JP2014018428A - Processing method of liquid waste containing chlorine - Google Patents
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Abstract
Description
本発明は、塩素を含む液状廃棄物の処理方法に関するものである。 The present invention relates to a method for treating liquid waste containing chlorine.
ポリ塩化ビフェニール（以下「ＰＣＢ」という。）は、水に難溶で有機溶媒とは相互に溶解し、難燃性、不燃性、化学的に安定しており絶縁性が高く、電気特性に優れているなどの性質を有することからトランス、コンデンサ、安定器や熱媒体として多方面に利用されていた。 Polychlorinated biphenyls (hereinafter referred to as “PCB”) are insoluble in water and mutually soluble in organic solvents, are flame retardant, incombustible, chemically stable, have high insulation, and have excellent electrical properties. It has been used in many fields as a transformer, capacitor, ballast and heat medium.
その一方で、生体に対する毒性が高く、脂肪組織に蓄積しやすく、発癌性があり、また皮膚障害、内臓障害、ホルモン異常を引き起こすことがわかっている。 On the other hand, it is known that it is highly toxic to living bodies, easily accumulates in adipose tissue, is carcinogenic, and causes skin disorders, visceral disorders, and hormonal abnormalities.
上記のように人体に影響を及ぼす為、1972年の「化学物質の審査及び製造等の規制に関する法律」により、特定化学物質に指定された。これにより製造・輸入・新規使用が原則禁止となった。 In order to affect the human body as described above, it was designated as a specified chemical substance by the “Law Concerning the Examination and Regulation of Chemical Substances” in 1972. As a result, manufacturing, imports, and new uses were prohibited in principle.
平成16年5月に残留性有害汚染物質に関するストックホルム条約（POPs条約）が発効し、この条約ではＰＣＢに関して、平成37年までの使用全廃、平成40年までの適正な処分を求めており、日本では平成14年8月にこの条約を締結した。 The Stockholm Convention on Persistent Hazardous Pollutants (POPs Convention) entered into force in May 2004, and this treaty calls for the complete abolition of PCBs until 2005 and proper disposal until 2004. Then, in August 2002, this treaty was signed.
しかし、現状ではほぼ30年の長期に亘りほとんど処理が行われず、結果として保管が続き、紛失や漏洩による環境汚染の進行が懸念されたことから、国により処理施設が設置されたが国内に数ヶ所しか設置されておらず、処理費用が高額でしかも処理能力に限界があり、平成28年7月までの処理が義務付けされているが、完了の延期が報告されている。 However, under the present circumstances, almost no treatment was performed for a long period of almost 30 years, and as a result, storage continued and there was concern about the progress of environmental pollution due to loss or leakage. Only one location is installed, the processing cost is high and the processing capacity is limited, and processing is required until July 2016, but postponement of completion has been reported.
ＰＣＢの処理方法としては脱塩素化分解処理装置での処理があり、この処理方法は、アルカリ剤や触媒等をＰＣＢと混合させ化学反応させることにより、ＰＣＢの塩素を水素などに置換し、ＰＣＢとは異なる物質にする方法があげられる。 As a method for treating PCB, there is a treatment in a dechlorination / decomposition treatment apparatus. In this treatment method, an alkali agent, a catalyst, or the like is mixed with PCB and chemically reacted to replace PCB chlorine with hydrogen, etc. There is a method to make it a different substance.
そのようなＰＣＢの処理方法の一つが、特許文献１に開示されている。特許文献１の処理方法は、「硫酸調製液２を加熱し、アルミニウム棒３を硫酸調製液２に浸漬するとともに補助的にアルミニウム棒からなる正電極４及び負電極５に直流電流を流通し、さらに超音波振動器を作用させる。これにより、硫酸調製液２とアルミニウム棒３とが反応して水素ラジカルを生じ、細かな水素の気泡が激しく発生する。そして、ＰＣＢを静かに注入すると気泡数が増大し泡沫層７が形成され、ＰＣＢはこの硫酸調製液２による泡沫層７を徐々に通過し、分解される。」というものである。 One such PCB processing method is disclosed in Patent Document 1. The treatment method of Patent Document 1 is “heating the sulfuric acid preparation solution 2 and immersing the aluminum rod 3 in the sulfuric acid preparation solution 2 and supplementarily flowing a direct current through the positive electrode 4 and the negative electrode 5 made of an aluminum rod, In addition, an ultrasonic vibrator is operated, whereby the sulfuric acid preparation solution 2 and the aluminum rod 3 react to generate hydrogen radicals, and fine hydrogen bubbles are generated vigorously. Is increased and a foam layer 7 is formed, and the PCB gradually passes through the foam layer 7 of the sulfuric acid preparation solution 2 and is decomposed.
