JP2012250175A - Method for suppressing resynthesis of dioxins and use of acid clay or activated acid clay as suppressant for resynthesis of dioxins - Google Patents
Method for suppressing resynthesis of dioxins and use of acid clay or activated acid clay as suppressant for resynthesis of dioxins Download PDFInfo
- Publication number
- JP2012250175A JP2012250175A JP2011124682A JP2011124682A JP2012250175A JP 2012250175 A JP2012250175 A JP 2012250175A JP 2011124682 A JP2011124682 A JP 2011124682A JP 2011124682 A JP2011124682 A JP 2011124682A JP 2012250175 A JP2012250175 A JP 2012250175A
- Authority
- JP
- Japan
- Prior art keywords
- dioxins
- clay
- resynthesis
- fly ash
- acid clay
- 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.)
- Granted
Links
- 239000004927 clay Substances 0.000 title claims abstract description 95
- 150000002013 dioxins Chemical class 0.000 title claims abstract description 64
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000010881 fly ash Substances 0.000 claims abstract description 56
- 239000000428 dust Substances 0.000 claims abstract description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 10
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 21
- 239000002243 precursor Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- -1 Mg and Fe are eluted Chemical class 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 101100002917 Caenorhabditis elegans ash-2 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Abstract
Description
本発明は、廃棄処分される飛灰中において、ダイオキシン類が再合成されるのを抑制する方法及びダイオキシン類再合成抑制剤としての酸性白土又は活性白土の使用に関する。 The present invention relates to a method for suppressing the resynthesis of dioxins in fly ash to be disposed of, and the use of acid clay or activated clay as a dioxin resynthesis inhibitor.
従来、溶融炉から発生する排ガス中に含まれる溶融飛灰、又は焼却炉から発生する排ガスに含まれる焼却飛灰は、集塵装置により分離除去されたのち廃棄処分されている。 Conventionally, molten fly ash contained in exhaust gas generated from a melting furnace or incinerated fly ash contained in exhaust gas generated from an incinerator is separated and removed by a dust collector and then discarded.
廃棄処分する際には、ダイオキシン類対策特別措置法第２４条第１項の環境省令で定める基準（飛灰１グラムにつき３ナノグラム）があり、それを遵守しなければならない。 There are standards (3 nanograms per gram of fly ash) established by the Ordinance of the Ministry of the Environment of Article 24, Paragraph 1 of the Special Measures Law for Countermeasures against Dioxins.
従来、特許文献１、２に記載のように、排ガス中のダイオキシンを吸着除去するために、活性炭や活性白土のような吸着剤を用いる技術は知られている。
Conventionally, as described in
これらの従来技術では、排ガス中のダイオキシンを活性炭などによって吸着除去して飛灰中に移行させれば大気中に放出される排ガスのダイオキシンが減少しているので、目的を達成していると考え、飛灰側に移行したダイオキシンについて、研究されていなかった。 In these conventional technologies, if dioxins in the exhaust gas are adsorbed and removed by activated carbon etc. and transferred to the fly ash, the dioxins in the exhaust gas released into the atmosphere are reduced, so the objective is considered to be achieved. The dioxins that migrated to the fly ash were not studied.
しかるに、本発明者らの研究によると、Ｄｅ Ｎｏｖｏ合成によるダイオキシン類再合成が起こりにくい飛灰であっても、ダイオキシン類の吸着剤として活性炭が飛灰に混ざれば、ダイオキシン類再合成が顕著に起こることを確認した。 However, according to the research of the present inventors, even if fly ash is difficult to re-synthesize dioxins by De Novo synthesis, if activated carbon is mixed with fly ash as an adsorbent for dioxins, re-synthesis of dioxins becomes remarkable. Confirmed that it happened.
活性炭は実際に稼働している排ガス処理プラントで大量に使用されており、飛灰の廃棄ができなければ、排ガス処理プラントを稼働できず、重大な社会問題になる可能性がある。 Activated carbon is used in large quantities in exhaust gas treatment plants that are actually in operation, and if the fly ash cannot be discarded, the exhaust gas treatment plant cannot be operated, which may become a serious social problem.
一方、酸性白土及び活性白土は、ダイオキシン吸着剤として、知られているが、飛灰中におけるダイオキシン類の挙動に与える影響については、全く研究されていない。 On the other hand, acid clay and activated clay are known as dioxin adsorbents, but the influence on the behavior of dioxins in fly ash has not been studied at all.
