JP2008207044A - Detoxification method of solid containing organohalogen compound - Google Patents
Detoxification method of solid containing organohalogen compound Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 150000002896 organic halogen compounds Chemical class 0.000 title claims abstract description 61
- 239000007787 solid Substances 0.000 title claims abstract description 39
- 238000001784 detoxification Methods 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002956 ash Substances 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 16
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 239000002689 soil Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000010881 fly ash Substances 0.000 claims description 9
- 238000000638 solvent extraction Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 150000002013 dioxins Chemical class 0.000 description 33
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 15
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 238000005695 dehalogenation reaction Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FPWNLURCHDRMHC-UHFFFAOYSA-N 4-chlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1 FPWNLURCHDRMHC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 dioxins Chemical class 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
Description
本発明は、ダイオキシン類に代表される有機ハロゲン化合物を含有する焼却灰、焼却飛灰、土壌などの固体を無害化する有機ハロゲン化合物を含有する固体の無害化方法に関する。 The present invention relates to a method for detoxifying a solid containing an organic halogen compound that detoxifies solids such as incineration ash, incineration fly ash, and soil containing an organic halogen compound typified by dioxins.
周知のように、ダイオキシン類に代表される有機ハロゲン化合物は、熱的に安定で分解され難い物質である。しかしながら有機ハロゲン化合物は、環境に悪影響を及ぼすことから、これを無害化することが必要であり、これまでにも多くの無害化技術が開示されている。その無害化技術としては、例えば（１）焼却法（２）溶融固化法（３）熱分解法（４）オゾン分解法（５）水熱分解法（６）アルカリ分解法（７）接触水素化による脱ハロゲン化法などがある。 As is well known, organohalogen compounds represented by dioxins are thermally stable and hardly decomposed. However, since organic halogen compounds have an adverse effect on the environment, it is necessary to make them harmless, and many harmless technologies have been disclosed so far. Examples of the detoxification technology include (1) incineration method, (2) melt solidification method, (3) thermal decomposition method, (4) ozonolysis method, (5) hydrothermal decomposition method, (6) alkali decomposition method, and (7) catalytic hydrogenation. There is a dehalogenation method.
焼却法は、空気中で約１５００〜１８００℃の温度で高温酸化反応させ、有機ハロゲン化合物を分解させる方法である。溶融固化法は、プラズマアーク炉などにより飛灰を溶融してスラグ化する際の熱で、有機ハロゲン化合物を分解させる方法である。また熱分解法は、還元雰囲気下において３００〜５００℃の温度で、脱塩素化、水素添加し、無害化する方法である。またオゾン分解法は、オゾンにより有機ハロゲン化合物を酸化分解させる方法である。また、水熱分解法は、超臨界水を用いて有機ハロゲン化合物を脱塩素化させる方法である。アルカリ分解法は、アルカリ水溶液を添加した後、加熱し有機ハロゲン化合物を脱塩素化させる方法である。接触水素化による脱ハロゲン化法は、貴金属触媒存在下において、水素ガスを導入して接触水素化させることにより、脱ハロゲン化を行う方法である。 The incineration method is a method in which an organic halogen compound is decomposed by a high-temperature oxidation reaction in air at a temperature of about 1500 to 1800 ° C. The melt-solidification method is a method in which an organic halogen compound is decomposed with heat when melting fly ash by a plasma arc furnace or the like to form slag. The thermal decomposition method is a method of detoxifying and dehydrogenating at a temperature of 300 to 500 ° C. in a reducing atmosphere. The ozonolysis method is a method of oxidizing and decomposing an organic halogen compound with ozone. The hydrothermal decomposition method is a method of dechlorinating an organic halogen compound using supercritical water. The alkali decomposition method is a method in which an aqueous alkali solution is added and then heated to dechlorinate the organic halogen compound. The dehalogenation method by catalytic hydrogenation is a method in which dehalogenation is performed by introducing hydrogen gas and catalytic hydrogenation in the presence of a noble metal catalyst.
上記の無害化方法は、（イ）高温又は高圧の条件下で行う必要があるなど操作条件が厳しい。（ロ）大掛かりな装置が必要である。（ハ）操作が複雑である。などの課題が指摘されている。また、ダイオキシン類に汚染された土壌の処理方法として、土壌そのものを溶融する方法は実用的な方法とは言えないとし、メカノケミカル法を利用した方法も提案されている。この方法は、第一にダイオキシン類に汚染された土壌を水で洗浄し、土壌を粗粒部と水を含む微粒部に分離する。引き続き微粒部から水を除去し、この微粒部に酸化カルシウムを混合し、メカノケミカル処理することでダイオキシン類を無害化する方法である（例えば特許文献１参照）。ダイオキシン類の分解に酸化カルシムを使用するメカノケミカル法は、このほかにも多くの研究がなされている（例えば非特許文献１参照）。 The above-mentioned detoxification methods are severe in operating conditions, for example, (i) need to be performed under high temperature or high pressure conditions. (B) A large-scale device is required. (C) The operation is complicated. Issues such as are pointed out. In addition, as a method for treating soil contaminated with dioxins, a method of melting the soil itself is not a practical method, and a method using a mechanochemical method has also been proposed. In this method, first, soil contaminated with dioxins is washed with water, and the soil is separated into a coarse part and a fine part containing water. Subsequently, water is removed from the fine particle part, calcium oxide is mixed into the fine particle part, and a mechanochemical treatment is performed to render the dioxins harmless (see, for example, Patent Document 1). Many other studies have been conducted on mechanochemical methods using calcium oxide for decomposition of dioxins (see, for example, Non-Patent Document 1).
