JP2006198549A - Method and apparatus for treating exhaust gas, and method for treating substance contaminated with agricultural chemicals - Google Patents

Method and apparatus for treating exhaust gas, and method for treating substance contaminated with agricultural chemicals Download PDF

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JP2006198549A
JP2006198549A JP2005014352A JP2005014352A JP2006198549A JP 2006198549 A JP2006198549 A JP 2006198549A JP 2005014352 A JP2005014352 A JP 2005014352A JP 2005014352 A JP2005014352 A JP 2005014352A JP 2006198549 A JP2006198549 A JP 2006198549A
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exhaust gas
oil
temperature
cleaning
treating
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Yoshiaki Murakami
吉明 村上
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Shinko Pantec Co Ltd
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Kobelco Eco Solutions Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To prevent a scale in a pipe from adhering when an exhaust gas is treated which is generated during thermal treatment of a contaminated substance such as soil contaminated with agricultural chemicals. <P>SOLUTION: A method for treating the exhaust gas that is generated by the thermal treatment of the contaminated substance contaminated with the agricultural chemicals comprises a high-temperature oil cleaning process which brings a high-temperature cleaning oil of 100°C or higher into gas-liquid contact with a high-temperature exhaust gas of 120°C or higher. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、排ガス処理方法および排ガス処理設備、並びに農薬汚染物質の処理方法に関する。   The present invention relates to an exhaust gas treatment method, an exhaust gas treatment facility, and a method for treating agricultural chemical contaminants.

農薬には、DDT、BHC、ドリン剤のような有機塩素系を始めとして、有機リン酸エステル系、有機硫黄剤、天然殺虫剤など、用途に応じて多種多様なものが使用されている。これらの農薬のうち、有機塩素系農薬等は、残留性が高く人体に対しても慢性毒性を生じやすいことが明らかとなり、現在ではその使用が禁止されている。
これらの農薬は、使用が禁止された以降、残存しているものは地中に埋設され、又は農家等で保管されたまま放置され、あるいは農薬の製造メーカーが回収して保管しているのが現状であり、これらの農薬は使用残農薬とも称されている。この使用残農薬については、近年採択されたストックホルム条約により、今後計画的に処理することが求められている。
A wide variety of pesticides are used depending on applications, such as organic chlorine-based organic compounds such as DDT, BHC, and drins, organic phosphate esters, organic sulfur agents, and natural insecticides. Among these pesticides, organochlorine pesticides and the like are known to have high persistence and are likely to cause chronic toxicity to the human body, and their use is now prohibited.
Since these pesticides have been banned, the remaining ones are either buried in the ground, left as they are stored by farmers, or collected and stored by pesticide manufacturers. At present, these pesticides are also called residual agricultural chemicals. This residual agricultural chemical is required to be systematically treated in the future according to the Stockholm Convention recently adopted.

前記有機塩素系農薬は、ダイオキシンやポリ塩化ビフェニル(PCB)等と同じく、広義には有機ハロゲン化合物に含まれるものであるため、上記のような使用残農薬や、農薬によって汚染された土壌等(本発明において、これらを総称して「農薬汚染物質」という)についても、有機ハロゲン化合物で汚染された汚染物質と同様の処理方法を適用することが考えられる。
有機ハロゲン化合物で汚染された汚染物質については、従来、例えば特許文献1に記載のように、還元雰囲気中で汚染物質を加熱することによって有機ハロゲン化合物を分解処理する方法が知られている。
また、該汚染物質を加熱処理した際に排出される排ガスについては、従来、例えば特許文献2に記載のように、洗浄油と気液接触させて排ガス中の有機ハロゲン化合物等を分離処理し、次いで活性炭によって吸着処理する方法が開示されている。
The organochlorine pesticides are included in the organic halogen compounds in a broad sense, like dioxins and polychlorinated biphenyls (PCB). Therefore, the residual agricultural chemicals used as described above, soil contaminated with pesticides, etc. ( In the present invention, it is conceivable to apply the same treatment method as that for pollutants contaminated with organic halogen compounds to these as “agrochemical contaminants”.
As for pollutants contaminated with an organic halogen compound, a method of decomposing an organic halogen compound by heating the pollutant in a reducing atmosphere has been conventionally known, as described in Patent Document 1, for example.
In addition, for the exhaust gas discharged when the pollutant is heat-treated, conventionally, for example, as described in Patent Document 2, the organic halogen compound or the like in the exhaust gas is separated and processed by contact with cleaning oil, Next, a method of adsorption treatment with activated carbon is disclosed.

特開2003−95990号公報JP 2003-95990 A 特開2003−225643号公報Japanese Patent Laid-Open No. 2003-225643

しかしながら、本発明者らが、農薬汚染物質を上記のような有機ハロゲン化合物に係る従来の方法で処理しようと試みたところ、該農薬汚染物質の加熱処理工程から排出される排ガスの配管等に多量のスケールが付着してしまい、運転に支障を来たすことを見出した。しかも、このようなスケールの付着は、排ガスと洗浄油との気液接触工程の付近において最も顕著であることを見出した。   However, when the present inventors tried to treat the agricultural chemical pollutant by the conventional method related to the organic halogen compound as described above, a large amount of the exhaust gas discharged from the heat treatment process of the agricultural chemical pollutant is large. It was found that the scales of the machine were attached and hindered driving. Moreover, it has been found that such scale adhesion is most noticeable in the vicinity of the gas-liquid contact process between the exhaust gas and the cleaning oil.

そこで本発明は、上記のような問題点に鑑みてなされたものであり、農薬汚染物質を加熱処理した際に生じる排ガスを処理するにあたり、配管等にスケールが付着するのを防止することを一の課題とする。   Accordingly, the present invention has been made in view of the above-described problems, and it is possible to prevent the scale from adhering to piping or the like when treating exhaust gas generated when heat treating agricultural chemical contaminants. It is an issue.