しかし特許文献１記載の処理方法は、それなりに大掛かりな設備が必要であり、また、爆発性のある水素ガスを用いる為、処理に危険を伴う。 However, the treatment method described in Patent Document 1 requires a large amount of equipment as it is, and uses explosive hydrogen gas.
本発明者は、過去に塩素を含有する工場廃水処理の依頼を受け、数々の実験及び研究を重ね、加熱装置を含む大掛かりな設備を必要とせず、前記工場廃水の塩素処理を可能にした経験を有している。そこで、現在処理が問題になっているＰＣＢの塩素を分解するために前記工場廃水処理に使用した塩素処理技術が応用できるのではないかということに着目し、本発明を完成するに至った。 The present inventor has received a request for the treatment of factory wastewater containing chlorine in the past, repeated numerous experiments and researches, and has made it possible to chlorinate the factory wastewater without requiring a large facility including a heating device. have. Therefore, the present invention has been completed by paying attention to the possibility that the chlorination technology used in the above-mentioned factory wastewater treatment can be applied to decompose the chlorine in PCBs which are currently problematic in the treatment.
（本発明の目的）
本発明は、大掛かりな設備を必要とせず、塩素を含む液状廃棄物を処理する方法を提供するものである。これによりベンゼン骨格に結合したＰＣＢの塩素を除去し安全な物質に置換することが可能となる。
(Object of the present invention)
The present invention provides a method for treating liquid waste containing chlorine without requiring large-scale equipment. This makes it possible to remove chlorine from PCB bonded to the benzene skeleton and replace it with a safe substance.
上記課題を解決するために本発明が講じた手段は次のとおりである。
本発明は、
攪拌機を備えた一の処理槽を使用し、当該処理槽内の塩素を含む液状廃棄物に、ホルムアルデヒド、トルエンスルホン酸、1.3-ジメチル‐2-イミダゾリジノン、ジメチルスルホルオキサイド、NN‐ジメチルホルムアミド、メチルヘキシルケトン、ネオペンチルグリコール、トリクロロエチレン、N‐メチル‐2-ピロリドン、スルフォラン、ステアリン酸アミド、及び2.5-ジメチル‐2.5-ヘキサンジオールを添加混合して、塩素を含む液状廃棄物から塩素イオンを低減した液状処理物を得る、
塩素を含む液状廃棄物の処理方法である。
Means taken by the present invention to solve the above problems are as follows.
The present invention
Using one treatment tank equipped with a stirrer, the liquid waste containing chlorine in the treatment tank is treated with formaldehyde, toluenesulfonic acid, 1.3-dimethyl-2-imidazolidinone, dimethylsulfuroxide, NN-dimethylformamide. , Methylhexyl ketone, neopentyl glycol, trichlorethylene, N-methyl-2-pyrrolidone, sulfolane, stearamide, and 2.5-dimethyl-2.5-hexanediol are added and mixed to remove chlorine ions from liquid waste containing chlorine. To obtain a reduced liquid processed product,
This is a method for treating liquid waste containing chlorine.
前記処理槽内の塩素を含む液状廃棄物に添加混合する化学物質の量は、塩素を含む液状廃棄物１００重量部に対して各々１〜３重量部が推奨される。 The amount of the chemical substance added to and mixed with the liquid waste containing chlorine in the treatment tank is recommended to be 1 to 3 parts by weight with respect to 100 parts by weight of the liquid waste containing chlorine.
前記液状処理物に、蟻酸及び無水酢酸を添加して発熱させ、液分を蒸発させて粉体物を得るのが好ましい。 It is preferable to add formic acid and acetic anhydride to the liquid treatment product to generate heat and evaporate the liquid to obtain a powder product.
蟻酸及び無水酢酸の添加量は、各々３〜５重量部であるのが好ましい。 The amount of formic acid and acetic anhydride added is preferably 3 to 5 parts by weight.
前記粉体物はコンクリートの骨材として使用するのが好ましい。 The powder is preferably used as a concrete aggregate.