本発明者らも、ダイオキシン類をはじめ有機ハロゲン化合物を無害化する研究を行っており、ダイオキシン類、アルコール類、金属カルシウム、及び有機酸などの反応促進剤を撹拌混合し、ダイオキシン類を無害化する技術を開示し、特許を取得している(例えば特許文献２参照)。さらに還元触媒を利用しダイオキシン類を無害化する技術についても特許を取得している(例えば特許文献３参照)。
ダイオキシン類の分解に酸化カルシムを使用するメカノケミカル法は、被処理物であるダイオキシン類又はダイオキシン類含む土壌に対して、重量比で同量程度の酸化カルシウムを添加する必要がある。このためダイオキシン類を無害化した後の容量が非常に大きくなってしまう。有機ハロゲン化合物を無害化する方法としては、（１）簡単な操作、数少ない工程で無害化できる。（２）操作条件が常温、大気圧近くであるなど温和な条件である。（３）処理費用が安い。（４）処理に伴い容量が増加しない。（５）廃棄物の発生が少ない。などの要件を満足する方法であることが好ましく、有機ハロゲン化合物を無害化するに当たり、上記要件を十分に満足させることは永遠の課題と言える。 In the mechanochemical method using calcium oxide for the decomposition of dioxins, it is necessary to add the same amount of calcium oxide in a weight ratio to the dioxins or dioxins containing soil to be treated. For this reason, the capacity | capacitance after detoxifying dioxins will become very large. As a method of detoxifying an organic halogen compound, (1) it can be detoxified with simple operations and few processes. (2) The operating conditions are mild such as normal temperature and near atmospheric pressure. (3) The processing cost is low. (4) The capacity does not increase with processing. (5) There is little generation of waste. It is preferable that the method satisfies the above requirements, and it can be said that it is an eternal problem to sufficiently satisfy the above requirements when detoxifying the organic halogen compound.
本発明の目的は、処理に伴い容量がほとんど増加することなく、かつ簡単な操作で有機ハロゲン化合物を含有する固体を無害化する方法を提供することである。 An object of the present invention is to provide a method for detoxifying a solid containing an organic halogen compound with a simple operation with little increase in capacity due to the treatment.
本発明は、有機ハロゲン化合物を含有する固体と、水に少なくとも一部は溶解し電子移動による還元力を有する金属とを水の存在下でメカノケミカル処理し、前記有機ハロゲン化合物を脱ハロゲン化することを特徴とする有機ハロゲン化合物を含有する固体の無害化方法である。 In the present invention, a solid containing an organic halogen compound and a metal that is at least partially dissolved in water and has a reducing power by electron transfer are mechanochemically treated in the presence of water to dehalogenate the organic halogen compound. This is a method for detoxifying a solid containing an organic halogen compound.
また本発明は、前記有機ハロゲン化合物を含有する固体の無害化方法において、前記有機ハロゲン化合物を含有する固体は、焼却灰、焼却飛灰、土壌又はこれらの混合物であり、前記水は、焼却灰、焼却飛灰、土壌又はこれらの混合物に予め含まれている水、又はこれら処理対象物を空気中に放置したとき吸着する水であることを特徴とする。 Further, the present invention is the method for detoxifying a solid containing an organic halogen compound, wherein the solid containing the organic halogen compound is incineration ash, incineration fly ash, soil or a mixture thereof, and the water is incineration ash It is characterized in that it is water previously contained in incineration fly ash, soil or a mixture thereof, or water that adsorbs when these treatment objects are left in the air.
また本発明は、有機ハロゲン化合物を含有する固体を水で洗浄、脱水する洗浄脱水工程と、洗浄脱水した水を含む有機ハロゲン化合物を含有する固体に、水に少なくとも一部は溶解し電子移動による還元力を有する金属を添加し、これら混合物をメカノケミカル処理し、前記有機ハロゲン化合物を脱ハロゲン化するメカノケミカル処理工程と、を含むことを特徴とする有機ハロゲン化合物を含有する固体の無害化方法である。 The present invention also provides a washing and dehydration step in which a solid containing an organic halogen compound is washed and dehydrated with water, and a solid containing the organic halogen compound containing the washed and dehydrated water is at least partially dissolved in water and is transferred by electron transfer. And a mechanochemical treatment step of adding a metal having a reducing power, mechanochemically treating the mixture, and dehalogenating the organic halogen compound, and detoxifying the solid containing the organic halogen compound, It is.
また本発明は、前記有機ハロゲン化合物を含有する固体の無害化方法において、さらに前記有機ハロゲン化合物を含有する固体を乾燥させる又は水を添加する水分調整工程を含み、水分調整を行った後に、前記水に少なくとも一部は溶解し電子移動による還元力を有する金属を添加し、これをメカノケミカル処理することを特徴とする。 The present invention further includes a moisture adjustment step of drying the solid containing the organic halogen compound or adding water in the method for detoxifying a solid containing the organic halogen compound, and after adjusting the moisture, It is characterized in that a metal having at least a part dissolved in water and having a reducing power by electron transfer is added and mechanochemically treated.