本発明者は、飛灰中におけるダイオキシン類の再合成抑制について鋭意検討し、大量使用されている活性炭に比べ、飛灰中のダイオキシン類の再合成抑制機能が格段に優れていることを見出し、本発明を完成させた。 The inventor diligently investigated the resynthesis suppression of dioxins in fly ash, and found that the resynthesis suppression function of dioxins in fly ash is significantly superior to activated carbon that is used in large quantities. The present invention has been completed.
そこで、本発明の課題は、排ガスから分離された飛灰中において、ダイオキシン類の再合成を抑制できる方法を提供することにある。 Then, the subject of this invention is providing the method which can suppress resynthesis of dioxins in the fly ash isolate | separated from waste gas.
また本発明の他の課題は、ダイオキシン類の再合成抑制剤として新規な酸性白土又は活性白土の使用を提供するものである。 Another object of the present invention is to provide use of novel acidic clay or activated clay as a dioxin resynthesis inhibitor.
また本発明の他の課題は、以下の記載によって明らかとなる。 Other problems of the present invention will become apparent from the following description.
上記課題は、以下の各発明によって解決される。 The above problems are solved by the following inventions.
（請求項１）
溶融炉から発生する排ガス中に含まれる溶融飛灰、又は焼却炉から発生する排ガスに含まれる焼却飛灰を集塵装置により分離除去する飛灰の処理方法において、
前記集塵装置の前段又は該集塵装置の内部に酸性白土又は活性白土を添加し、該集塵装置で分離された飛灰中におけるダイオキシン類の再合成を抑制することを特徴とするダイオキシン類の再合成抑制方法。
(Claim 1)
In the fly ash treatment method in which the molten fly ash contained in the exhaust gas generated from the melting furnace or the incineration fly ash contained in the exhaust gas generated from the incinerator is separated and removed by a dust collector,
Dioxins characterized by adding acid clay or activated clay to the front stage of the dust collector or inside the dust collector to suppress resynthesis of dioxins in fly ash separated by the dust collector Resynthesis inhibition method.
（請求項２）
前記酸性白土又は活性白土が、該表面に、鉄酸化物からなる酸化触媒を担持させたものであることを特徴とする請求項１記載のダイオキシン類の再合成抑制方法。
(Claim 2)
2. The method for inhibiting the resynthesis of dioxins according to claim 1, wherein the acid clay or activated clay has an oxidation catalyst made of iron oxide supported on the surface.
（請求項３）
前記酸性白土又は活性白土が、該酸性白土又は活性白土と、鉄酸化物からなる酸化触媒との混合物からなることを特徴とする請求項１記載のダイオキシン類の再合成抑制方法。
(Claim 3)
The method for inhibiting resynthesis of dioxins according to claim 1, wherein the acid clay or the activated clay comprises a mixture of the acid clay or the activated clay and an oxidation catalyst made of iron oxide.
（請求項４）
前記鉄酸化物がＦｅ２Ｏ３酸化物であることを特徴とする請求項２又は３記載のダイオキシン類の再合成抑制方法。
(Claim 4)
The method for inhibiting resynthesis of dioxins according to
（請求項５）
溶融炉から発生する排ガス中に含まれる溶融飛灰、又は焼却炉から発生する排ガスに含まれる焼却飛灰を集塵装置により分離除去する飛灰の処理方法に用いられる酸性白土又は活性白土の使用において、
該集塵装置で分離された飛灰中におけるダイオキシン類の再合成を抑制するダイオキシン類再合成抑制剤としての酸性白土又は活性白土の使用。
(Claim 5)
Use of acid clay or activated clay used in the processing method of fly ash that separates and removes the molten fly ash contained in the exhaust gas generated from the melting furnace or the incineration fly ash contained in the exhaust gas generated from the incinerator with a dust collector In
Use of acid clay or activated clay as a dioxin resynthesis inhibitor that suppresses resynthesis of dioxins in fly ash separated by the dust collector.
（請求項６）
前記酸性白土又は活性白土が、該表面に、Ｆｅ２Ｏ３酸化物からなる酸化触媒を担持させたものであることを特徴とする請求項５記載のダイオキシン類再合成抑制剤としての酸性白土又は活性白土の使用。
(Claim 6)
The acidic clay or activated clay as defined in claim 5, wherein the surface is supported with an oxidation catalyst composed of Fe 2 O 3 oxide. Use of activated clay.