前記課題を解決すべく発明者らが鋭意研究したところ、上記のような汚染物質を加熱処理すると農薬又はその分解物(以下、これらを総称して農薬等ともいう)が比較的高濃度で含まれた排ガスが発生すること、及び洗浄油により排ガスの大幅な温度低下が起こってしまい、その結果として、気液接触工程への導入部付近において多量のスケール付着を招来させていることを見出した。
即ち、本発明は、農薬汚染物質の加熱処理によって生じる排ガスの処理方法において、100℃以上の高温の洗浄油と前記加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄工程を備えたことを特徴とする。また、本発明は、農薬に汚染された汚染物質を加熱処理する際に生じる排ガスの処理設備において、100℃以上の高温の洗浄油と前記加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄手段を備えたことを特徴とする。
As a result of extensive research conducted by the inventors to solve the above-mentioned problems, when the above-mentioned contaminants are heat-treated, pesticides or decomposition products thereof (hereinafter collectively referred to as pesticides) are contained at a relatively high concentration. It has been found that exhaust gas is generated and that the temperature of the exhaust gas is greatly lowered by the cleaning oil, resulting in a large amount of scale adhesion in the vicinity of the introduction to the gas-liquid contact process. .
That is, the present invention relates to a method for treating exhaust gas generated by heat treatment of agricultural chemical pollutants, and a high-temperature oil that makes gas-liquid contact between high-temperature cleaning oil of 100 ° C. or higher and high-temperature exhaust gas of 120 ° C. or higher generated by the heat treatment A cleaning process is provided. In addition, the present invention provides a treatment facility for exhaust gas generated when heat treating a pollutant contaminated with agricultural chemicals, cleaning oil at a high temperature of 100 ° C. or higher and exhaust gas at a high temperature of 120 ° C. or higher generated by the heat treatment. A high-temperature oil cleaning means for contacting with gas and liquid is provided.

100℃以上の高温の洗浄油と農薬汚染物質の加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させることにより、排ガスの温度低下が防止されるため、農薬等の析出によるスケールの発生を抑制することができる。   Since the temperature drop of the exhaust gas is prevented by gas-liquid contact between the high-temperature cleaning oil of 100 ° C. or higher and the exhaust gas in a high temperature state of 120 ° C. or higher generated by the heat treatment of the agricultural chemical pollutant, the scale due to precipitation of agricultural chemicals, etc. Can be suppressed.

本発明においては、好ましくは前記高温油洗浄工程を経た排ガスを冷却し、洗浄油を凝縮させる凝縮工程を備える。
高温油洗浄工程を経た排ガスを冷却して洗浄油を凝縮させることにより、該洗浄油を排ガスから分離回収して再利用できるのみならず、排ガス中に残留している極めて微量の農薬等も冷却されて洗浄油中に溶解又は析出し、洗浄油とともに排ガス中から分離回収することができる。
The present invention preferably includes a condensation step of cooling the exhaust gas that has undergone the high temperature oil washing step and condensing the washing oil.
By cooling the exhaust gas that has passed through the high-temperature oil cleaning process and condensing the cleaning oil, the cleaning oil can be separated and recovered from the exhaust gas and reused, as well as extremely small amounts of agricultural chemicals remaining in the exhaust gas. And dissolved or precipitated in the cleaning oil, and separated and recovered from the exhaust gas together with the cleaning oil.

本発明においては、好ましくは前記高温油洗浄工程を経た排ガスと、50℃以下の低温の洗浄油とを気液接触させる低温油洗浄工程を備える。高温油洗浄工程を経た排ガスと、50℃以下の低温の洗浄油とを気液接触させる低温油洗浄工程を備えたことにより、排ガス中に含まれる洗浄油を凝縮させて分離し、しかも排ガス中に残留している極めて微量の農薬等も除去することができる。また、前段に高温油洗浄工程を備えており、排ガス中の農薬等は十分に除去されているため、該低温油洗浄工程においてはスケールの付着が問題となることもない。   The present invention preferably includes a low-temperature oil cleaning step in which the exhaust gas that has undergone the high-temperature oil cleaning step and a low-temperature cleaning oil of 50 ° C. or less are in gas-liquid contact. By providing a low-temperature oil cleaning process that makes gas-liquid contact between the exhaust gas that has undergone the high-temperature oil cleaning process and a low-temperature cleaning oil of 50 ° C. or less, the cleaning oil contained in the exhaust gas is condensed and separated, and in the exhaust gas It is possible to remove a very small amount of agricultural chemicals remaining on the surface. Moreover, since the high temperature oil washing | cleaning process is provided in the front | former stage and the pesticide etc. in exhaust gas are fully removed, adhesion of a scale does not become a problem in this low temperature oil washing | cleaning process.

本発明においては、好ましくは前記高温油洗浄工程を曝気方式とする。洗浄油中に排ガスを曝気させる曝気方式を採用することにより、該高温油洗浄工程において排ガスの温度低下をより確実に防止でき、スケールの付着をより確実に防止できる。   In the present invention, the high temperature oil washing step is preferably an aeration method. By adopting an aeration system in which the exhaust gas is aerated in the cleaning oil, it is possible to more reliably prevent the temperature of the exhaust gas from decreasing in the high-temperature oil cleaning step, and to more reliably prevent the scale from adhering.

本発明においては、好ましくは前記低温油洗浄工程をスクラバー方式とする。排ガス中に洗浄油を散布するスクラバー方式を採用することにより、排ガスとの接触面積を大きくでき、気液間での熱交換効率を高くすることができる。その結果、排ガスの温度を効率よく低下させることができる。   In the present invention, the low temperature oil washing step is preferably a scrubber system. By adopting a scrubber system for spraying cleaning oil into the exhaust gas, the contact area with the exhaust gas can be increased, and the heat exchange efficiency between the gas and liquid can be increased. As a result, the temperature of the exhaust gas can be efficiently reduced.