本発明によれば、攪拌機を備えた一の処理槽で塩素を含む液状廃棄物の処理が可能であり、加熱や電流を流したり超音波振動などの作業が一切必要としないので、設備費用も安価で、施設面積が小さくてすむ。また、攪拌機を備えた一の処理槽で塩素を含む液状廃棄物の処理が可能であるから、固定式の処理施設の設置だけではなく、トラックなどの運搬手段に積載した可動式の処理施設の製造も可能である。
更に、粉体化した脱塩素廃棄物はセメント等と混合固化しブロック、骨材として土木資材としてのリサイクルも可能である。
According to the present invention, it is possible to treat liquid waste containing chlorine in one treatment tank equipped with a stirrer, and no work such as heating, passing an electric current or ultrasonic vibration is required, so the equipment cost is also low. It is inexpensive and requires a small facility area. In addition, since it is possible to treat liquid waste containing chlorine in one treatment tank equipped with a stirrer, not only fixed treatment facilities but also mobile treatment facilities loaded on transportation means such as trucks can be used. Manufacture is also possible.
Furthermore, the pulverized dechlorination waste can be mixed and solidified with cement or the like, and recycled as a block or aggregate as a civil engineering material.
本発明を実施例に基づき詳細に説明する。 The present invention will be described in detail based on examples.
ＰＣＢは保管場所から持出し不可の為入手不可能であり、その代替品として塩素を含むＰＣＢ油類似品（以下「塩素含有油」という。）を作成し、当該塩素含有油からの脱塩素実験を試みた。作成した塩素含有油の原材料及び配合量は、下記の表１の通りである。 PCB is not available because it cannot be taken out from the storage location. As an alternative, a PCB oil-like product containing chlorine (hereinafter referred to as “chlorine-containing oil”) is prepared, and dechlorination experiments from the chlorine-containing oil are conducted. Tried. The raw materials and blending amounts of the prepared chlorine-containing oil are as shown in Table 1 below.
前記塩素含有油について簡易残留塩素試験紙（日産化学工業株式会社 日産アクアチェックTC）にて総残留塩素を測定したところ、総残留塩素は、3.0mg／L以上であった。
前記塩素含有油から塩素を除くことができれば、ＰＣＢからも塩素をを除くことができると考えられ、ＰＣＢの無害化が可能となる。
When the total residual chlorine was measured for the chlorine-containing oil using a simple residual chlorine test paper (Nissan Chemical Industry Co., Ltd., Nissan Aqua Check TC), the total residual chlorine was 3.0 mg / L or more.
If chlorine can be removed from the chlorine-containing oil, it is considered that chlorine can also be removed from the PCB, and the PCB can be rendered harmless.
塩素含有油からの脱塩素は、次の工程にしたがって行った。
〔工程１〕
前記塩素含有油を攪拌容器に5,550g投入した。撹拌容器は、一般的に入手可能な攪拌機を使用した（アーム産業株式会社 型番ＭＳＤ−４０）。
Dechlorination from the chlorine-containing oil was performed according to the following steps.
[Step 1]
5,550 g of the chlorine-containing oil was put into a stirring vessel. The stirring container used the generally available stirrer (Arm Sangyo Co., Ltd. model number MSD-40).
〔工程２〕
塩素含有油がはいった攪拌容器に、表２に掲げた下記薬品を１分毎に順次投入攪拌を行った。なお、投入間隔は１分間隔に限定されるものではなく、充分な撹拌が行われるのであれば、前記間隔より長くても短くても良い。
そして、最後の投入物である2.5-ジメチル‐2.5-ヘキサンジオールを投入後５〜１０分間撹拌を続けた。撹拌時には反応熱を生じた。
[Step 2]
The following chemicals listed in Table 2 were sequentially added and stirred every 1 minute in a stirring vessel containing chlorine-containing oil. Note that the charging interval is not limited to one minute interval, and may be longer or shorter than the interval as long as sufficient stirring is performed.
And stirring was continued for 5 to 10 minutes after adding the final charge of 2.5-dimethyl-2.5-hexanediol. Heat of reaction was generated during stirring.
上記化学物質は塩素の含有量に応じて、原料物質重量に対して、１〜５％の範囲で添加量を変更することができる。
前記で使用した簡易残留塩素試験紙にて前記物質で処理を終了した液状処理物について総残留塩素を測定したところ、残留塩素は0mg／Lであり、本工程によって塩素処理は終了したと考えられる。
Depending on the chlorine content, the chemical substance can be added in an amount of 1 to 5% with respect to the weight of the raw material.
When the total residual chlorine was measured for the liquid processed product that had been treated with the above substances using the simple residual chlorine test paper used above, the residual chlorine was 0 mg / L, and it is considered that the chlorination was completed by this step. .
なお、念のために処理前の塩素含有油と工程２を経て得られた処理物の塩化物イオンの残留塩素の量を、外部の分析機関にて測定したところ、下記のような結果となった。 As a precaution, the amount of residual chlorine in the chlorine-containing oil before treatment and the chloride ion of the treated product obtained through step 2 was measured by an external analysis organization, and the following results were obtained. It was.