（請求項７）
前記酸性白土又は活性白土が、該酸性白土又は活性白土とＦｅ２Ｏ３酸化物との混合物であることを特徴とする請求項５記載のダイオキシン類再合成抑制剤としての酸性白土又は活性白土の使用。
(Claim 7)
The acid clay or activated clay is a mixture of the acid clay or activated clay and Fe 2 O 3 oxide. The acid clay or activated clay as a dioxin resynthesis inhibitor according to claim 5, use.
本発明によれば、排ガスから分離された飛灰中において、ダイオキシン類の再合成を抑制できる方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the method which can suppress the resynthesis of dioxins in the fly ash isolate | separated from waste gas can be provided.
また本発明によれば、ダイオキシン類の再合成抑制剤として新規な酸性白土又は活性白土の使用を提供できる。 Moreover, according to this invention, use of novel acidic clay or activated clay can be provided as a resynthesis inhibitor of dioxins.
以下、本発明の実施の形態を説明する。 Embodiments of the present invention will be described below.
本発明において、飛灰の処理方法は、溶融炉から発生する排ガス中に含まれる溶融飛灰、又は焼却炉から発生する排ガスに含まれる焼却飛灰を集塵装置により分離除去し、その後、たとえば、必要により加熱処理を施して、ダイオキシン類を含まない（含んでも基準値以下の状態にある）飛灰を廃棄処分する。 In the present invention, the fly ash treatment method separates and removes the molten fly ash contained in the exhaust gas generated from the melting furnace, or the incinerated fly ash contained in the exhaust gas generated from the incinerator, and then, for example, If necessary, heat treatment is performed to dispose of fly ash that does not contain dioxins (even if it is in the state below the standard value).
集塵装置は、飛灰を分離除去できれば、格別限定されず、ガラスフィルタ、ＰＴＦＥメンブレンガラスフィルタ、ＰＴＦＥフィルタ、ＰＴＦＥフェルト等のろ布を用いたバグフィルタを用いることができる。 The dust collector is not particularly limited as long as fly ash can be separated and removed, and a bag filter using a filter cloth such as a glass filter, a PTFE membrane glass filter, a PTFE filter, or a PTFE felt can be used.
本明細書において、ダイオキシン類とは、例えばポリ塩化ジベンゾパラジオキシン（ＰＣＤＤ）、ポリ塩化ジベンゾフラン（ＰＣＤＦ）、コプラナーＰＣＢ（Ｃｏ−ＰＣＢ）などを含む。 In the present specification, dioxins include, for example, polychlorinated dibenzopararadioxin (PCDD), polychlorinated dibenzofuran (PCDF), coplanar PCB (Co-PCB) and the like.
溶融炉や焼却炉と、集塵装置の間は、排ガスダクトによって連結されており、本発明では、酸性白土又は活性白土を集塵装置の前段である前記ダクト内に添加したり、あるいは、集塵装置の内部に添加する。 The melting furnace, the incinerator and the dust collector are connected by an exhaust gas duct. In the present invention, acid clay or activated clay is added to the duct, which is a front stage of the dust collector, or is collected. Add to the inside of the dust device.
添加する酸性白土又は活性白土は、ダイオキシン類及びその前駆体に対して物理吸着作用と化学吸着作用を有するものを用いる。 The acid clay or activated clay to be added is one having a physical adsorption action and a chemical adsorption action on dioxins and their precursors.
本発明に使用する酸性白土は、主としてモンモリロナイトから成り、ＳｉＯ４四面体層−ＡｌＯ６八面体層−ＳｉＯ４四面体層から成る三層構造を基本構造とし、このような三層構造が数枚積層した微小な単結晶の集合体である。また、このような三層構造の積層層間に、Ｃａ、Ｋ、Ｎａ等の陽イオンとそれに配位している水分子が存在している。 Acid clay used in the present invention is mainly composed of montmorillonite, a three-layer structure consisting of SiO 4 tetrahedral layers -AlO 6 octahedral layer -SiO 4 tetrahedral layers as a basic structure, several sheets is such a three-layer structure It is an aggregate of minute single crystals stacked. In addition, cations such as Ca, K, and Na and water molecules coordinated therewith exist between the laminated layers having such a three-layer structure.