本発明においては、好ましくは前記高温油洗浄工程における洗浄油の温度を、150〜160℃とする。斯かる温度の洗浄油を用いれば、排ガス流量が低下して配管出口付近で排ガス温度が低下した場合であっても、該洗浄油と接触する配管が150〜160℃に保たれることとなり、スケールの付着をより確実に防止することができる。   In this invention, Preferably the temperature of the washing | cleaning oil in the said high temperature oil washing | cleaning process shall be 150-160 degreeC. If the cleaning oil at such a temperature is used, even if the exhaust gas flow rate decreases and the exhaust gas temperature decreases near the piping outlet, the piping that contacts the cleaning oil will be maintained at 150 to 160 ° C. Scale adhesion can be more reliably prevented.

さらに、本発明は、農薬汚染物質を加熱処理する加熱処理工程と、100℃以上の高温の洗浄油と前記加熱処理工程によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄工程を備えたことを特徴とする農薬汚染物質の処理方法を提供する。   Furthermore, the present invention provides a heat treatment step for heat-treating a pesticide contaminant, a high-temperature oil wash that causes gas-liquid contact between a high-temperature cleaning oil of 100 ° C. or higher and a high-temperature exhaust gas of 120 ° C. or higher generated by the heat treatment step. Provided is a method for treating agricultural chemical pollutants characterized by comprising a process.

本発明に係る農薬汚染物質の処理方法によれば、100℃以上の高温の洗浄油と農薬汚染物質の加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させることにより、排ガスの温度低下が防止され、農薬等の析出によるスケールの発生を抑制でき、農薬汚染物質を好適に処理することができる。   According to the method for treating agricultural chemical pollutants according to the present invention, the exhaust gas in the exhaust gas is brought into gas-liquid contact with a high-temperature cleaning oil of 100 ° C. or higher and a high temperature exhaust gas of 120 ° C. or higher generated by the heat treatment of the agricultural chemical pollutants. Temperature drop is prevented, generation of scale due to precipitation of agricultural chemicals and the like can be suppressed, and agricultural chemical contaminants can be appropriately treated.

以上のように、本発明に係る排ガス処理方法および排ガス処理設備、並びに農薬汚染物質の処理方法によれば、農薬汚染物質の加熱処理によって生じる排ガスを無害化処理するに際し、排ガスの配管等にスケールが付着するのを防止することができ、農薬汚染物質の処理に支障を来たす虞も無い。   As described above, according to the exhaust gas treatment method, the exhaust gas treatment facility, and the agricultural chemical pollutant treatment method according to the present invention, when exhaust gas generated by heat treatment of agricultural chemical pollutants is detoxified, the exhaust gas is scaled to the exhaust pipes and the like. Can be prevented, and there is no risk of hindering the treatment of the pesticide contaminants.

以下、本発明の実施形態について説明する。
図1は、本発明に係る農薬汚染物質の処理方法および排ガス処理方法の一実施形態を示した概略フロー図である。図1に示すように、本実施形態の処理方法は、農薬汚染物質Aを加熱して処理する加熱処理工程2と、前記加熱処理工程2より排出された排ガスB中のダストを除去する集塵工程3と、該集塵工程3を経て依然120℃以上の高温状態にある排ガスBと100℃以上の高温の洗浄油とを気液接触させる高温油洗浄工程4と、該高温油洗浄工程4から排出された排ガスと50℃以下の低温の洗浄油とを気液接触させる低温油洗浄工程5と、前記高温油洗浄工程4から排出される洗浄油Bを無害化する無害化工程6とを備える。
Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a schematic flow diagram showing an embodiment of a method for treating agricultural chemical contaminants and an exhaust gas treatment method according to the present invention. As shown in FIG. 1, the treatment method of the present embodiment includes a heat treatment process 2 for heating and treating a pesticide contaminant A, and dust collection for removing dust in the exhaust gas B discharged from the heat treatment process 2. Step 3, a high temperature oil cleaning step 4 in which the exhaust gas B still in a high temperature state of 120 ° C. or higher after the dust collection step 3 and a high temperature cleaning oil of 100 ° C. or higher are in gas-liquid contact, and the high temperature oil cleaning step 4 A low-temperature oil cleaning step 5 in which the exhaust gas discharged from the gas and a low-temperature cleaning oil of 50 ° C. or less are brought into gas-liquid contact, and a detoxification step 6 for detoxifying the cleaning oil B discharged from the high-temperature oil cleaning step 4 Prepare.