上記方法によれば、塩素を含む液状廃棄物の処理が可能である。しかし、処理物は液体であり、そのままでは、廃棄処分が困難であることから、液分を蒸発させて残渣物を粉体化し、例えばコンクリートの骨材などとして再利用できるようにするのが好ましい。
次の工程３〜５は、脱塩素処理後の処理物を粉体化する工程である。
According to the above method, it is possible to treat liquid waste containing chlorine. However, since the treated product is a liquid and is difficult to dispose of as it is, it is preferable to evaporate the liquid and pulverize the residue so that it can be reused, for example, as a concrete aggregate. .
The next steps 3 to 5 are steps for pulverizing the processed product after the dechlorination treatment.
〔工程３〕
工程２で得られた処理物に対して、水道水5重量部（275cc）、ゼオライト、活性炭を各々10重量部（550g）を添加して、混合攪拌を10分間程度行った。この工程で発熱（120〜150℃）するとともに水蒸気とガスが発生する。この発生する水蒸気とガスはヒートパイプを使用した冷却装置を通過しタングステンとアンモニア等の触媒を通過し大気に放出できる。この工程３を終えた状態では、多少水分を含んだ粉体物となる。
[Step 3]
To the treated product obtained in step 2, 5 parts by weight of tap water (275 cc), 10 parts by weight (550 g) of zeolite and activated carbon were added, and the mixture was stirred for about 10 minutes. In this process, heat is generated (120 to 150 ° C.) and water vapor and gas are generated. The generated water vapor and gas can pass through a cooling device using a heat pipe, pass through a catalyst such as tungsten and ammonia, and be released to the atmosphere. In the state where Step 3 is finished, a powder material containing a little moisture is obtained.
〔工程４〕
更に、含まれる液分をなくす為に、工程３で得られた処理物に対して蟻酸（CAS番号64-18-6）、無水酢酸（CAS番号108-24-7）を各々3重量部（165cc）添加し、混合攪拌する。これらの物質の添加により、発熱し（約150〜200℃）、更に残留していた液分が蒸発し、工程２で得られた液状処理物から、乾燥された粉体物が得られた。
[Step 4]
Further, in order to eliminate the contained liquid, 3 parts by weight of formic acid (CAS No. 64-18-6) and acetic anhydride (CAS No. 108-24-7) were respectively added to the processed product obtained in Step 3 ( 165 cc) is added and mixed and stirred. By adding these substances, heat was generated (about 150 to 200 ° C.), and the remaining liquid was evaporated, and a dried powder product was obtained from the liquid processed product obtained in step 2.
なお、上記工程４で得られた粉体物を、セメント等、に添加・混合することによってブロック等の土木・建築用資材として使用することができる。 In addition, it can be used as civil engineering and building materials, such as a block, by adding and mixing the powder substance obtained at the said process 4 with cement etc.
なお、本明細書で使用している用語と表現は、あくまでも説明上のものであって、なんら限定的なものではなく、本明細書に記述された特徴およびその一部と等価の用語や表現を除外する意図はない。また、本発明の技術思想の範囲内で、種々の変形態様が可能であるということは言うまでもない。 Note that the terms and expressions used in this specification are merely explanatory and are not limiting at all, and terms and expressions equivalent to the features described in this specification and parts thereof. There is no intention to exclude. It goes without saying that various modifications are possible within the scope of the technical idea of the present invention.
Claims (5)
塩素を含む液状廃棄物の処理方法。 Using one treatment tank equipped with a stirrer, the liquid waste containing chlorine in the treatment tank is treated with formaldehyde, toluenesulfonic acid, 1.3-dimethyl-2-imidazolidinone, dimethylsulfuroxide, NN-dimethylformamide. , Methylhexyl ketone, neopentyl glycol, trichlorethylene, N-methyl-2-pyrrolidone, sulfolane, stearamide, and 2.5-dimethyl-2.5-hexanediol are added and mixed to remove chlorine ions from liquid waste containing chlorine. To obtain a reduced liquid processed product,
A method for treating liquid waste containing chlorine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104998370A (en) * | 2015-07-11 | 2015-10-28 | 卞洪锋 | Preparation method of formaldehyde eliminating agent and application |
| CN105013127A (en) * | 2015-07-11 | 2015-11-04 | 卞洪锋 | Formaldehyde elimination agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104998370A (en) * | 2015-07-11 | 2015-10-28 | 卞洪锋 | Preparation method of formaldehyde eliminating agent and application |
| CN105013127A (en) * | 2015-07-11 | 2015-11-04 | 卞洪锋 | Formaldehyde elimination agent and application thereof |
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