上記のモンモリロナイトでは、基本三層構造中のＡｌの一部がＭｇやＦｅ（II）に置換し、Ｓｉの一部がＡｌに置換しており、結晶格子はマイナスの電荷を有しているため、固体酸として機能する。従って、その酸性は、基本層間に存在するアルカリイオンの量に応じて中和され、プロトンの量に応じて、その酸性度が異なったものとなっており、例えば、結晶中に存在しているＳｉ−ＯＨ基がＨイオンを放出するブレンステッド酸として機能し、Ａｌ-ＯＨ２から水が脱離すると、電子受容性を示すルイス酸として機能する。 In the above montmorillonite, a part of Al in the basic three-layer structure is replaced with Mg or Fe (II), a part of Si is replaced with Al, and the crystal lattice has a negative charge. Functions as a solid acid. Therefore, the acidity is neutralized according to the amount of alkali ions present between the basic layers, and the acidity differs depending on the amount of protons, for example, present in the crystal. The Si—OH group functions as a Bronsted acid that releases H ions, and when water is desorbed from Al—OH 2, it functions as a Lewis acid that exhibits electron accepting properties.
また、酸性白土の酸処理物は、活性白土と称されるものであり、上記の酸性白土を硫酸等の鉱酸でモンモリロナイトの基本構造の全部を破壊しない程度に酸処理することにより得られるもので、ＭｇやＦｅ等の金属酸化物が溶出し、比表面積や細孔容積を増大させたものである。 In addition, the acid-treated product of acid clay is called activated clay, and is obtained by acid-treating the acid clay to a degree that does not destroy the entire basic structure of montmorillonite with a mineral acid such as sulfuric acid. Thus, metal oxides such as Mg and Fe are eluted, and the specific surface area and pore volume are increased.
従って、酸性白土又は活性白土に存在する多数の細孔が物理吸着作用を示し、固体酸、特にルイス酸となるＡｌ-ＯＨ２基が、ルイス塩基となるダイオキシン類及びその前駆体
のπ電子を受容して、配位錯体を形成し化学吸着作用を示す。
Therefore, a large number of pores present in the acid clay or the activated clay exhibit a physical adsorption action, and the solid acid, particularly the Al—OH 2 group that becomes a Lewis acid, dioxins that become a Lewis base and π electrons of the precursor thereof. Accepts and forms a coordination complex and exhibits chemisorption.
これらの物理吸着作用と化学吸着作用とが協働する結果、本発明の酸性白土又は活性白土は、排ガス中のダイオキシン類及びその前駆体を効率的に吸着し、更に以下に説明するダイオキシン類及びその前駆体の分解反応を促進する触媒作用によりこれらを分解して、飛灰中に移行しても、飛灰中でダイオキシン類が再合成されることを抑制できる。 As a result of the cooperation between the physical adsorption action and the chemical adsorption action, the acid clay or the activated clay of the present invention efficiently adsorbs dioxins and their precursors in the exhaust gas, and further dioxins described below and Even if these are decomposed by the catalytic action that promotes the decomposition reaction of the precursor and transferred to the fly ash, dioxins can be prevented from being re-synthesized in the fly ash.
本発明の酸性白土又は活性白土は、ダイオキシン類及びその前駆体の分解反応を促進する触媒作用を有する。特に、活性白土の表面には、活性点が多数存在し、その活性点が固体酸触媒機能を発揮し、ダイオキシン類の再合成が更に抑制される効果を発揮しているものと推定される。 The acidic clay or activated clay of the present invention has a catalytic action that promotes the decomposition reaction of dioxins and their precursors. In particular, it is presumed that there are many active sites on the surface of the activated clay, the active sites exhibit a solid acid catalyst function, and the effect of further suppressing the resynthesis of dioxins is exhibited.
また、本発明の酸性白土又は活性白土の触媒機能を上げるために、表面に機能性酸化触媒を担持させるか、もしくは鉄酸化物を混合することも好ましい。 In order to improve the catalytic function of the acid clay or activated clay of the present invention, it is also preferable to support a functional oxidation catalyst on the surface or to mix an iron oxide.
機能性酸化触媒としては、Ｆｅ２Ｏ３酸化物等の酸化鉄触媒を好ましく例示でき、中でもダイオキシン類及びその前駆体の分解反応に対し強い触媒作用を有するＦｅ２Ｏ３酸化物が最も好ましい。 As the functional oxidation catalyst, an iron oxide catalyst such as Fe 2 O 3 oxide can be preferably exemplified, and among them, Fe 2 O 3 oxide having a strong catalytic action for the decomposition reaction of dioxins and their precursors is most preferable.