加熱処理工程2は、農薬汚染物質Aを好ましくは還元雰囲気下(具体的には酸素濃度が3体積%以下、好ましくは1体積%以下)において、所望の温度(例えば、350〜600℃、好ましくは450〜600℃)に加熱し、汚染物質Aに含まれる農薬を熱分解するものである。該加熱処理工程において用いられる加熱処理装置としては、例えば、汚染物質Aを内部で加熱する加熱炉と、該加熱炉の周壁に配されたジャケットとを備え、該ジャケットに供給される熱媒体によって汚染物質Aを上記の所望の温度に加熱しうる構成のものが挙げられる。また、好ましくは、該加熱炉内を還元雰囲気とするべく、例えば窒素ガス等の不活性ガスが供給されるように構成される。
また、加熱処理工程2においては、汚染物質Aが農薬以外の有機物を多く含む場合に該有機物の酸化処理を行なうべく、前段に酸化雰囲気(空気)を導入して加熱する酸化処理部を備え、該加熱処理工程の前段において酸化処理し、後段において還元処理するようにしてもよい。
斯かる加熱処理工程2からは、350〜600℃という高温の排ガスBが排出される。
In the heat treatment step 2, the pesticide contaminant A is preferably reduced under a reducing atmosphere (specifically, the oxygen concentration is 3% by volume or less, preferably 1% by volume or less) at a desired temperature (eg, 350 to 600 ° C., preferably Is heated to 450-600 ° C. to thermally decompose the pesticide contained in the pollutant A. The heat treatment apparatus used in the heat treatment step includes, for example, a heating furnace for heating the pollutant A inside, and a jacket disposed on the peripheral wall of the heating furnace, and a heat medium supplied to the jacket The thing of the structure which can heat the pollutant A to said desired temperature is mentioned. Preferably, an inert gas such as nitrogen gas is supplied so that the inside of the heating furnace has a reducing atmosphere.
In addition, in the heat treatment step 2, when the pollutant A contains a large amount of organic substances other than agricultural chemicals, an oxidation treatment unit is provided that introduces an oxidizing atmosphere (air) and heats the organic substances in order to perform oxidation treatment of the organic substances. The oxidation treatment may be performed before the heat treatment step, and the reduction treatment may be performed after the heat treatment step.
From such heat treatment step 2, exhaust gas B having a high temperature of 350 to 600 ° C. is discharged.

集塵工程3は、前記加熱処理工程2から排出された排ガスB中のダストを集塵し、除去する工程である。該集塵工程において用いられる集塵装置としては、例えば、排ガスB中のダストを遠心力により集塵し除去する高温式サイクロンと、該高温式サイクロンを経た排ガス中のダストを濾過により除去する高温式バグフィルターとを併用したものが挙げられる。集塵されたダストは、前記加熱処理工程2へと戻され、再度加熱処理される。   The dust collection process 3 is a process of collecting and removing dust in the exhaust gas B discharged from the heat treatment process 2. Examples of the dust collector used in the dust collecting process include a high temperature cyclone that collects and removes dust in the exhaust gas B by centrifugal force, and a high temperature that removes dust in the exhaust gas that has passed through the high temperature cyclone by filtration. A combination with an expression bug filter can be mentioned. The collected dust is returned to the heat treatment step 2 and is heat-treated again.

高温油洗浄工程4は、前記加熱処理工程2から排出され集塵工程3を経て、依然として120℃以上の高温状態(好ましくは、150〜160℃)にある排ガスBと100℃以上の高温の洗浄油とを気液接触させることにより、該排ガス中の農薬等を除去する工程である。該高温油洗浄工程4において排ガスBと洗浄油Cとを接触させる方式については特に限定されず、例えば、高温の洗浄油C中に高温の排ガスを曝気させて排ガスと洗浄油とを気液接触させるように曝気方式や、排ガス中に洗浄油を噴霧して洗浄油と排ガスとを気液接触させるスクラバー方式などを採用できる。その他にも、ロートクロン方式、エジェクター方式、回転噴霧塔方式、ベンチュリー方式などを例示できる。
これらのうち、特に好ましくは、図1に示したような曝気方式を採用することができる。曝気方式であれば、高温の洗浄油によって排ガスBや配管等の温度が維持されやすく、排ガスの温度低下によるスケールの付着をより確実に防止できる。
The high-temperature oil washing step 4 is exhausted from the heat treatment step 2 and passed through the dust collection step 3, and the exhaust gas B still in a high temperature state of 120 ° C. or higher (preferably 150 to 160 ° C.) and a high temperature wash of 100 ° C. or higher. This is a step of removing agricultural chemicals and the like in the exhaust gas by bringing the oil into gas-liquid contact. The method for bringing the exhaust gas B and the cleaning oil C into contact with each other in the high temperature oil cleaning step 4 is not particularly limited. For example, the high temperature exhaust oil is aerated in the high temperature cleaning oil C and the exhaust gas and the cleaning oil are brought into gas-liquid contact. It is possible to employ an aeration method, a scrubber method in which cleaning oil is sprayed into exhaust gas and the cleaning oil and exhaust gas are brought into gas-liquid contact. Other examples include a rotoclon system, an ejector system, a rotary spray tower system, and a venturi system.
Among these, it is particularly preferable to employ an aeration system as shown in FIG. If it is an aeration system, it is easy to maintain the temperature of exhaust gas B, piping, etc. with a high temperature washing oil, and it can prevent more reliably the scale adhesion by the temperature fall of exhaust gas.