また本発明は、前記有機ハロゲン化合物を含有する固体の無害化方法において、水に少なくとも一部は溶解し電子移動による還元力を有する金属は、アルカリ金属、アルカリ土類金属、第３族元素、鉄、亜鉛及びこれらを含む合金のうち少なくともいずれか１を含むことを特徴とする。 Further, the present invention is the method for detoxifying a solid containing an organic halogen compound, wherein the metal having at least a part dissolved in water and having a reducing power by electron transfer is an alkali metal, an alkaline earth metal, a Group 3 element, It contains at least any one of iron, zinc, and an alloy containing these.
また本発明は、前記有機ハロゲン化合物を含有する固体の無害化方法において、さらにメカノケミカル処理後の被処理物に溶媒を加え、残留する有機ハロゲン化合物を溶媒抽出する溶媒抽出工程と、溶媒抽出後の抽出溶媒を分離する溶媒分離工程と、を含むことを特徴とする。 Further, the present invention provides a method for detoxifying a solid containing an organic halogen compound, a solvent extraction step of adding a solvent to an object to be processed after mechanochemical treatment and extracting the remaining organic halogen compound by solvent, and after solvent extraction And a solvent separation step of separating the extraction solvent.
本発明の有機ハロゲン化合物を含有する固体の無害化方法を用いることにより、処理に伴い容量がほとんど増加することなく、かつ簡単な操作で有機ハロゲン化合物を含有する固体を無害化することができる。 By using the method for detoxifying a solid containing an organic halogen compound according to the present invention, the solid containing the organic halogen compound can be made harmless with a simple operation with almost no increase in capacity due to the treatment.
本発明の有機ハロゲン化合物を含有する固体の無害化方法の一例を示す。本発明の有機ハロゲン化合物を含有する固体の無害化方法の被処理物としては、ダイオキシン類を含有する焼却灰、飛灰、土壌又はこれら混合物などが例示される。以下、ダイオキシン類を含有する焼却灰（以下ダイオキシン類含有焼却灰と記す）を例として基本的な手順を示す。まず、被処理物であるダイオキシン類含有焼却灰に水を加え、ダイオキシン類含有焼却灰を洗浄する（洗浄工程）。洗浄工程に引続き、ダイオキシン類含有焼却灰と水との混合物を脱水する（脱水工程）。脱水工程で得られた洗浄後のダイオキシン類含焼却灰をさらに乾燥させ水分量を所定の範囲内に調整する（水分調整工程）。続いて、水分量を調整したダイオキシン類含有焼却灰に、水に少なくとも一部は溶解し電子移動による還元力を有する金属を加え、これら混合物をメカノケミカル処理する（メカノケミカル処理工程）。これによりダイオキシン類含有焼却灰に含まれるダイオキシン類を無害化することができる。 An example of a method for detoxifying a solid containing the organic halogen compound of the present invention will be shown. Examples of the object to be treated of the solid detoxification method containing the organic halogen compound of the present invention include incinerated ash, fly ash, soil, or a mixture thereof containing dioxins. Hereinafter, the basic procedure will be described by taking incineration ash containing dioxins (hereinafter referred to as dioxin-containing incineration ash) as an example. First, water is added to the dioxin-containing incinerated ash that is the object to be treated, and the dioxin-containing incinerated ash is washed (cleaning step). Following the washing process, the mixture of dioxin-containing incinerated ash and water is dehydrated (dehydration process). The washed dioxin-containing incinerated ash obtained in the dehydration step is further dried to adjust the water content within a predetermined range (moisture adjustment step). Subsequently, a metal having at least a part dissolved in water and having a reducing power by electron transfer is added to the dioxin-containing incinerated ash whose water content is adjusted, and the mixture is mechanochemically treated (mechanochemical treatment step). Thereby, the dioxins contained in the dioxin-containing incinerated ash can be rendered harmless.
被処理物であるダイオキシン類含有焼却灰に水を加え、ダイオキシン類含有焼却灰を洗浄する洗浄工程は、ダイオキシン類含有焼却灰に含まれる無機塩素化合物、例えば塩化ナトリウム、塩化カルシウムなどを水に溶解させこれらを除去する目的で行う操作である。ダイオキシン類含有焼却灰に含まれる無機塩素化合物を水に溶解させ除去することで、メカノケミカル処理工程で添加する、水に少なくとも一部は溶解し電子移動による還元力を有する金属の添加量を減少させることができる。このように洗浄工程は、ダイオキシン類含有焼却灰に含まれる無機塩素化合物を除去する目的で行う操作であるから、被処理物に無機塩素化合物を含んでいないか、含有量が少ない場合は、本洗浄工程は必ずしも必要ではない。また屋外の風雨にさらされている土壌を被処理物とするような場合であって、すでに無機塩素化合物が雨で洗い流されているようなケースにおいては、必ずしも洗浄操作は必要ではない。なお洗浄操作は、後述の実施例からも分かるように、水に可溶する成分が被処理物から除去されるため、被処理物の量を少なくする効果もある。 The washing process of adding water to the incinerated ash containing dioxins and washing the dioxins containing incinerated ash, which is the object to be treated, dissolves inorganic chlorine compounds such as sodium chloride and calcium chloride contained in the dioxins containing incinerated ash in water. This is an operation performed for the purpose of removing them. Inorganic ash compounds contained in dioxin-containing incineration ash are dissolved in water and removed, reducing the amount of metal added in the mechanochemical treatment process and dissolved in water and having reducing power by electron transfer Can be made. As described above, the cleaning process is an operation performed for the purpose of removing the inorganic chlorine compound contained in the dioxin-containing incinerated ash, so if the object to be treated does not contain the inorganic chlorine compound or the content is small, A cleaning step is not always necessary. Further, in the case where the soil exposed to outdoor wind and rain is used as the object to be treated, and the case where the inorganic chlorine compound has already been washed away by rain, the washing operation is not necessarily required. As can be seen from the examples described later, the washing operation also has an effect of reducing the amount of the object to be processed because the components soluble in water are removed from the object to be processed.
