, adsorbing heavy metals in the flue well, and in water It becomes easy to dissolve well. Therefore, as the (a) ferrous sulfate hydrate salt powder, monohydrate to 7 hydrate salt of ferrous sulfate hydrate salt is preferable and monohydrate to trihydrate powder is more preferable from the viewpoint of production and price. Further, (b) aluminum sulfate hexahydrate to 18 hydrate is used, and among them aluminum sulfate octahydrate to 16 hydrate is preferable. Either (a) ferrous sulfate or (b) aluminum sulfate used as a dust treatment agent may be used, or both may be used together, but both are (a) :( b) = 30 by weight ratio. It is preferable to add so that it may become a ratio of -80: 20-70, and it is preferable to add so that it may become a ratio of 40-70: 30-60 especially.
煤塵処理剤は、集塵機から分離した煤塵の溶出試験における溶出液のｐＨが１０．５〜１２．０となるように添加する。上記溶出試験における溶出液のｐＨは、集塵機で分離した煤塵１００重量部当たり、３０重量部の水を加えて混練した後、この混練物５０重量部当たり、５００重量部のイオン交換水（ｐＨ＝６）を加えて１０〜６０分間攪拌した時の溶出液のｐＨである。本発明方法では、集塵機出口の塩化水素ガス濃度が１００ｐｐｍ以下となるようにするために過剰の消石灰を添加しているため、煤塵処理剤を添加しないと上記溶出試験における溶出液のｐＨは通常、１２．０を超えている。このため溶出液のｐＨが１０．５〜１２．０の範囲となるように、排煙が排ガス急冷塔を通過した後で煤塵処理剤を添加すればよい。溶出試験における溶出液のｐＨは１〜６時間毎に１回測定することが好ましい。集塵機で得られる煤塵の溶出液のｐＨを１０．５〜１２．０の範囲に調整するための煤塵処理剤の添加量は次のような予備試験によって決定することができる。即ち、得られた煤塵に所定量の煤塵処理剤を加え良くかき混ぜ、上記の如く煤塵と煤塵処理剤混合物の溶出試験を行い、溶出液のｐＨが１０．５〜１２．０となる煤塵処理剤の量から求めることができる。 The soot treating agent is added so that the pH of the eluate in the elution test of the soot separated from the dust collector is 10.5 to 12.0. The pH of the eluate in the dissolution test was determined by adding 500 parts by weight of ion-exchanged water (pH = 50 parts by weight) after adding 30 parts by weight of water per 100 parts by weight of the dust separated by the dust collector. This is the pH of the eluate when 6) is added and stirred for 10-60 minutes. In the method of the present invention, excessive slaked lime is added so that the hydrogen chloride gas concentration at the dust collector outlet is 100 ppm or less, so that the pH of the eluate in the elution test is usually 12.0 is exceeded. For this reason, the dust treatment agent may be added after the flue gas passes through the exhaust gas quenching tower so that the pH of the eluate is in the range of 10.5 to 12.0. The pH of the eluate in the dissolution test is preferably measured once every 1 to 6 hours. The addition amount of the dust treating agent for adjusting the pH of the dust eluate obtained by the dust collector to the range of 10.5 to 12.0 can be determined by the following preliminary test. That is, a predetermined amount of dust treatment agent is added to the obtained dust and mixed well, and the dissolution test of the dust and the dust treatment agent mixture is performed as described above, so that the pH of the eluate becomes 10.5 to 12.0. It can be calculated from the amount.