斯かる高温油洗浄工程4において用いる洗浄油Cとしては、排ガスB中の農薬等を溶解しうるものであれば特に限定されず、鎖式の炭化水素、芳香族炭化水素、脂環式炭化水素などの各種の炭化水素油を使用することができる。後段の処理において、汚染油をNa分散体を利用して無害化する際には、有機ハロゲン化合物を溶解させつつ、Na分散体と反応しにくいものが好ましく、炭素数9〜13のノルマルパラフィン(直鎖式の炭化水素)を好適に使用することができる。また、本発明においては、芳香族系炭化水素、又は脂環式炭化水素からなる溶剤も、好適に使用することができる。これは、処理対象となる農薬等、特に、BHC、HCB、ドリン剤、DDTなどが芳香族系又は脂環式状の構造であることから、洗浄油としても芳香族系や脂環式の炭化水素を用いることにより、農薬等を速やかに溶解しうるためである。芳香族系炭化水素および脂環式炭化水素の具体例としては、キシレン、ジメチルベンゼン等を挙げることができ、市販品としては、商品名「EMクリーン」(ジャパンエナジー社製)等を挙げることができる。
特に、除去対象である農薬等との沸点差が大きい方が、蒸留によって洗浄油と農薬等とを容易に分離することができる点で好ましく、また、洗浄油の沸点が水よりも低いと、蒸留による水と油の分離が困難となることから、沸点100℃以上の炭化水素系溶剤が好ましく、沸点170℃以上の炭化水素系溶剤がより好ましい。
The washing oil C used in the high temperature oil washing step 4 is not particularly limited as long as it can dissolve the agricultural chemicals in the exhaust gas B, and is a chain hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon. Various hydrocarbon oils such as can be used. In the subsequent treatment, when decontaminating the contaminated oil using the Na dispersion, it is preferable to dissolve the organic halogen compound and hardly react with the Na dispersion. The normal paraffin having 9 to 13 carbon atoms ( Straight chain hydrocarbons) can be preferably used. In the present invention, a solvent comprising an aromatic hydrocarbon or an alicyclic hydrocarbon can also be suitably used. This is because the agricultural chemicals to be treated, in particular, BHC, HCB, drins, DDT, etc. have an aromatic or alicyclic structure, so that aromatic or alicyclic carbonization can be used as a cleaning oil. This is because pesticides and the like can be dissolved quickly by using hydrogen. Specific examples of aromatic hydrocarbons and alicyclic hydrocarbons include xylene and dimethylbenzene, and commercially available products include “EM Clean” (manufactured by Japan Energy). it can.
In particular, it is preferable that the difference in boiling point with the agricultural chemicals to be removed is larger in that the cleaning oil and the agricultural chemicals can be easily separated by distillation, and when the boiling point of the cleaning oil is lower than that of water, Since separation of water and oil by distillation becomes difficult, a hydrocarbon solvent having a boiling point of 100 ° C. or higher is preferable, and a hydrocarbon solvent having a boiling point of 170 ° C. or higher is more preferable.

該高温油洗浄工程4における洗浄油Cの温度は100℃以上であればよく、好ましくは150〜160℃とする。
該高温油洗浄工程において洗浄油Cに水か混入すると、該洗浄油Cをアルカリ金属分散体によって処理する際に混入した水とアルカリ金属とが反応してアルカリ金属が浪費してしまうため、洗浄油Cをアルカリ金属で処理する前に、蒸留等によって油水分離する必要がある。しかし、本発明の処理対象である農薬等は同様の工程において従来処理対象とされていたPCB等に比べて沸点が低く、また、高温油洗浄工程の洗浄油には農薬等が高濃度で含まれていることから、蒸留によって回収される水に対しても高度の無害化処理が必要となる。
しかし、洗浄油Cの温度が100℃以上であれば、農薬等の析出によるスケールの付着を防止しうるのみならず、排ガスB中に含まれる水蒸気が凝縮して洗浄油Cに混入することがない。従って、該洗浄油Cをアルカリ金属分散体によって処理する際には、水との反応でアルカリ金属が浪費するのを防止でき、油水分離工程なども不要となる。
さらに、洗浄油Cの温度が150〜160℃であれば、加熱処理工程から排出される排ガス流量が低下し、配管出口付近(即ち、高温油洗浄工程への導入部)で排ガス温度が低下した場合であっても、該洗浄油と接触する配管が150〜160℃に保たれることとなり、スケールの付着をより確実に防止することができる。
また、温度の上限を160℃とすることにより、洗浄油の蒸気圧が高くなりすぎず、洗浄油自体の揮発を防止でき、安全性の点からも好ましい。
The temperature of the cleaning oil C in the high-temperature oil cleaning step 4 may be 100 ° C. or higher, and preferably 150 to 160 ° C.
If water is mixed into the cleaning oil C in the high-temperature oil cleaning step, the mixed water reacts with the alkali metal when the cleaning oil C is treated with the alkali metal dispersion, and the alkali metal is wasted. Before the oil C is treated with an alkali metal, it is necessary to separate the oil and water by distillation or the like. However, the agricultural chemicals and the like to be treated in the present invention have a lower boiling point than PCBs and the like that have been conventionally treated in the same process, and the cleaning oil in the high temperature oil washing process contains a high concentration of agricultural chemicals and the like. Therefore, a high degree of detoxification treatment is required for water recovered by distillation.
However, if the temperature of the cleaning oil C is 100 ° C. or higher, not only can the scale adhere due to precipitation of agricultural chemicals and the like, but also water vapor contained in the exhaust gas B can be condensed and mixed into the cleaning oil C. Absent. Therefore, when the cleaning oil C is treated with the alkali metal dispersion, it is possible to prevent the alkali metal from being wasted due to the reaction with water, and an oil-water separation step is not required.
Further, if the temperature of the cleaning oil C is 150 to 160 ° C., the exhaust gas flow rate discharged from the heat treatment process is decreased, and the exhaust gas temperature is decreased in the vicinity of the pipe outlet (that is, the introduction part to the high temperature oil cleaning process). Even if it is a case, piping which contacts this washing | cleaning oil will be maintained at 150-160 degreeC, and adhesion of a scale can be prevented more reliably.
Further, by setting the upper limit of the temperature to 160 ° C., the vapor pressure of the cleaning oil does not become too high, and the cleaning oil itself can be prevented from volatilizing, which is preferable from the viewpoint of safety.

また、排ガスBは、前記加熱処理工程2から排出された際には概ね350〜600℃となっているが、この高温油洗浄工程4に至るまでは120℃以上の高温状態に保つ必要があり、好ましくは150℃以上に保つものとする。
排ガスBを高温状態に保つための具体的手段としては、排ガスBの配管等をライニング材等によって被覆する方法が挙げられる。
Further, the exhaust gas B is approximately 350 to 600 ° C. when discharged from the heat treatment step 2, but it is necessary to keep the temperature at 120 ° C. or higher until the high temperature oil washing step 4 is reached. Preferably, it shall be kept at 150 ° C. or higher.
As a specific means for keeping the exhaust gas B in a high temperature state, a method of covering the exhaust gas B with a lining material or the like can be mentioned.