洗浄工程での水の添加量、洗浄操作も、ダイオキシン類含有焼却灰に含まれる無機塩素化合物を水に溶解させることができれば特定の方法に限定されるものではない。よって、ダイオキシン類含有焼却灰に水を添加し、これを撹拌機で撹拌する方法、空気を吹き込みバブリングさせる方法、又はダイオキシン類含有焼却灰に水を添加し撹拌させることなく所定の時間静置させる方法であってもよい。さらに水分を多く含む土壌、焼却炉を解体する際、高圧水で壁面に付着した焼却灰を剥離させた回収物など多くの水分を含む焼却灰にあっては、新たに水を加えることなく、被処理物に含まれる水を利用することができる。 The amount of water added and the washing operation in the washing step are not limited to a specific method as long as the inorganic chlorine compound contained in the dioxins-containing incinerated ash can be dissolved in water. Therefore, add water to incinerated ash containing dioxins and stir it with a stirrer, bubbling air, or adding water to incinerated ash containing dioxins and let it stand for a predetermined time without stirring It may be a method. In addition, when disassembling the soil containing a lot of moisture and the incinerator, the incineration ash containing a lot of moisture, such as the recovered incineration ash attached to the wall surface with high-pressure water, without adding new water, Water contained in the workpiece can be used.
脱水操作は、ダイオキシン類含有焼却灰と水との混合物から水を脱水除去するための操作であり、これより無機塩素化合物を含まない含水率の小さいダイオキシン類含有焼却灰を得ることができる。脱水操作は特定の方法に限定されるものではなく、ろ過、沈降分離を用いることができる。この際、水側に出来るだけ固形分が含まれないように固液分離を行うことが重要である。周知のようにダイオキシン類を初め有機ハロゲン化合物は、水への溶解度が非常に小さいため、固液分離を十分に行えば、水側には有機ハロゲン化合物が殆ど含まれることはない。一方、水側に被処理物である固形分が多く含まれると、固形分に有機ハロゲン化合物が含まれているため、水側の処理も必要となることによる。 The dehydration operation is an operation for dehydrating and removing water from a mixture of dioxin-containing incinerated ash and water, and dioxin-containing incinerated ash having a low water content and containing no inorganic chlorine compound can be obtained. The dehydration operation is not limited to a specific method, and filtration and sedimentation can be used. At this time, it is important to perform solid-liquid separation so that the solid content is not contained in the water side as much as possible. As is well known, organic halogen compounds such as dioxins have a very low solubility in water. Therefore, if sufficient solid-liquid separation is carried out, the organic halogen compound is hardly contained on the water side. On the other hand, when the solid content that is the object to be treated is large on the water side, since the organic halogen compound is contained in the solid content, the treatment on the water side is also necessary.
脱水又は固液分離装置としては、加圧ろ過装置、減圧ろ過装置、遠心分離機、沈降槽、フィルタープレス装置などを使用することが可能であり、含水率は低いほど好ましい。但し、ダイオキシン類含有焼却灰の含水率は、後の水分調整工程でも低減させることが可能なため、脱水操作と水分調整操作を一体として考え、効率的かつ安価となるように脱水工程での被処理物の含水率を決めればよい。なお初めから多量の水分を含む被処理物でなく、洗浄操作を行わないときには、脱水工程も必要がない。さらに洗浄操作と脱水操作とを同時に行ってもよい。例えば、ろ材をセットした容器に被処理物であるダイオキシン類含有焼却灰を仕込み、上部から水を注入すれば、洗浄とろ過とを同時に行うことができる。 As the dehydration or solid-liquid separation device, a pressure filtration device, a vacuum filtration device, a centrifuge, a sedimentation tank, a filter press device or the like can be used, and the lower the water content, the better. However, since the water content of the incinerated ash containing dioxins can be reduced in the subsequent moisture adjustment process, the dehydration operation and the moisture adjustment operation are considered as a unit, and the dehydration process can be performed efficiently and inexpensively. What is necessary is just to determine the moisture content of a processed material. Note that a dehydration step is not necessary when the cleaning operation is not performed since the object to be processed does not contain a large amount of moisture from the beginning. Further, the washing operation and the dehydrating operation may be performed simultaneously. For example, if a dioxin-containing incinerated ash that is an object to be treated is charged into a container in which a filter medium is set and water is injected from above, washing and filtration can be performed simultaneously.