本発明の好ましい酸性白土としては、ＳｉＯ２含有量が７０乃至８５重量％、Ａｌ２Ｏ３が８乃至１２％にあることが好ましく、更に、酸性白土粒子の表面に、酸性白土（１１０℃乾燥基準）１００重量部に対し、Ｆｅ２Ｏ３酸化物の微粒子を０．５乃至１０．０重量％、特に０．５乃至５．０重量％を担持、もしくは酸性白土（１１０℃乾燥基準）１００重量部に対し、Ｆｅ２Ｏ３酸化物の微粒子を０．５乃至３０重量％、特に、１乃至２５重量％を混合することが好ましい。 The preferred acidic clay of the present invention preferably has a SiO 2 content of 70 to 85% by weight and Al 2 O 3 of 8 to 12%. (Standard) 0.5 to 10.0% by weight, particularly 0.5 to 5.0% by weight of fine particles of Fe 2 O 3 oxide with respect to 100 parts by weight, or acidic clay (110 ° C. dry standard) 100 It is preferable to mix 0.5 to 30% by weight, particularly 1 to 25% by weight, of Fe 2 O 3 oxide fine particles with respect to parts by weight.
また、活性白土の製法例としては、一般に酸性白土を硫酸等の鉱酸によって処理する方法を例示できる。本発明に用いられる活性白土は、硫酸３０乃至５０重量％の濃度で、温度６０乃至９０℃で酸処理して得られるもので、その物性はＢＥＴ比表面積が５０乃至４００ｍ２／ｇの範囲、細孔容積は、０．２乃至０．３ｃｍ３／ｇの範囲であることが好ましい。 Moreover, as an example of a manufacturing method of activated clay, generally the method of processing acidic clay with mineral acids, such as a sulfuric acid, can be illustrated. The activated clay used in the present invention is obtained by acid treatment at a temperature of 60 to 90 ° C. at a concentration of 30 to 50% by weight of sulfuric acid, and its physical properties are in the range of BET specific surface area of 50 to 400 m 2 / g, The pore volume is preferably in the range of 0.2 to 0.3 cm 3 / g.
更に、本発明においては、活性白土の表面にＦｅ２Ｏ３酸化物の微粒子を０．５乃至１０．０重量％、好ましくは０．５乃至５．０重量％を担持させる（乾式法）、もしくは活性白土の酸処理後に鉄塩水溶液を加水分解してＦｅ２Ｏ３酸化物として０．５重量％以上沈着させる（湿式法）か、活性白土（１１０℃乾燥基準）１００重量部に対し、Ｆｅ２Ｏ３酸化物の微粒子を０．５乃至３０重量％、好ましくは１乃至２５重量％を混合する。 Further, in the present invention, 0.5 to 10.0% by weight, preferably 0.5 to 5.0% by weight of Fe 2 O 3 oxide fine particles are supported on the surface of the activated clay (dry method), Alternatively, after acid treatment of the activated clay, the aqueous iron salt solution is hydrolyzed to deposit 0.5 wt% or more as Fe 2 O 3 oxide (wet method), or 100 parts by weight of activated clay (110 ° C. dry basis) Fe 2 O 3 oxide fine particles are mixed in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight.
更にまた、本発明において、酸性白土又は活性白土の平均粒子径は、好ましくは、２０乃至６０μｍ、より好ましくは、３５乃至５０μｍであり、酸化鉄、特にＦｅ２Ｏ３酸化物の平均粒子径は、好ましくは、０．１乃至１０．０μｍ、より好ましくは、０．１乃至５．０μｍであることである。酸性白土、活性白土又は酸化鉄の平均粒子径が上記範囲内であれば、集塵装置で分離された飛灰中におけるダイオキシン類の再合成を更に抑制する効果が得られる。 Furthermore, in the present invention, the average particle size of the acid clay or the activated clay is preferably 20 to 60 μm, more preferably 35 to 50 μm, and the average particle size of iron oxide, particularly Fe 2 O 3 oxide, is The thickness is preferably 0.1 to 10.0 μm, and more preferably 0.1 to 5.0 μm. If the average particle diameter of acid clay, activated clay, or iron oxide is within the above range, an effect of further suppressing resynthesis of dioxins in the fly ash separated by the dust collector can be obtained.