本実施形態において、低温油洗浄工程5は、高温油洗浄工程4から排出された排ガスBと低温の洗浄油Dとを気液接触させることにより排ガスB中に含まれる極めて微量の農薬等を除去する工程である。該低温油洗浄工程5において排ガスBと低温の洗浄油Dとを接触させる方式については特に限定されず、前記高温油洗浄工程4と同様に、例えば、曝気方式、スクラバー方式、ロートクロン方式、エジェクター方式、回転噴霧塔方式、ベンチュリー方式などを採用できる。これらのうち、特に好ましくは、図1に示したようなスクラバー方式が採用される。スクラバー方式であれば、排ガスと洗浄油との接触面積が大きくなり、熱交換の効率が高くなる。その結果、排ガスの温度を効率よく低下させることができるという効果がある。   In this embodiment, the low temperature oil cleaning process 5 removes an extremely small amount of agricultural chemicals contained in the exhaust gas B by bringing the exhaust gas B discharged from the high temperature oil cleaning process 4 and the low temperature cleaning oil D into gas-liquid contact. It is a process to do. In the low-temperature oil cleaning step 5, the method for contacting the exhaust gas B and the low-temperature cleaning oil D is not particularly limited. For example, as in the high-temperature oil cleaning step 4, for example, an aeration method, a scrubber method, a funnel method, an ejector method Rotating spray tower method, venturi method, etc. can be adopted. Of these, a scrubber system as shown in FIG. 1 is particularly preferably employed. With the scrubber system, the contact area between the exhaust gas and the cleaning oil increases, and the efficiency of heat exchange increases. As a result, there is an effect that the temperature of the exhaust gas can be efficiently reduced.

低温油洗浄工程5において用いる低温の洗浄油としては、前記高温油洗浄工程4において使用しうる上記洗浄油と同様の洗浄油を使用することができるが、洗浄油を共用できるという観点から、前記高温油洗浄工程4において使用する洗浄油と同種の洗浄油を使用することが好ましい。
また、該低温油洗浄工程5における洗浄油の温度は50℃以下とするが、好ましくは10〜30℃とする。低温油洗浄工程5における洗浄油の温度が50℃を超えると、油の蒸気圧が高くなり、油の揮散量が多くなり後段の活性炭処理工程(図示せず)等に油が混入し、後段の負荷が高くなるため、好ましくない。油や排ガス中に混入した水分等の揮散を防止する観点から、低温油洗浄工程5における洗浄油の温度は低い方が好ましいが、水分が混じっているため、凍結防止の観点から0℃以上、好ましくは10℃以上とする。
As the low-temperature cleaning oil used in the low-temperature oil cleaning step 5, the same cleaning oil as the cleaning oil that can be used in the high-temperature oil cleaning step 4 can be used, but from the viewpoint that the cleaning oil can be shared, It is preferable to use the same type of cleaning oil as that used in the hot oil cleaning step 4.
The temperature of the cleaning oil in the low-temperature oil cleaning step 5 is 50 ° C. or less, preferably 10 to 30 ° C. When the temperature of the cleaning oil in the low temperature oil cleaning process 5 exceeds 50 ° C., the vapor pressure of the oil increases, the amount of oil volatilization increases, and the oil is mixed in the subsequent activated carbon treatment process (not shown), etc. This is not preferable because the load of From the viewpoint of preventing volatilization of moisture mixed in oil and exhaust gas, the temperature of the cleaning oil in the low temperature oil cleaning step 5 is preferably low, but since water is mixed, 0 ° C. or more from the viewpoint of freezing prevention, Preferably it shall be 10 degreeC or more.

本実施形態において、高温油洗浄工程4から排出された洗浄油Cは無害化工程6へと送られる。無害化工程6は、洗浄油中に含まれる農薬等を分解又は除去することにより、洗浄油を無害化する工程である。該無害化工程6としては、例えば、金属ナトリウム等のアルカリ金属を用いて農薬等を脱ハロゲン化処理する方式を採用できる。斯かる方式の無害化工程6としては、例えば、農薬等を含む汚染油とアルカリ金属分散体とを反応させる反応工程と、該反応工程において反応せずに残ったアルカリ金属を水和する水和工程と、アルカリ性の処理液を中和する中和工程と、水と洗浄油とを分離する分離工程と、さらに、前記反応工程から発生する排ガスを処理するための活性炭処理工程とを備えたものとすることができる。   In the present embodiment, the cleaning oil C discharged from the high temperature oil cleaning process 4 is sent to the detoxification process 6. The detoxification step 6 is a step of detoxifying the cleaning oil by decomposing or removing agricultural chemicals and the like contained in the cleaning oil. As the detoxification step 6, for example, a method of dehalogenating agrochemicals using an alkali metal such as metallic sodium can be employed. Examples of such a detoxification step 6 include a reaction step of reacting a contaminated oil containing agricultural chemicals and the like with an alkali metal dispersion, and hydration for hydrating the remaining alkali metal in the reaction step. A process, a neutralization process for neutralizing an alkaline treatment liquid, a separation process for separating water and cleaning oil, and an activated carbon treatment process for treating exhaust gas generated from the reaction process It can be.

該無害化工程6によって無害化された洗浄油Cは、再び所定の温度に加熱された後、高温油洗浄工程4へと返送され、再利用される。   The cleaning oil C detoxified by the detoxification step 6 is heated again to a predetermined temperature, then returned to the high temperature oil cleaning step 4 and reused.