水分調整工程は、後のメカノケミカル処理工程に先立ち、被処理物に含まれる水分量を調整するものである。この後に行うメカノケミカル処理工程では、水に少なくとも一部は溶解し電子移動による還元力を有する金属を使用するため、被処理物に含まれる水分量が多いと、それに比例して添加すべき還元力を有する金属の量が多くなる。また被処理物に含まれる水分量が多いと、メカノケミカル処理を行う際、被処理物に機械的、物理的エネルギが加わりにくい。一方、水はプロトン性溶媒として機能し、水素イオンを供与することから、被処理物に全く水が含まれていない状態では、ダイオキシン類の無害化が進まない。これらのことから被処理物であるダイオキシン類含有焼却灰に含まれる水分濃度を０．０５〜２０重量％に調整することが好ましい。 The moisture adjustment step adjusts the amount of moisture contained in the workpiece prior to the subsequent mechanochemical treatment step. In the subsequent mechanochemical treatment process, a metal that is at least partially dissolved in water and has a reducing power by electron transfer is used. The amount of powerful metal increases. In addition, when the amount of moisture contained in the object to be processed is large, it is difficult to add mechanical and physical energy to the object to be processed when mechanochemical processing is performed. On the other hand, since water functions as a protic solvent and donates hydrogen ions, the detoxification of dioxins does not proceed in the state where water is not contained in the object to be treated. From these things, it is preferable to adjust the water concentration contained in the dioxin containing incineration ash which is a to-be-processed object to 0.05 to 20 weight%.
空気中に放置しておくと空気中の水分を吸着する焼却灰、飛灰などがあるが、このような焼却灰、飛灰などにあって、洗浄操作を行う必要のない場合には、何ら水分の調整をすることなくそのまま使用することができる。また、飛散防止のために散水を行っているような場合にも、極端に水分が多い場合を除いて何ら水分調整を行う必要はない。土壌の場合も同様である。一方、洗浄、脱水工程を経た被処理物、始めから多くの水分を含む被処理物にあっては、被処理物から水分を除去する操作を行うことが好ましい。但し先の脱水工程で十分に水分が除去されている場合には、特に水分調整を行う必要はない。水分の除去方法は、特定の方法に限定されるものではないので、乾燥操作を行うことで水分を除去することができる。乾燥操作も特定の方法に限定されないので、セメント工場、レンガ製造工場、溶鉱炉、発電所、焼却炉から排出される廃熱を利用すれば、効率的である。一方、水分を全く含んでいない被処理物にあっては、水を添加すればよい。 If left in the air, there are incineration ash, fly ash, etc. that adsorbs moisture in the air, but if it is in such incineration ash, fly ash, etc., there is no need to perform cleaning operations. It can be used as it is without adjusting the moisture. Further, even when water is sprayed to prevent scattering, it is not necessary to adjust the water content except when the amount of water is extremely high. The same applies to soil. On the other hand, it is preferable to perform an operation of removing moisture from the object to be processed after the cleaning and dehydration processes and the object to be processed that contains a lot of moisture from the beginning. However, when water is sufficiently removed in the previous dehydration step, it is not necessary to adjust the water content. The method for removing moisture is not limited to a specific method, and therefore moisture can be removed by performing a drying operation. Since the drying operation is not limited to a specific method, it is efficient if waste heat discharged from a cement factory, a brick manufacturing factory, a blast furnace, a power plant, or an incinerator is used. On the other hand, in the case of an object to be processed that does not contain any moisture, water may be added.
メカノケミカル処理工程では、適当な水分を含む被処理物、又は洗浄、脱水、水分調整工程を経た被処理物に、水に少なくとも一部は溶解し電子移動による還元力を有する金属を添加し、これらをメカノケミカル処理する。これにより還元力を有する金属と水との化学反応により生成した水素を、還元反応の水素源として被処理物に含まれる有機ハロゲン化合物が脱ハロゲン化される。水に少なくとも一部は溶解し電子移動による還元力を有する金属は、水に溶解し電子を供与することが可能な物質であって、具体的には、アルカリ金属、金属カルシウムなどのアルカリ土類金属、アルミニウムなどの第３族元素、鉄、亜鉛、及びこれら元素を含む合金が例示される。これは単独で使用してもよく、混合して使用してもよい。水に溶解し電子移動による還元力を有する金属の種類は、特に限定されないけれども、金属カルシウムを好適に使用することができる。これら金属の被処理物に対する添加割合は、被処理物に含まれる有機ハロゲン化合物の量、水分、無機塩素化合物の量などにより異なるけれども、後述の実施例で示すように被処理物に対し、重量比で１／１００の量を添加すればよい。この値は、従来の酸化カルシウムを用いたメカノケミカル法で使用する酸化カルシウムの量の１／５〜１／２００程度であり、非常に少ない。この結果、被処理物を処理した後の量が、処理前の被処理物の量と比較しほとんど増加しない。この点は、本発明の特徴の一つである。 In the mechanochemical treatment process, a metal containing an appropriate water content, or a process object that has undergone washing, dehydration, and moisture adjustment process, is added with a metal that has at least a part of the water and has a reducing power by electron transfer, These are mechanochemically processed. As a result, the organic halogen compound contained in the object to be treated is dehalogenated using hydrogen generated by a chemical reaction between a metal having reducing power and water as a hydrogen source for the reduction reaction. A metal that is at least partially dissolved in water and has a reducing power by electron transfer is a substance that can be dissolved in water and donate electrons, specifically, alkaline earths such as alkali metals and metallic calcium Examples include metals, Group 3 elements such as aluminum, iron, zinc, and alloys containing these elements. These may be used alone or in combination. The type of metal dissolved in water and having a reducing power by electron transfer is not particularly limited, but metallic calcium can be preferably used. The addition ratio of these metals to the object to be processed varies depending on the amount of organic halogen compound contained in the object to be processed, moisture, the amount of inorganic chlorine compound, etc. What is necessary is just to add the quantity of 1/100 by ratio. This value is about 1/5 to 1/200 of the amount of calcium oxide used in the mechanochemical method using conventional calcium oxide, and is very small. As a result, the amount after processing the object to be processed hardly increases compared to the amount of the object to be processed before the processing. This is one of the features of the present invention.