本発明において、排煙から分離した煤塵に、水とともに重金属固定化剤を添加し、混練して煤塵を処理しても良い。重金属固定化剤としては、無機系および有機系化合物が知られているが、添加量、重金属に対する処理効果、および使い易さの点から有機系がより好ましい。無機系重金属固定化剤としては、正燐酸や、ポリ燐酸、メタ燐酸、ピロ燐酸、過燐酸、トリポリ燐酸、ヘキサメタ燐酸等の重合燐酸、亜燐酸、次亜燐酸とそれらのアルカリ金属塩、珪酸とそのアルカリ塩類、硫酸第一鉄、硫酸第二鉄、硫酸アルミニウム、塩化第二鉄、ポリ塩化アルミニウム等が挙げられるが、正燐酸とその塩類、珪酸とその塩類、硫酸第一鉄、硫酸アルミニウムが好ましい。また、市販品としてアッシュナイトＲ−１０２、Ｒ−２０２、Ｒ−７０１、Ｒ−７０２；栗田工業株式会社、コウエイキレート３００、４００；ラサ晃栄株式会社、アッシュガードＡＧ−１００、ＡＧ−２００、ＡＧ−３００；株式会社ジコー等が挙げられる。
ジチオカルバミン酸系重金属固定化剤としてはポリアミン類の窒素に少なくとも１個のジチオ酸基やそのアルカリ塩基が官能基として結合した化合物等を用いることができる。ポリアミン類としては、例えばモノエチルアミン、モノプロピルアミン、モノイソプロピルアミン、モノブチルアミン、モノイソブチルアミン、アミルアミン、２−エチルヘキシルアミン、シクロへキシルアミン、ベンジルアミン等のモノアルキルアミン；ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン、ジブチルアミン、ジイソブチルアミン、エチルメチルアミン、メチルプロピルアミン、イソプロピルメチルアミン、ブチルメチルアミン、イソブチルメチルアミン、エチルプロピルアミン、エチルイソプロピルアミン、ブチルエチルアミン、エチルイソブチルアミン、イソプロピルプロピルアミン、ブチルプロピルアミン、ブチルイソブチルアミン、ジアミルアミン、ジ−２−エチルヘキシルアミン等のジアルキルアミン；エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、ジブチレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、トリブチレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン、イミノビスプロピルアミン、モノメチルアミノプロピルアミン、メチルイミノビスプロピルアミン、１，３−プロパンジアミン、１，４−ブタンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、Ｎ，Ｎ´−ジメチルエチレンジアミン、Ｎ，Ｎ′−ジエチルプロピレンジアミン、Ｎ，Ｎ′−ジエチルエチレンジアミン、Ｎ，Ｎ′−ジエチルプロピレンジアミン、モルホリン；ピペラジン；ピロリジン、ポリエチレンイミン、ポリプロピレンイミン、ポリビニルアミン、ポリアリルアミン等が挙げられる。また、本発明において、ジチオカルバミン酸型重金属固定剤としては市販のものを使用することが出来る。市販品として株式会社荏原製作所製のアッシュクリーン（アッシュクリーンＣ−５００、Ｃ−５０５、Ｃ−５０８等）、栗田工業株式会社製のアッシュナイトＳ−８０３、東ソー株式会社製のＴＳ−２７５、ＴＳ−３００、不二サッシ株式会社製のアルサイトＬ−１０５、ミヨシ油脂株式会社製のエポルバ（ＮＥＷエポルバ８００、ＮＥＷエポルバ８００Ａ、ＮＥＷエポルバ８１０等）、エポアッシュＭ−１、日本曹達株式会社製のハイジオン−ＶＧ、ラサ晃栄株式会社製のコウエイキレート（コウエイ１００シリーズ、コウエイ５００シリーズ等）等が挙げられる。
これらの重金属固定化剤はごく一般的なゴミ焼却場のアルカリ性煤塵に対して、無機系の場合：１０〜２０重量％、有機系の場合：３〜５重量％添加することにより煤塵中の重金属の溶出を防止できるが、本発明で得られる煤塵に対して重金属固定化剤の添加量は無機系の場合：１〜５重量％、有機系の場合：０．０５〜０．５重量％で良い。
In the present invention, the heavy metal fixing agent may be added together with water to the dust separated from the flue gas and kneaded to treat the dust. As the heavy metal immobilizing agent, inorganic and organic compounds are known, but an organic type is more preferable from the viewpoint of the amount added, the treatment effect on heavy metals, and ease of use. Examples of inorganic heavy metal fixing agents include orthophosphoric acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, superphosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, and the like, phosphorous acid, hypophosphorous acid and their alkali metal salts, silicic acid, and the like. Alkaline salts, ferrous sulfate, ferric sulfate, aluminum sulfate, ferric chloride, polyaluminum chloride, etc. are listed, but orthophosphoric acid and its salts, silicic acid and its salts, ferrous sulfate and aluminum sulfate preferable. As commercial products, Ashnite R-102, R-202, R-701, R-702; Kurita Kogyo Co., Ltd., Koei Chelate 300, 400; Rasa Soei Co., Ltd., Ashguard AG-100, AG-200, AG-300; Zico Corporation and the like.