また、前記低温油洗浄工程5にて使用される洗浄油Dについても、農薬等の濃度が高くなった場合等には、必要に応じて油水分離した後、同様の無害化工程により無害化することができる。なお、高温油洗浄工程における洗浄油の油水分離について、分離後の水中への農薬等の混入が問題となることは前述した通りであるが、低温油洗浄工程においては、油中の農薬等の濃度は高温油洗浄工程における洗浄油中の農薬等の濃度に比べて十分に低いため、減圧蒸留等により油水分離を行っても水中に混入する農薬等の量は極めて少なく、水処理に大きな負担がかかることもない。   Further, the cleaning oil D used in the low-temperature oil cleaning step 5 is also rendered harmless by the same detoxification step after oil-water separation if necessary when the concentration of agricultural chemicals or the like is increased. be able to. As described above, the oil-water separation of the washing oil in the high-temperature oil washing process has the problem of mixing agricultural chemicals into the water after separation, but in the low-temperature oil washing process, the pesticides in the oil Since the concentration is sufficiently lower than the concentration of agricultural chemicals in the cleaning oil in the high temperature oil cleaning process, the amount of agricultural chemicals mixed into the water is extremely small even if oil-water separation is performed by vacuum distillation, etc., and a heavy burden on water treatment It will not take.

本実施形態の農薬汚染物質の処理方法および排ガスの処理方法によれば、加熱処理工程2から排出される排ガスBは、高温油洗浄工程4に至るまで高温状態に保持され、高温油洗浄工程4において高温の洗浄油Cと気液接触されるため、排ガスB中に含まれる農薬等は配管中に析出することなく、洗浄油C中に溶解又は分散され、排ガスBが浄化されることとなる。特に、本実施形態のように曝気方式の高温油洗浄工程4を採用した場合には、配管の先端部分が全て高温の洗浄油Cと接触した状態となるため、配管の先端部分が温度低下することなくスケールの付着を確実に防止できるという効果がある。
このように、本実施形態の処理方法によれば、配管等にスケールが付着して汚染物質の処理運転が阻害されることがない。
According to the agricultural chemical contaminant treatment method and the exhaust gas treatment method of the present embodiment, the exhaust gas B discharged from the heat treatment step 2 is maintained in a high temperature state until reaching the high temperature oil washing step 4, and the high temperature oil washing step 4 In this case, the pesticide contained in the exhaust gas B is dissolved or dispersed in the cleaning oil C without being deposited in the pipe, and the exhaust gas B is purified. . In particular, when the aeration-type high temperature oil cleaning step 4 is employed as in the present embodiment, the tip portion of the pipe is in contact with the high temperature cleaning oil C, so that the temperature of the tip portion of the pipe decreases. There is an effect that the adhesion of the scale can be surely prevented.
Thus, according to the treatment method of the present embodiment, the scale does not adhere to the piping or the like, and the pollutant treatment operation is not hindered.

本実施形態においては、排ガスBは、さらに低温油洗浄工程5において低温の洗浄油Dと気液接触されるため、排ガスBが冷却されるともに、排ガスB中に含まれる極めて微量の農薬等、及び洗浄油の蒸気や飛沫などを低温の洗浄油Dによって除去することができる。   In the present embodiment, the exhaust gas B is further brought into gas-liquid contact with the low temperature cleaning oil D in the low temperature oil cleaning step 5, so that the exhaust gas B is cooled and an extremely small amount of agricultural chemicals contained in the exhaust gas B, etc. Also, the cleaning oil vapor and splashes can be removed by the low temperature cleaning oil D.

尚、前記実施形態においては、高温油洗浄工程4から排出された排ガスBを低温油洗浄工程5によって処理する場合について説明したが、本発明はこのような実施形態に限定されるものではない。即ち、例えば図2に示したように、前記低温油洗浄工程5に代えて、高温油洗浄工程4から排出された排ガスBを冷却して該排ガスB中に含まれる洗浄油を凝縮させる凝縮工程7を備えても良い。
該凝縮工程7としては、例えば、水等の冷媒によって排ガスBを間接的に冷却し、洗浄油Cの沸点以下、好ましくは10〜30℃にまで冷却するものを好適に採用できる。
In the above embodiment, the case where the exhaust gas B discharged from the high temperature oil cleaning process 4 is processed by the low temperature oil cleaning process 5 has been described, but the present invention is not limited to such an embodiment. That is, for example, as shown in FIG. 2, instead of the low temperature oil cleaning step 5, the condensation step of cooling the exhaust gas B discharged from the high temperature oil cleaning step 4 and condensing the cleaning oil contained in the exhaust gas B 7 may be provided.
As this condensation process 7, what cools exhaust gas B indirectly with refrigerant | coolants, such as water, and is cooled to below the boiling point of the washing oil C, Preferably it is 10-30 degreeC, for example can be employ | adopted suitably.

斯かる凝縮工程7を備えた場合には、高温油洗浄工程4において蒸発した洗浄油Cを回収して洗浄油として再利用することができ、しかも排ガスB中に微量の農薬等が残留している場合には、これを析出させて洗浄油とともに分離回収することができる。
また、該凝縮工程7で回収される凝縮液中に水分が多く含まれている場合には、適宜、油水分離工程を設け、洗浄油と水とを油水分離し、分離された水を別途無害化処理してもよい。
When such a condensation process 7 is provided, the cleaning oil C evaporated in the high-temperature oil cleaning process 4 can be recovered and reused as cleaning oil, and a trace amount of agricultural chemicals or the like remains in the exhaust gas B. If it is, it can be deposited and separated and recovered together with the cleaning oil.
In addition, when the condensate recovered in the condensation step 7 contains a large amount of water, an oil / water separation step is appropriately provided to separate the cleaning oil and water from oil and water, and the separated water is harmless separately. May be processed.