本発明でメカノケミカル処理とは、ボールミル、撹拌装置などを用いて機械的に固体に衝突、せん断エネルギなどを加え、固体に化学的変化を生じさせる処理、操作を言い、従来から一般的に用いられている内容と同じである。メカノケミカル処理を可能ならしめる装置としては、特定の装置に限定されないけれども、従来から一般的に使用されている遊星ボールミルを好適に使用することができる。遊星ボールミルの操作条件もメカノケミカル効果を発揮する条件であれば特定の条件に限定されるものではないが、被処理物に与える機械的、物理的エネルギを大きくすれば、脱ハロゲン化を短時間に行うことが可能となる。 In the present invention, mechanochemical treatment refers to a treatment or operation that mechanically impacts a solid using a ball mill, a stirrer, or the like to apply a shearing energy or the like to cause a chemical change in the solid. It is the same as the contents that have been described. The device that enables mechanochemical treatment is not limited to a specific device, but a planetary ball mill that has been generally used in the past can be preferably used. The operation conditions of the planetary ball mill are not limited to specific conditions as long as the mechanochemical effect is exhibited. However, if the mechanical and physical energy applied to the object to be processed is increased, dehalogenation can be performed in a short time. Can be performed.
上記のように本発明の有機ハロゲン化合物を含有する固体の無害化方法は、簡単な操作で、有機ハロゲン化合物を含有する固体を無害化することができる。特に洗浄、脱水及び水分調整操作は必ずしも必要な操作ではないので、ケースによっては、被処理物に金属カルシムを加え、これをメカノケミカル処理することで被処理物を無害化することができる。また、被処理物に添加する、水に少なくとも一部は溶解し電子移動による還元力を有する金属の添加量が非常に少ないため、安価にまた処理に伴い容量をほとんど増加させることなく無害化することができる。 As described above, the method for detoxifying a solid containing an organic halogen compound according to the present invention can detoxify a solid containing an organic halogen compound by a simple operation. In particular, since washing, dehydration and moisture adjustment operations are not necessarily required operations, depending on the case, it is possible to detoxify the workpiece by adding metal calcium to the workpiece and subjecting it to mechanochemical treatment. In addition, the amount of metal added to the material to be treated, which is at least partially dissolved in water and has a reducing power due to electron transfer, is very small, making it harmless at low cost and with little increase in capacity due to processing. be able to.
また用途によっては、被処理物の脱ハロゲン化率をほぼ１００％としたいとの要求もある。この場合、被処理物の性状によっては、上記工程だけでは脱ハロゲン化率を１００％近傍にすることができない場合も想定されるが、このような場合は、上記工程に引続き、溶媒抽出を行えばよい。溶媒抽出は、上記工程が終了した被処理物に、有機ハロゲン化合物を溶解させる、例えばトルエン、プロパノール又はこれら混合物などの溶媒を加え、この溶媒に残留する有機ハロゲン化合物を溶解させることで行う。溶媒抽出が終了した後、溶媒と被処理物とを分離すればよい。これにより被処理物の脱ハロゲン化率をほぼ１００％とすることができる。なお、処理後の溶媒は、例えば本発明者らが取得した特許第３７８５５５６号公報に記載の方法で無害化すればよい。 Further, depending on the application, there is a demand for the dehalogenation rate of the object to be processed to be almost 100%. In this case, depending on the properties of the material to be treated, it may be assumed that the dehalogenation rate cannot be made close to 100% only by the above process. In such a case, solvent extraction is performed following the above process. Just do it. The solvent extraction is performed by adding a solvent such as toluene, propanol, or a mixture thereof, which dissolves the organic halogen compound, to the object to be processed after the above-described process is completed, and dissolving the remaining organic halogen compound in the solvent. After the solvent extraction is completed, the solvent and the object to be processed may be separated. Thereby, the dehalogenation rate of a to-be-processed object can be made into 100%. In addition, what is necessary is just to detoxify the solvent after a process, for example by the method as described in the patent 3785556 which the present inventors acquired.