酸性白土もしくは活性白土、又は、酸化鉄含有酸性白土もしくは活性白土の添加量は、排ガスに対して、５０乃至１５０ｍｇ／ｍ３Ｎ−ｄｒｙとなるように添加することが好ましい。添加量が上記範囲内であれば、集塵装置で分離された飛灰中におけるダイオキシン類の再合成を更に抑制する効果が得られる。 The amount of acid clay or activated clay, or the amount of iron oxide-containing acid clay or activated clay is preferably 50 to 150 mg / m 3 N-dry with respect to the exhaust gas. If the addition amount is within the above range, an effect of further suppressing the resynthesis of dioxins in the fly ash separated by the dust collector can be obtained.
本発明においては、飛灰中で、ダイオキシン前駆体が好適に除去されるために、飛灰中のダイオキシン類の再合成が十分に抑制される。 In the present invention, since the dioxin precursor is suitably removed in the fly ash, the resynthesis of dioxins in the fly ash is sufficiently suppressed.
本発明において、排ガスの大気放出に際して、排ガス中の塩化水素濃度を低下させるための脱塩剤の使用は、適宜行うことができる。 In the present invention, when the exhaust gas is released into the atmosphere, the use of a desalting agent for reducing the hydrogen chloride concentration in the exhaust gas can be appropriately performed.
以下に、本発明の実施例を説明するが、本発明はかかる実施例によって限定されない。 Examples of the present invention will be described below, but the present invention is not limited to such examples.
＜飛灰中におけるダイオキシン類の再合成挙動確認試験＞
実機バグフィルタ入口部に粉末活性炭を噴霧して得られた飛灰１と、バグフィルタへの粉末活性炭噴霧を行わずに得られた飛灰に粉末活性炭を混合した飛灰２について、２５０℃に再加熱してダイオキシン類の再合成挙動を確認したところ、いずれもダイオキシン類の量が増加する挙動を示すことが確認されている。
<Test for confirming resynthesis of dioxins in fly ash>
About fly ash 1 obtained by spraying powdered activated carbon on the actual bag filter inlet, and fly
本試験では、飛灰に粉末活性炭等を混合した後、加熱しダイオキシン類の増加の程度を確認することにした。試験に使用する飛灰は、ダイオキシン類再合成の影響を極力少なくするために、ダイオキシン類をほとんど含まない飛灰を使用し、ダイオキシン類の増加の程度の差異を明らかにするために、試験ではダイオキシン類の再合成が起こりやすい温度雰囲気である３２０〜３２５℃に再加熱する方法を採用した。 In this test, powdered activated carbon and the like were mixed with fly ash and then heated to confirm the degree of increase in dioxins. The fly ash used in the test is a fly ash that contains almost no dioxins in order to minimize the effects of dioxin resynthesis, and in order to clarify the difference in the increase in dioxins, A method of reheating to 320 to 325 ° C., which is a temperature atmosphere in which dioxins are easily re-synthesized, was adopted.
以下に試験の詳細を示す。 Details of the test are shown below.
ダイオキシン類（ＤＸＮｓ）をほとんど含まない飛灰（試料１）に、排ガス中のＤＸＮｓ吸着剤として市販されている粉末活性炭又は活性白土を飛灰に対して３重量％混合してなる試料２、試料３及び試料４をそれぞれ３５０ｇ作成した。これらの試料を３２０〜３２５℃の温度下において、２時間加熱した。自然冷却後、ダイオキシン類濃度を測定した。結果を表１に示す。
ダイオキシン類の濃度の測定は、廃棄物焼却炉に係るばいじん等に含まれるダイオキシン類の量の基準及び測定の方法に関する省令（平成１２年厚生省令第１号）を簡略化した方法で分析した。 The concentration of dioxins was analyzed by a simplified method of the ministerial ordinance (Ministry of Health and Welfare Ordinance No. 1 of 2000) concerning the standard and measurement method of the amount of dioxins contained in the dust associated with waste incinerators.
試料１：ダイオキシン類をほとんど含まない飛灰。その組成分析結果を表２に示す。 Sample 1: Fly ash containing almost no dioxins. The composition analysis results are shown in Table 2.