As the dithiocarbamic acid heavy metal immobilizing agent, a compound in which at least one dithioacid group or an alkali base thereof is bonded as a functional group to nitrogen of polyamines can be used. Examples of polyamines include monoalkylamines such as monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, amylamine, 2-ethylhexylamine, cyclohexylamine, benzylamine; dimethylamine, diethylamine, dipropyl Amine, diisopropylamine, dibutylamine, diisobutylamine, ethylmethylamine, methylpropylamine, isopropylmethylamine, butylmethylamine, isobutylmethylamine, ethylpropylamine, ethylisopropylamine, butylethylamine, ethylisobutylamine, isopropylpropylamine, Dibutyl propylamine, butylisobutylamine, diamylamine, di-2-ethylhexylamine, etc. Alkylamine; ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, Hexaethyleneheptamine, iminobispropylamine, monomethylaminopropylamine, methyliminobispropylamine, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine, octamethylenediamine, N, N'-dimethylethylenediamine N, N'-diethylpropylenediamine, N, N'-diethylethylenediamine, N, N'-diethylpropylene Diamine, morpholine; piperazine; pyrrolidine, polyethyleneimine, polypropyleneimine, polyvinylamine, polyallylamine and the like. In the present invention, a commercially available dithiocarbamic acid type heavy metal fixing agent can be used. Commercially available Ashclean manufactured by Ebara Corporation (Ashclean C-500, C-505, C-508, etc.), Ashnite S-803 manufactured by Kurita Kogyo Co., Ltd., TS-275 manufactured by Tosoh Corporation, TS -300, Fuji Sash Co., Ltd. Alcite L-105, Miyoshi Oil Co., Ltd. Epolva (NEW Epolva 800, NEW Epolva 800A, NEW Epolva 810, etc.), Epoash M-1, Hydion manufactured by Nippon Soda Co., Ltd. -VG, Kasachei made by Rasa Soei Co., Ltd. (Kaway 100 series, Kaway 500 series, etc.) and the like.
These heavy metal immobilizing agents are added to 10 to 20% by weight in the case of inorganic type and 3 to 5% by weight in the case of organic type with respect to alkaline soot in a general garbage incineration plant, thereby adding heavy metal in the dust. The amount of heavy metal fixing agent added to the dust obtained in the present invention is 1 to 5% by weight in the case of an inorganic system, and 0.05 to 0.5% by weight in the case of an organic system. good.
消石灰及び煤塵処理剤は、排煙を排ガス急冷塔で２００℃以下に冷却した後に添加するが、排煙温度が１５０〜２００℃で添加することがより好ましい。従って、通常は排煙を、排煙急冷反応塔（排ガス急冷塔）を通過させ、排煙温度が２００℃以下としてから、排煙が集塵機を通過する前の工程において、消石灰、煤塵処理剤を煙道に噴霧する等の方法で添加する。排ガス急冷塔を通過した排煙に消石灰と煤塵処理剤を同時に添加するのが一般的であるが、それぞれ別々に添加しても効果は変わらない。 The slaked lime and the dust treatment agent are added after the flue gas is cooled to 200 ° C. or lower in the exhaust gas quenching tower, and it is more preferable that the flue gas temperature is 150 to 200 ° C. Therefore, in general, the flue gas is passed through the flue gas quenching reaction tower (exhaust gas quenching tower) and the flue gas temperature is set to 200 ° C. or lower, and before the flue gas passes through the dust collector, the slaked lime and the dust treatment agent are used. Add by spraying into the flue. It is common to add slaked lime and dust treatment agent to the flue gas that has passed through the exhaust gas quenching tower at the same time, but the effect will not change even if each is added separately.