さらに、本実施形態においては図示していないが、油洗浄工程により洗浄された排ガスは、大気放出前に活性炭で処理するのが好ましい。また、本発明の排ガス処理工程より排出される水については、膜処理、生物処理、活性炭処理等の水処理を行ない、系外に汚染物質が排出されない構成とする。
また、本実施形態においては、高温油洗浄工程は1段としているが、本発明はこれに限定されず、排ガス中の農薬等の濃度に合わせて適宜、2段、3段というように多段にしても良い。
Further, although not shown in the present embodiment, the exhaust gas cleaned by the oil cleaning process is preferably treated with activated carbon before being released into the atmosphere. Moreover, about the water discharged | emitted from the waste gas treatment process of this invention, it is set as the structure which performs water treatment, such as a membrane treatment, biological treatment, activated carbon treatment, and a contaminant is not discharged | emitted out of the system.
In the present embodiment, the high temperature oil washing step is a single step, but the present invention is not limited to this, and is appropriately multistaged such as two steps or three steps according to the concentration of agricultural chemicals in the exhaust gas. May be.

図1は、本発明に係る農薬汚染物質の処理方法および排ガス処理方法の一実施形態を示す概略フロー図である。FIG. 1 is a schematic flow diagram showing an embodiment of a method for treating agricultural chemical contaminants and an exhaust gas treatment method according to the present invention. 図2は、本発明に係る農薬汚染物質の処理方法および排ガス処理方法の他の実施形態を示す概略フロー図である。FIG. 2 is a schematic flow diagram showing another embodiment of the method for treating agricultural chemical contaminants and the method for treating exhaust gas according to the present invention.

符号の説明Explanation of symbols

A 汚染物質
B 排ガス
C 高温の洗浄油
D 低温の洗浄油
2 加熱処理工程
3 集塵工程
4 高温油洗浄工程
5 低温油洗浄工程
6 無害化工程
7 凝縮工程
A Pollutant B Exhaust gas C High temperature cleaning oil D Low temperature cleaning oil 2 Heat treatment process 3 Dust collection process 4 High temperature oil cleaning process 5 Low temperature oil cleaning process 6 Detoxification process 7 Condensation process

Claims (8)

農薬汚染物質の加熱処理によって生じる排ガスの処理方法であって、100℃以上の高温の洗浄油と前記加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄工程を備えたことを特徴とする排ガス処理方法。   A method for treating exhaust gas generated by heat treatment of agricultural chemical pollutants, comprising a high-temperature oil washing step in which a high-temperature cleaning oil of 100 ° C. or higher and a high-temperature exhaust gas of 120 ° C. or higher generated by the heat treatment are in gas-liquid contact. An exhaust gas treatment method characterized by that. 前記高温油洗浄工程を経た排ガスを冷却し、洗浄油を凝縮させる凝縮工程を備えたことを特徴とする請求項1記載の排ガス処理方法。   The exhaust gas treatment method according to claim 1, further comprising a condensing step for cooling the exhaust gas that has undergone the high-temperature oil washing step and condensing the washing oil. 前記高温油洗浄工程を経た排ガスと、50℃以下の低温の洗浄油とを気液接触させる低温油洗浄工程を備えたことを特徴とする請求項1に記載の排ガス処理方法。   The exhaust gas treatment method according to claim 1, further comprising a low-temperature oil cleaning step in which the exhaust gas that has undergone the high-temperature oil cleaning step and a low-temperature cleaning oil of 50 ° C or less are in gas-liquid contact. 前記高温油洗浄工程が曝気方式であることを特徴とする請求項1〜3の何れかに記載の排ガス処理方法。   The exhaust gas treatment method according to any one of claims 1 to 3, wherein the high-temperature oil washing step is an aeration method. 前記低温油洗浄工程がスクラバー方式であることを特徴とする請求項3又は4に記載の排ガス処理方法。   The exhaust gas treatment method according to claim 3 or 4, wherein the low-temperature oil cleaning step is a scrubber system. 前記高温油洗浄工程における洗浄油の温度が、150〜160℃であることを特徴とする請求項1〜5の何れかに記載の排ガス処理方法。   The exhaust gas treatment method according to any one of claims 1 to 5, wherein the temperature of the cleaning oil in the high-temperature oil cleaning step is 150 to 160 ° C. 農薬汚染物質を加熱処理する際に生じる排ガスの処理設備であって、
100℃以上の高温の洗浄油と前記加熱処理によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄手段を備えたことを特徴とする排ガス処理設備。
A facility for treating exhaust gas generated when heat treating pesticide pollutants,
An exhaust gas treatment facility comprising high-temperature oil cleaning means for bringing gas-liquid contact between a high-temperature cleaning oil of 100 ° C or higher and an exhaust gas in a high-temperature state of 120 ° C or higher generated by the heat treatment.
農薬汚染物質を加熱処理する加熱処理工程と、100℃以上の高温の洗浄油と前記加熱処理工程によって生じる120℃以上の高温状態の排ガスとを気液接触させる高温油洗浄工程とを備えたことを特徴とする農薬汚染物質の処理方法。   A heat treatment process for heat-treating agricultural chemical contaminants, and a high-temperature oil washing process for causing gas-liquid contact between a high-temperature cleaning oil of 100 ° C. or higher and a high-temperature exhaust gas of 120 ° C. or higher generated by the heat treatment step A method for treating pesticide pollutants.
JP2005014352A 2005-01-21 2005-01-21 Method and apparatus for treating exhaust gas, and method for treating substance contaminated with agricultural chemicals Withdrawn JP2006198549A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010134775A2 (en) * 2009-05-22 2010-11-25 금광개발주식회사 Method for treating contaminated soil comprising a steaming process, and apparatus for same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010134775A2 (en) * 2009-05-22 2010-11-25 금광개발주식회사 Method for treating contaminated soil comprising a steaming process, and apparatus for same
WO2010134775A3 (en) * 2009-05-22 2011-03-03 금광개발주식회사 Method for treating contaminated soil comprising a steaming process, and apparatus for same

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