実施例１
ダイオキシン類濃度４０００ｐｇＴＥＱ／ｇ、含水率１．１重量％の焼却灰１０．０ｇに蒸留水１０００ｍｌを加え、最大出力６００Ｗの超音波洗浄機を用いて３０分間超音波洗浄を行った。その後、０．４５μｍのメンブレンフィルタを用いて吸引ろ過を行った。吸引ろ過後の焼却灰の含水率は３２．６％重量％であった。この焼却灰を真空乾燥し、５．６０７７ｇの乾燥焼却灰を得た。この乾燥焼却灰の含水率は１．４重量％であった。含水率は、ＪＩＳ法に従って求めた。この乾燥焼却灰５．６０７７ｇに対して金属カルシウムを重量比で１／１００添加し、これらを遊星ボールミル（Ｒｅｔｓｃｈ社製）を用いてメカノケミカル処理した。遊星ボールミルの操作条件は、室温下で、公自転比＝１／−２、回転数４００ｒｐｍ、ボールの数２０個、処理時間２０時間で行った。その結果、真空乾燥後の焼却灰（乾燥焼却灰）中のダイオキシン類の濃度は５２００ｐｇＴＥＱ／ｇであり、メカノケミカル処理を行った後の焼却灰中のダイオキシン類濃度は、９００ｐｇＴＥＱ／ｇであった。
Example 1
1000 ml of distilled water was added to 10.0 g of incinerated ash having a dioxin concentration of 4000 pgTEQ / g and a water content of 1.1 wt%, and ultrasonic cleaning was performed for 30 minutes using an ultrasonic cleaner with a maximum output of 600 W. Thereafter, suction filtration was performed using a 0.45 μm membrane filter. The water content of the incinerated ash after suction filtration was 32.6% by weight. This incineration ash was vacuum-dried to obtain 5.6077 g of dry incineration ash. The moisture content of the dry incinerated ash was 1.4% by weight. The water content was determined according to the JIS method. Metal calcium was added 1/100 by weight to 5.6077 g of this dry incinerated ash, and these were mechanochemically processed using a planetary ball mill (manufactured by Retsch). The operating conditions of the planetary ball mill were room temperature, revolution ratio = 1 / −2, rotation speed 400 rpm, number of balls 20 and treatment time 20 hours. As a result, the concentration of dioxins in the incineration ash (dry incineration ash) after vacuum drying was 5200 pgTEQ / g, and the concentration of dioxins in the incineration ash after mechanochemical treatment was 900 pgTEQ / g. .
実施例２
実施例１のメカノケミカル処理後の被処理物に１−プロパノール５０重量％＋トルエン５０重量％の混合溶媒を加え、溶媒抽出を行った。その後溶媒を除去し被処理物（焼却灰）中のダイオキシン類の濃度を測定した結果、ダイオキシン類の濃度は、７９ｐｇＴＥＱ／ｇであった。
Example 2
A solvent mixture was extracted by adding a mixed solvent of 50% by weight of 1-propanol + 50% by weight of toluene to the workpiece after the mechanochemical treatment of Example 1. Thereafter, the solvent was removed, and the concentration of dioxins in the object to be treated (incinerated ash) was measured. As a result, the concentration of dioxins was 79 pgTEQ / g.
実施例３
実施例１と同じ要領で得た乾燥焼却灰１０．００３６ｇに対してアルミニウムを重量比で１／１００添加し、これらを遊星ボールミル（Ｒｅｔｓｃｈ社製）を用いてメカノケミカル処理した。遊星ボールミルの操作条件は、実施例１と同じであり、室温下で、公自転比＝１／−２、回転数４００ｒｐｍ、ボールの数２０個、処理時間２０時間で行った。その結果、メカノケミカル処理を行った後の焼却灰中のダイオキシン類濃度は、３３００ｐｇＴＥＱ／ｇであった
Example 3
Aluminum was added 1/100 by weight to 10.0036 g of dry incinerated ash obtained in the same manner as in Example 1, and these were mechanochemically treated using a planetary ball mill (manufactured by Retsch). The operating conditions of the planetary ball mill were the same as those in Example 1, and were carried out at room temperature with a revolution ratio = 1 / -2, a rotation speed of 400 rpm, a number of balls of 20, and a treatment time of 20 hours. As a result, the concentration of dioxins in the incinerated ash after the mechanochemical treatment was 3300 pgTEQ / g.
比較例１
ダイオキシン類濃度が４０００ｐｇＴＥＱ／ｇ、含水率１．１重量％の焼却灰１０．０ｇを、洗浄、脱水、乾燥することなく、かつ金属カルシウムを添加することなく遊星ボールミル（Ｒｅｔｓｃｈ社製）を用いてメカノケミカル処理した。遊星ボールミルの操作条件は、室温下で、公自転比＝１／−２、回転数４００ｒｐｍ、ボールの数２０個、処理時間２０時間で行った。その結果、焼却灰中のダイオキシン類濃度は、５２００ｐｇＴＥＱ／ｇであった。
Comparative Example 1
Using a planetary ball mill (manufactured by Retsch), 10.0 g of incinerated ash with a dioxin concentration of 4000 pgTEQ / g and a moisture content of 1.1 wt% is not washed, dehydrated, dried, and without adding metallic calcium. Mechanochemical treatment. The operating conditions of the planetary ball mill were room temperature, revolution ratio = 1 / −2, rotation speed 400 rpm, number of balls 20 and treatment time 20 hours. As a result, the concentration of dioxins in the incinerated ash was 5200 pgTEQ / g.