試料２：試料１に対して３重量％に相当する、排ガス中のＤＸＮｓ吸着剤として市販されている粉末活性炭Ａを混合した試料
試料３：試料１に対して３重量％に相当する、排ガス中のＤＸＮｓ吸着剤として市販されている粉末活性炭Ｂを混合した試料
試料４：試料１に対して３重量％に相当する活性白土（水澤化学工業（株）製「ミズカキャッチャー」：比表面積１００ｍ２／ｇ、平均粒子径４２．０μｍ）を混合した試料
Sample 2: Sample mixed with powdered activated carbon A commercially available as a DXNs adsorbent in exhaust gas corresponding to 3% by weight with respect to Sample 1 Sample 3: In exhaust gas corresponding to 3% by weight with respect to Sample 1 Sample mixed with powdered activated carbon B commercially available as a DXNs adsorbent of No. 4 Sample: Activated clay corresponding to 3% by weight with respect to Sample 1 (“Mizuka Catcher” manufactured by Mizusawa Chemical Co., Ltd.): specific surface area 100 m 2 / g, average particle size 42.0 μm)
表１の結果（試料２〜４）を図１に示す。
The results of Table 1 (
＜評価＞
ダイオキシン類をほとんど含まない飛灰を用いているにも関わらず、粉末活性炭を混合した試料２や試料３を３２０〜３２５℃に加熱すると、環境省令で定める基準である１グラムにつき３ナノグラム−ＴＥＱ／ｇを超える高濃度のダイオキシン類が再合成されていることがわかる。これに対して、活性白土を混合した試料４を３２０〜３２５℃に加熱しても、環境省令で定める基準を大幅に下回る濃度であり、ダイオキシン類の再合成が大幅に抑制されていることが分かる。
<Evaluation>
Despite the use of fly ash containing almost no dioxins, when
Claims (7)
前記集塵装置の前段又は該集塵装置の内部に酸性白土又は活性白土を添加し、該集塵装置で分離された飛灰におけるダイオキシン類の再合成を抑制することを特徴とするダイオキシン類の再合成抑制方法。 In the fly ash treatment method in which the molten fly ash contained in the exhaust gas generated from the melting furnace or the incineration fly ash contained in the exhaust gas generated from the incinerator is separated and removed by a dust collector,
An acid clay or activated clay is added to the front stage of the dust collector or the inside of the dust collector to suppress the resynthesis of dioxins in the fly ash separated by the dust collector. Resynthesis inhibition method.
該集塵装置で分離された飛灰中におけるダイオキシン類の再合成を抑制するダイオキシン類再合成抑制剤としての酸性白土又は活性白土の使用。 Use of acid clay or activated clay used in the processing method of fly ash that separates and removes the molten fly ash contained in the exhaust gas generated from the melting furnace or the incineration fly ash contained in the exhaust gas generated from the incinerator with a dust collector In
Use of acid clay or activated clay as a dioxin resynthesis inhibitor that suppresses resynthesis of dioxins in fly ash separated by the dust collector.
The acid clay or activated clay is a mixture of the acid clay or activated clay and Fe 2 O 3 oxide. The acid clay or activated clay as a dioxin resynthesis inhibitor according to claim 5, use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011124682A JP5734103B2 (en) | 2011-06-02 | 2011-06-02 | Method for inhibiting resynthesis of dioxins and use of acid clay or activated clay as a dioxin resynthesis inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011124682A JP5734103B2 (en) | 2011-06-02 | 2011-06-02 | Method for inhibiting resynthesis of dioxins and use of acid clay or activated clay as a dioxin resynthesis inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012250175A true JP2012250175A (en) | 2012-12-20 |
| JP5734103B2 JP5734103B2 (en) | 2015-06-10 |
Family
ID=47523511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011124682A Active JP5734103B2 (en) | 2011-06-02 | 2011-06-02 | Method for inhibiting resynthesis of dioxins and use of acid clay or activated clay as a dioxin resynthesis inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5734103B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10328534A (en) * | 1997-05-29 | 1998-12-15 | Hitachi Zosen Corp | Method for preventing deposition of acid ammonium sulfate and ammonium sulfate |
| JP2001079352A (en) * | 1999-07-09 | 2001-03-27 | Toda Kogyo Corp | Treatment of exhaust gas containing dioxin and combined catalyst for controlling dioxin |
| JP2002136821A (en) * | 2000-10-31 | 2002-05-14 | Kawasaki Heavy Ind Ltd | Method and device for treating exhaust gas |
| JP2003161586A (en) * | 2001-07-06 | 2003-06-06 | Hitachi Zosen Corp | Gas cooling method and gas cooler |
| JP2006263587A (en) * | 2005-03-24 | 2006-10-05 | Mizusawa Shoji Kk | Method for treatment of combustion exhaust-gas |
| JP2009228974A (en) * | 2008-03-24 | 2009-10-08 | Furukawa Electric Co Ltd:The | Exhaust gas treating facility and exhaust gas treating method |
-
2011