本発明の排煙処理方法は、都市ゴミ焼却場、産業廃棄物焼却場、石炭を燃料とする火力発電所等で発生する排煙等、酸性ガス、ダイオキシン類、重金属類を含む排煙の処理に好適である。本発明方法は、また、鉛、カドミウム、水銀、銅、亜鉛、クロム,マンガン、鉄などの陽イオンとして溶出する重金属類の他に、セレン、クロム（ＶＩ）、砒素、アンチモン、ホウ素等のオキソ陰イオンとして溶出する重金属類も処理する事が可能である。 The method for treating flue gas of the present invention is a method for treating flue gas containing acid gas, dioxins, heavy metals, etc. generated in municipal waste incinerators, industrial waste incinerators, coal-fired thermal power plants, etc. It is suitable for. In addition to heavy metals eluting as cations such as lead, cadmium, mercury, copper, zinc, chromium, manganese, iron, etc., the method of the present invention can also be used for oxo such as selenium, chromium (VI), arsenic, antimony, boron, etc. It is also possible to treat heavy metals that elute as anions.
以下、実施例を挙げて本発明を更に詳細に説明する。
実施例１〜６、比較例１〜２
都市ゴミ焼却場焼却炉設備の排ガス急冷塔通過後における、消石灰無添加時の排ガス運転条件は、ＨＣｌガス濃度７００〜７５０ｐｐｍ（Ｏ２：１２％換算）、排煙量：１０００ｍ３Ｎ−ｗｅｔ／ｈｒ、煤塵濃度４ｇ／ｍ３Ｎ−ｄｒｙである。排ガス急冷塔を通過した後の煙道内において（排煙温度１８０℃）、表１に示す添加量の消石灰単独、及び消石灰と煤塵処理剤を煙道内に添加して、塩化水素ガス濃度はＪＩＳ Ｋ０１０７に準じて１分毎に測定した。薬剤を添加してから２時間後までのｐＨの値を表２に示す。また、薬剤を添加して２時間後、バグフィルターで集塵された煤塵をサンプリングし、煤塵１００重量部に対し３０重量部の水を加え混練した。混練処理した煤塵５０重量部をイオン交換水（ｐＨ＝６）５００重量部に加え、３０分間攪拌して溶出試験を行い１μｍのグラスファイバーろ紙でろ過し、ろ液（溶出液）のｐＨを測定した。また、前記と同様の２時間後サンプリングした煤塵を同様に混練処理して得られたサンプルを環境庁告示１３号法により溶出試験を行い重金属濃度とｐＨを測定した結果を表２に示す。なお、比較例１および実施例１〜５で使用した消石灰はＪＩＳ特号（１５ｍ２／ｇ)である。また、比較例２及び実施例６で使用した多機能消石灰は奥多摩工業株式会社製、タマカルクースポンジアカル（ＴＫ−ＳＰ）(比表面積：４５ｍ２／ｇ)である。
Hereinafter, the present invention will be described in more detail with reference to examples.
Examples 1-6, Comparative Examples 1-2
After city gas quenching tower passage of waste incineration incinerator equipment, exhaust gas operating conditions at the time of slaked lime no added, HCl gas concentration 700~750ppm (O 2: 12% conversion), Haikemuriryou: 1000m 3 N-wet / hr, the dust concentration is 4 g / m 3 N-dry. In the flue after passing through the exhaust gas quenching tower (exhaust temperature 180 ° C.), the addition amount of slaked lime as shown in Table 1 and slaked lime and dust treatment agent are added into the flue, and the hydrogen chloride gas concentration is JIS K0107. The measurement was performed every minute according to the above. Table 2 shows the pH values up to 2 hours after the addition of the drug. Further, 2 hours after adding the chemical, the dust collected by the bag filter was sampled, and 30 parts by weight of water was added to 100 parts by weight of the dust and kneaded. Add 50 parts by weight of the kneaded dust to 500 parts by weight of ion-exchanged water (pH = 6), stir for 30 minutes, conduct an elution test, filter through 1 μm glass fiber filter, and measure the pH of the filtrate (eluate). did. Table 2 shows the results of measuring the heavy metal concentration and pH by conducting a dissolution test on the sample obtained by similarly kneading the soot dust sampled after 2 hours in the same manner as described above by the Environmental Agency Notification No. 13 method. In addition, the slaked lime used in the comparative example 1 and Examples 1-5 is a JIS special name (15m < 2 > / g). Moreover, the multifunctional slaked lime used in Comparative Example 2 and Example 6 is Tamakaruku Sponge Acal (TK-SP) (specific surface area: 45 m 2 / g) manufactured by Okutama Kogyo Co., Ltd.
実施例７〜１０、比較例３
産業廃棄物焼却場の焼却炉設備の排ガス急冷塔通過後における、消石灰無添加時の排ガス運転条件は、ＨＣｌガス濃度７５０〜８００ｐｐｍ（Ｏ２：１２％換算）、排煙量：５０，０００ｍ３Ｎ−ｗｅｔ／ｈｒ、煤塵濃度２．５ｇ／ｍ３Ｎ−ｄｒｙである。排ガス急冷塔を通過した後の煙道内において（排煙温度１５０℃）、表３に示す添加量の消石灰単独、及び消石灰と煤塵処理剤を塩道内に添加して、塩化水素ガス濃度はＪＩＳ Ｋ０１０７に準じて１分毎に測定した。薬剤を添加してから２時間後までのｐＨの値を表４に示す。また、薬剤を添加して２時間後バグフィルターで集塵された煤塵をサンプリングし、煤塵１００重量部に対し３０重量部の水を加え混練した。混練処理した煤塵５０重量部をイオン交換水（ｐＨ＝６）５００重量部に加え、３０分間攪拌して溶出試験を行い１μｍのグラスファイバーろ紙でろ過してろ液（溶出液）のｐＨを測定した。また、前記と同様の２時間後サンプリングした煤塵を同様に混練処理して得られたサンプルを環境庁告示１３号法により溶出試験を行い重金属濃度とｐＨを測定した結果を表４に示す。なお、比較例３および実施例７〜１０で使用した多機能消石灰は奥多摩工業株式会社製、タマカルクースポンジアカル（ＴＫ−ＳＰ）(比表面積：４５ｍ２／ｇ)である。
Examples 7 to 10, Comparative Example 3
After gas quenching tower passage of industrial waste incineration plant incinerator equipment, exhaust gas operating conditions at the time of slaked lime no added, HCl gas concentration 750~800ppm (O 2: 12% conversion), Haikemuriryou: 50,000 m 3 N-wet / hr, dust concentration 2.5 g / m 3 N-dry. In the flue after passing through the exhaust gas quenching tower (exhaust temperature 150 ° C.), the addition amount of slaked lime as shown in Table 3 and slaked lime and dust treatment agent are added into the salt passage, and the hydrogen chloride gas concentration is JIS K0107. The measurement was performed every minute according to the above. Table 4 shows the pH values up to 2 hours after the addition of the drug. Further, 2 hours after adding the chemical, the dust collected by the bag filter was sampled, and 30 parts by weight of water was added to 100 parts by weight of the dust and kneaded. 50 parts by weight of the kneaded dust was added to 500 parts by weight of ion-exchanged water (pH = 6), stirred for 30 minutes and subjected to an elution test, and filtered through a 1 μm glass fiber filter to measure the pH of the filtrate (eluate). . In addition, Table 4 shows the results of measuring the heavy metal concentration and pH by conducting a dissolution test on the sample obtained by similarly kneading the dust sampled after 2 hours in the same manner as described above by the Environmental Agency Notification No. 13 method. In addition, the multifunctional slaked lime used by the comparative example 3 and Examples 7-10 is Okutama Kogyo Co., Ltd. product, and is Tamakaruku sponge sponge (TK-SP) (specific surface area: 45 m < 2 > / g).
実施例１１〜１５、比較例４、５
産業廃棄物焼却場の焼却炉設備の排ガス急冷塔通過後における、消石灰無添加時の排ガス運転条件は、ＨＣｌガス濃度４５０〜５００ｐｐｍ（Ｏ２：１２％換算）、排煙量：２３，０００ｍ３Ｎ−ｗｅｔ／ｈｒ、ばいじん濃度３ｇ／ｍ３Ｎ−ｄｒｙである。排ガス急冷塔を通過した後の煙道内において（排煙温度１８０℃）、表５に示す添加量の消石灰単独、及び消石灰と煤塵処理剤を煙道内に添加して、塩化水素ガス濃度はＪＩＳ Ｋ０１０７に準じて１分毎に測定した。薬剤を添加してから２時間後までのｐＨの値を表６に示す。また、薬剤を添加して２時間後バグフィルターで集塵された煤塵をサンプリングし、煤塵１００重量部に対し３０重量部の水を加え混練した。混練処理した煤塵５０重量部をイオン交換水（ｐＨ＝６）５００重量部に加え、３０分間攪拌して溶出試験を行い１μｍのグラスファイバーろ紙でろ過してろ液（溶出液）のｐＨを測定した。
また、前記と同様の２時間後、サンプリングした煤塵を同様に混練処理して得られたサンプルを環境庁告示１３号法により溶出試験を行い重金属濃度とｐＨを測定した結果を表４に示す。なお、比較例４および実施例１１で使用した消石灰はＪＩＳ特号（１５ｍ２／ｇ)である。また、比較例５及び実施例１２〜１５で使用した多機能消石灰は吉澤石灰工業株式会社製、カルミユーメソックスＤ(比表面積：４０〜５０ｍ２／ｇ)である。
Examples 11 to 15 and Comparative Examples 4 and 5
After passing through the exhaust gas quenching tower of the incinerator facility of the industrial waste incineration plant, the exhaust gas operation conditions when no slaked lime is added are HCl gas concentration 450 to 500 ppm (O 2 : 12% conversion), smoke emission amount: 23,000 m 3 N-wet / hr, dust concentration 3 g / m 3 N-dry. In the flue after passing through the exhaust gas quenching tower (exhaust temperature 180 ° C.), the addition amount of slaked lime as shown in Table 5 and slaked lime and dust treatment agent are added into the flue, and the hydrogen chloride gas concentration is JIS K0107. The measurement was performed every minute according to the above. Table 6 shows the pH values until 2 hours after the addition of the drug. Further, 2 hours after adding the chemical, the dust collected by the bag filter was sampled, and 30 parts by weight of water was added to 100 parts by weight of the dust and kneaded. 50 parts by weight of the kneaded dust was added to 500 parts by weight of ion-exchanged water (pH = 6), stirred for 30 minutes and subjected to an elution test, and filtered through a 1 μm glass fiber filter to measure the pH of the filtrate (eluate). .
Table 4 shows the results of measuring the heavy metal concentration and pH of the sample obtained by similarly kneading the sampled dust after 2 hours in the same manner as described above, and conducting an elution test by the Environmental Agency Notification No. 13 method. In addition, the slaked lime used in Comparative Example 4 and Example 11 is a JIS special name (15 m 2 / g). Also, multifunctional slaked lime used in Comparative Example 5 and Examples 12-15 Yoshizawasekkaikogyo Co., Carmi user menu socks D: a (specific surface area 40~50m 2 / g).
実施例１６〜２５、比較例６〜１３
実施例1、３、１０、１３、比較例１、３、５において、バグフィルターで集塵された煤塵１００重量部に水３０重量部、ジチオカルバミン酸系重金属固定剤を表７、８に示す量加え、混練機で混練した。処理飛灰からの重金属類の溶出試験を環境庁告示１３号法により行った。これらの結果を表７、表８に示す。
Examples 16-25, Comparative Examples 6-13
In Examples 1, 3, 10, and 13 and Comparative Examples 1, 3, and 5, the amount shown in Tables 7 and 8 is 30 parts by weight of water and the dithiocarbamic acid heavy metal fixing agent in 100 parts by weight of the dust collected by the bag filter. In addition, the mixture was kneaded with a kneader. An elution test for heavy metals from the treated fly ash was conducted by the Environmental Agency Notification No. 13 method. These results are shown in Tables 7 and 8.
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| CN105327927A (en) * | 2015-11-09 | 2016-02-17 | 中国天楹股份有限公司 | Method and system for disposing incineration fly ash of household garbage |
| WO2020148955A1 (en) * | 2019-01-15 | 2020-07-23 | 栗田工業株式会社 | Exhaust gas treatment system and exhaust gas treatment method |
| CN112774405A (en) * | 2021-01-13 | 2021-05-11 | 河南红东方化工股份有限公司 | Tail gas treatment system is used in chloroacetic acid production |
| JP7390431B2 (en) | 2017-03-31 | 2023-12-01 | 三菱重工業株式会社 | Non-drainage exhaust gas treatment system and non-drainage exhaust gas treatment method |
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| CN112774405A (en) * | 2021-01-13 | 2021-05-11 | 河南红东方化工股份有限公司 | Tail gas treatment system is used in chloroacetic acid production |
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