表１に実施例１から実施例３及び比較例１の結果をまとめて示した。
Claims (6)
前記水は、焼却灰、焼却飛灰、土壌又はこれらの混合物に予め含まれている水、又はこれら処理対象物を空気中に放置したとき吸着する水であることを特徴とする請求項１に記載の有機ハロゲン化合物を含有する固体の無害化方法。 The solid containing the organic halogen compound is incineration ash, incineration fly ash, soil or a mixture thereof,
2. The water according to claim 1, wherein the water is water preliminarily contained in incineration ash, incineration fly ash, soil or a mixture thereof, or water adsorbed when these treatment objects are left in the air. A method for detoxifying a solid containing the described organohalogen compound.
洗浄脱水した水を含む有機ハロゲン化合物を含有する固体に、水に少なくとも一部は溶解し電子移動による還元力を有する金属を添加し、これら混合物をメカノケミカル処理し、前記有機ハロゲン化合物を脱ハロゲン化するメカノケミカル処理工程と、
を含むことを特徴とする有機ハロゲン化合物を含有する固体の無害化方法。 A washing and dehydration step of washing and dehydrating a solid containing an organic halogen compound with water;
A metal containing an organic halogen compound including water that has been washed and dehydrated is added with a metal that is at least partially dissolved in water and has a reducing power by electron transfer, and the mixture is mechanochemically treated to dehalogenate the organic halogen compound. A mechanochemical treatment process,
A method for detoxifying a solid containing an organic halogen compound, comprising:
水分調整を行った後に、前記水に少なくとも一部は溶解し電子移動による還元力を有する金属を添加し、これをメカノケミカル処理することを特徴とする請求項１から３のいずれか１に記載の有機ハロゲン化合物を含有する固体の無害化方法。 And further comprising a moisture adjustment step of drying the solid containing the organic halogen compound or adding water,
The metal according to any one of claims 1 to 3, wherein after the moisture adjustment, a metal having at least a part dissolved in the water and having a reducing power by electron transfer is added and mechanochemically treated. A method for detoxifying a solid containing an organic halogen compound.
溶媒抽出後の抽出溶媒を分離する溶媒分離工程と、
を含むことを特徴とする請求項１から５のいずれか１に記載の有機ハロゲン化合物を含有する固体の無害化方法。 Further, a solvent extraction step of adding a solvent to the object to be processed after mechanochemical treatment and extracting the remaining organic halogen compound,
A solvent separation step for separating the extraction solvent after solvent extraction;
The method for detoxifying a solid containing an organohalogen compound according to any one of claims 1 to 5, wherein
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011161218A (en) * | 2010-01-14 | 2011-08-25 | Prefectural Univ Of Hiroshima | Detoxification method of solid containing organohalogen compound |
| JP2012224926A (en) * | 2011-04-21 | 2012-11-15 | Tohoku Univ | Method for producing rare metal |
| KR20140126335A (en) * | 2012-02-17 | 2014-10-30 | 시오노 케미컬 가부시키가이샤 | Method for producing hydrogen or deuterium, method for producing hydrogenated or deuterated organic compound, method for hydrogenating or deterating organic compound, method for dehalogenating organic compound having halogen, and ball for use in mechanochemical reaction |
| EP2607300A4 (en) * | 2010-08-18 | 2017-05-31 | Shiono Chemical Co., Ltd. | Process for producing hydrogen or heavy hydrogens, and hydrogenation (protiation, deuteration or tritiation) of organic compounds using same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011161218A (en) * | 2010-01-14 | 2011-08-25 | Prefectural Univ Of Hiroshima | Detoxification method of solid containing organohalogen compound |
| EP2607300A4 (en) * | 2010-08-18 | 2017-05-31 | Shiono Chemical Co., Ltd. | Process for producing hydrogen or heavy hydrogens, and hydrogenation (protiation, deuteration or tritiation) of organic compounds using same |
| US9676622B2 (en) | 2010-08-18 | 2017-06-13 | Shiono Chemical Co., Ltd. | Process for producing hydrogen or heavy hydrogens, and hydrogenation (protiation, deuteration or tritiation) of organic compounds using same |
| JP2012224926A (en) * | 2011-04-21 | 2012-11-15 | Tohoku Univ | Method for producing rare metal |
| KR20140126335A (en) * | 2012-02-17 | 2014-10-30 | 시오노 케미컬 가부시키가이샤 | Method for producing hydrogen or deuterium, method for producing hydrogenated or deuterated organic compound, method for hydrogenating or deterating organic compound, method for dehalogenating organic compound having halogen, and ball for use in mechanochemical reaction |
| JPWO2013121997A1 (en) * | 2012-02-17 | 2015-05-11 | シオノケミカル株式会社 | Method for producing hydrogen or deuterium, method for producing hydrogenated or deuterated organic compound, method for hydrogenating or deuterating organic compound, method for dehalogenating halogen-containing organic compound, ball for mechanochemical reaction |
| KR102003095B1 (en) * | 2012-02-17 | 2019-07-23 | 시오노 케미컬 가부시키가이샤 | Method for producing hydrogen or heavy hydrogens |
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