- 2011-06-02 JP JP2011124682A patent/JP5734103B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10328534A (en) * | 1997-05-29 | 1998-12-15 | Hitachi Zosen Corp | Method for preventing deposition of acid ammonium sulfate and ammonium sulfate |
| JP2001079352A (en) * | 1999-07-09 | 2001-03-27 | Toda Kogyo Corp | Treatment of exhaust gas containing dioxin and combined catalyst for controlling dioxin |
| JP2002136821A (en) * | 2000-10-31 | 2002-05-14 | Kawasaki Heavy Ind Ltd | Method and device for treating exhaust gas |
| JP2003161586A (en) * | 2001-07-06 | 2003-06-06 | Hitachi Zosen Corp | Gas cooling method and gas cooler |
| JP2006263587A (en) * | 2005-03-24 | 2006-10-05 | Mizusawa Shoji Kk | Method for treatment of combustion exhaust-gas |
| JP2009228974A (en) * | 2008-03-24 | 2009-10-08 | Furukawa Electric Co Ltd:The | Exhaust gas treating facility and exhaust gas treating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5734103B2 (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10730011B2 (en) | Multi-functional composition of matter for rapid removal of mercury from a flue gas | |
| Tan et al. | Preparation and characterization of Fe2O3–SiO2 composite and its effect on elemental mercury removal | |
| He et al. | Catalytic behavior and synergistic effect of nanostructured mesoporous CuO-MnOx-CeO2 catalysts for chlorobenzene destruction | |
| Yang et al. | Recent developments on gas–solid heterogeneous oxidation removal of elemental mercury from flue gas | |
| EP2956230B1 (en) | Enhanced sorbent formulation for removal of mercury from flue gas | |
| JP2021506583A (en) | Catalysts for catalyzing formaldehyde oxidation and their preparation and use | |
| JP5722888B2 (en) | Solid inorganic composition for reducing dioxins and heavy metals in combustion exhaust gas, its production method and its utilization | |
| Chiu et al. | Control of mercury emissions from coal-combustion flue gases using CuCl2-modified zeolite and evaluating the cobenefit effects on SO2 and NO removal | |
| WO2007064500A1 (en) | Pollutant emission control sorbents and methods of manufacture | |
| CN1929897B (en) | Method for reducing heavy metals of flue gases | |
| WO2013082157A1 (en) | Multi-functional composition for rapid removal of mercury from a flue gas | |
| CN106110881A (en) | A kind of exhaust gas treating agent | |
| EP2864022B1 (en) | Means for purifying fluids, method of its preparation and its use | |
| JP5734103B2 (en) | Method for inhibiting resynthesis of dioxins and use of acid clay or activated clay as a dioxin resynthesis inhibitor | |
| JP4596944B2 (en) | Combustion exhaust gas treatment method | |
| US10058814B2 (en) | Process for purifying fluids | |
| CN109589972A (en) | A kind of oil smoke cleaning material | |
| Huang et al. | Effect of NiFe 2 O 4 on PCDF byproducts formation during thermal degradation of decachlorobiphenyl | |
| JP2013166142A (en) | Adsorbent of aromatic chlorine compound | |
| Amayreh et al. | High performance adsorptive removal of N-nitrosodiphenylamine from aqueous solutions by jute stick–derived activated carbon: characteristics, isotherm, kinetic and thermodynamic, and reusability studies | |
| JP2017148764A (en) | Aldehyde removing catalyst composition, manufacturing method therefor and a removing method of aldehyde gas | |
| JP5528890B2 (en) | Dioxin generation inhibitor and combustion exhaust gas treatment method | |
| Hung et al. | Use of regenerated ferric oxide for CO destruction and suppressing dioxin formation in flue gas in a pilot-scale incinerator | |
| JP3928872B2 (en) | PCB removal agent and removal method | |
| JP3521730B2 (en) | How to remove organic chlorine compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140225 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141015 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141021 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150120 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150218 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150317 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150414 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5734103 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |