JP5383595B2 - Detoxification treatment facility for insulating oil mixed in with PCB - Google Patents

Detoxification treatment facility for insulating oil mixed in with PCB Download PDF

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JP5383595B2
JP5383595B2 JP2010129601A JP2010129601A JP5383595B2 JP 5383595 B2 JP5383595 B2 JP 5383595B2 JP 2010129601 A JP2010129601 A JP 2010129601A JP 2010129601 A JP2010129601 A JP 2010129601A JP 5383595 B2 JP5383595 B2 JP 5383595B2
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賢治 徳政
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Chugoku Electric Power Co Inc
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Description

本発明は、ＰＣＢ混入絶縁油を金属ナトリウムで無害化するＰＣＢ混入絶縁油の無害化処理設備に関する。   The present invention relates to a PCB-mixed insulating oil detoxifying treatment facility that detoxifies PCB-mixed insulating oil with metallic sodium.

ＰＣＢ（ポリ塩化ビフェニル）は、不燃性で化学安定性及び電気絶縁性に優れるため、従来、電気機器の絶縁油などとして使用されていたが、その有害性から現在では使用が禁止され、保管されているＰＣＢ及びＰＣＢを含有する廃油などについても、平成１３年に制定された「ポリ塩化ビフェニル廃棄物の適正な処理の推進に関する特別措置法（ＰＣＢ特措法）」により、平成２８年７月までに処理を完了することが義務付けられている。   PCB (polychlorinated biphenyl) is nonflammable and excellent in chemical stability and electrical insulation, so it was conventionally used as an insulating oil for electrical equipment, but its use is now prohibited and stored due to its harmfulness. PCBs and waste oils containing PCBs, etc., by July 2016, according to the “Special Measures Law for Promotion of Proper Treatment of Polychlorinated Biphenyl Waste (PCB Special Measures Law)” enacted in 2001 Completion of processing is required.

ＰＣＢの脱塩素化技術は、これまでに多くの方法が提案されており、幾つかの方法は実用化されている。金属ナトリウムとＰＣＢとを反応させＰＣＢを脱塩素化させる方法は、ＰＣＢ混入絶縁油の無害化処理に使用され、処理プラントも稼働中である。金属ナトリウムとＰＣＢとを反応させるとＰＣＢが脱塩素化され、ビフェニル、塩化ナトリウム、ビフェニルが重合したビフェニル重合物、水酸化ナトリウムが生成するが、この生成物に関しては幾つかの問題が指摘され、これに対する対策案が提案されている（例えば特許文献１参照）。   Many methods have been proposed for PCB dechlorination techniques, and several methods have been put to practical use. The method of dechlorinating PCB by reacting sodium metal with PCB is used for detoxification treatment of PCB mixed insulating oil, and the processing plant is also in operation. When metal sodium and PCB are reacted, PCB is dechlorinated to produce biphenyl, sodium chloride, a biphenyl polymer obtained by polymerizing biphenyl, and sodium hydroxide. Several problems have been pointed out regarding this product, A countermeasure for this has been proposed (see, for example, Patent Document 1).

また不純物を含むＰＣＢ混入絶縁油を処理すると処理設備、処理プロセスに悪影響を及ぼす。例えば、ＰＣＢ混入絶縁油を抜き出した後に柱上変圧器を破砕しこれを真空加熱し回収される留出液には水溶性の有機酸が含まれ、これが配管を腐食させることがある。またＰＣＢと金属ナトリウムとを反応させるに先立ち行なわれる被処理油中の水分除去操作により、タール状のスラッジが析出し、これがストレーナを閉塞させることがある。これに対し本出願人は、既に有機酸を除去する装置を開発し特許出願中である（特願２００８−３１８１１４）。またＰＣＢ汚染物を真空加熱し回収される回収物には、ＰＣＢを含む炭化水素系油状物の他、熱分解生成物である木酢液、タール状物質が含まれ、これらがＰＣＢの分解処理に悪影響を及ぼすとし、ＰＣＢの分解処理に先立ち、蒸留操作により低沸点熱分解生成物を除去し、さらに吸着剤を使用しタール状物質を吸着除去する技術が提案されている（例えば特許文献２参照）。   Moreover, if the PCB mixed insulating oil containing impurities is treated, the treatment equipment and the treatment process are adversely affected. For example, a distillate collected by extracting a PCB-mixed insulating oil after crushing a pole transformer and heating it in a vacuum contains water-soluble organic acid, which may corrode piping. Moreover, tar-like sludge may be deposited by the water removal operation in the oil to be treated prior to the reaction between PCB and metallic sodium, which may block the strainer. On the other hand, the present applicant has already developed a device for removing an organic acid and has applied for a patent (Japanese Patent Application No. 2008-318114). In addition to the hydrocarbon-based oils containing PCB, the recovered materials collected by vacuum heating of PCB contaminants include pyrolysis products, such as pyroligneous acid and tar-like substances, which are used for PCB decomposition. A technique has been proposed in which a low boiling point pyrolysis product is removed by a distillation operation prior to PCB decomposition, and a tar-like substance is adsorbed and removed using an adsorbent (see, for example, Patent Document 2). ).

特開２００５−３１９４１５号公報JP 2005-319415 A 特開２００４−１７４２９４号公報JP 2004-174294 A

上記以外に不純物を含むＰＣＢ混入絶縁油を金属ナトリウムで無害化処理すると、反応槽内にスケールが析出し、これが剥離し配管を閉塞させる、さらには金属ナトリウムの消費量が多くなる等の問題が発生する。以上のように不純物を含むＰＣＢ混入絶縁油を無害化処理するとき、無害化処理設備、運転に多くのトラブル又は悪影響が発生するが、これまでこのような問題点は指摘されておらず、これらを効果的に防止する方法の開発が待たれている。上記問題を解決する手段が廃棄物、廃液又は排水を発生させるとこれらに対する新たなＰＣＢ汚染対策が必要となるため、上記問題を解決する手段は、廃棄物、廃液及び排水を発生することなく上記問題を解決できることが非常に重要である。   In addition to the above, if PCB-containing insulating oil containing impurities is detoxified with metallic sodium, scale precipitates in the reaction tank, which peels off and closes the piping, and further increases the consumption of metallic sodium. Occur. As described above, when PCB-insulated insulating oil containing impurities is detoxified, many troubles or adverse effects occur in the detoxification equipment and operation, but such problems have not been pointed out so far. The development of a method to effectively prevent this is awaited. If the means for solving the above problems generate waste, waste liquid or waste water, a new PCB contamination countermeasure is required for these, so the means for solving the above problems is the above without generating waste, waste liquid and waste water. It is very important to be able to solve the problem.

本発明の目的は、廃棄物、廃液及び排水を発生させることなく不純物を含むＰＣＢ混入絶縁油を浄化し、ＰＣＢ混入絶縁油の無害化処理を安定的に行うことが可能でかつ金属ナトリウムの消費量を低減可能なＰＣＢ混入絶縁油の無害化処理設備を提供することである。   It is an object of the present invention to purify PCB-containing insulating oil containing impurities without generating waste, waste liquid and waste water, to stably perform the detoxification treatment of PCB-containing insulating oil, and to consume metal sodium An object of the present invention is to provide a detoxification facility for PCB-mixed insulating oil capable of reducing the amount.

本発明者らは、鋭意検討を重ねた結果、ＰＣＢ混入絶縁油の無害化処理において、不純物を含むＰＣＢ混入絶縁油を被処理油とするとき発生する種々のトラブル、悪影響は、被処理油に含まれる酸化変質油に起因し、この酸化変質油を取り除くことでトラブル、悪影響を抑制することができること、この酸化変質油は極性を持つため吸着剤で吸着除去可能なこと、さらに酸化変質油を吸着した吸着剤を廃棄物、廃液及び排水を発生させることなく再生可能な手段を見出し、本発明を完成するに至った。   As a result of intensive studies, the present inventors have found that various troubles and adverse effects that occur when the PCB-mixed insulating oil containing impurities is treated in the detoxification treatment of PCB-mixed insulating oil, It is possible to suppress troubles and adverse effects by removing this oxidized modified oil due to the oxidized modified oil contained in it, and because this oxidized modified oil has polarity, it can be adsorbed and removed by an adsorbent. The present invention has been completed by finding means capable of regenerating the adsorbent adsorbed without generating waste, waste liquid or waste water.

すなわち本発明は、ＰＣＢ混入絶縁油に含まれる酸化変質油を化学吸着及び／又は物理吸着する吸着剤と、前記吸着剤を洗浄する水を供給する洗浄水供給手段と、酸化変質油を含む洗浄後の水を電気分解する電解装置と、洗浄後の吸着剤を乾燥させる乾燥手段とを含む油浄化装置と、ＰＣＢ混入絶縁油中のＰＣＢを金属ナトリウムで脱塩素化する無害化処理装置と、を備え、前記吸着剤を洗浄する水は、酸化変質油を含む洗浄後の水を前記電解装置で電気分解した水であり、水を循環使用し系外に排出しないことを特徴とするＰＣＢ混入絶縁油の無害化処理設備である。 That is, the present invention relates to an adsorbent that chemically and / or physically adsorbs oxidized denatured oil contained in PCB-mixed insulating oil, cleaning water supply means that supplies water for washing the adsorbent, and cleaning that includes oxidized denatured oil and electrolysis of the electrolytic apparatus of water after an oil purification device and a drying device to dry the adsorbent after washing, and detoxification apparatus for dechlorination of PCB in P CB contamination insulating oil with sodium metal The water for washing the adsorbent is water obtained by electrolyzing the washed water containing the oxidized denatured oil with the electrolyzer, and does not discharge water out of the system by circulating water. This is a detoxification facility for mixed insulating oil.

また本発明において、前記水は、硫酸塩、炭酸塩、塩化ナトリウムのうち１種以上の電解質を含み、前記電気分解で過酸化物が生成し、該過酸化物が前記酸化変質油を酸化分解することを特徴とする。 In the present invention, the water contains one or more electrolytes of sulfate, carbonate, and sodium chloride, and a peroxide is generated by the electrolysis, and the peroxide oxidizes and decomposes the oxidized and modified oil. It is characterized by doing.

また本発明において、前記酸化変質油は、Ｃ＝Ｏ結合及びＣ−Ｏ結合を含むことを特徴とする。 In the present invention, the oxidized modified oil includes a C.dbd.O bond and a C-O bond.

また本発明において、前記酸化変質油は、ＰＣＢ汚染物を真空加熱し回収される回収絶縁油に含まれることを特徴とする。   In the present invention, the oxidized and altered oil is contained in a recovered insulating oil that is recovered by vacuum heating of PCB contaminants.

本発明に係るＰＣＢ混入絶縁油の無害化処理設備は、ＰＣＢ混入絶縁油中の酸化変質油を吸着剤で吸着除去する油浄化装置を有するので、酸化変質油が除去又は低減されたＰＣＢ混入絶縁油を金属ナトリウムと反応させることが可能となる。これにより従来見られた酸化変質油に起因するＰＣＢ混入絶縁油無害化処理設備のトラブルを解消又は低減させ、ＰＣＢ混入絶縁油の無害化処理を安定的に行うことができる。さらに金属ナトリウムの消費量を低減させることができる。また前記油浄化装置は、吸着剤を再生する再生手段を備えるので吸着剤を繰り返し使用することが可能であり、さらに吸着剤の再生を廃棄物、廃液及び排水を発生させることなく行うことができるので、新たな廃棄物、廃液及び排水処理対策が不要であり実用的である。 Since the PCB-mixed insulating oil detoxification treatment facility according to the present invention has an oil purification device that adsorbs and removes the oxidized and denatured oil in the PCB-mixed insulating oil with an adsorbent, the PCB-mixed insulation in which the oxidized and denatured oil is removed or reduced is provided. It becomes possible to react the oil with metallic sodium. Thereby, the trouble of the PCB-mixed insulating oil detoxification processing equipment caused by the oxidized and deteriorated oil , which has been conventionally seen, can be eliminated or reduced, and the PCB-mixed insulating oil can be stably detoxified. Furthermore, the consumption of metallic sodium can be reduced. In addition, since the oil purifier includes a regeneration means for regenerating the adsorbent, the adsorbent can be used repeatedly, and the adsorbent can be regenerated without generating waste, waste liquid, and waste water. Therefore, new waste, waste liquid and wastewater treatment measures are unnecessary and practical.

本発明の実施の一形態であるＰＣＢ混入絶縁油無害化処理設備１の概略的構成を示す図である。It is a figure which shows schematic structure of the PCB mixing insulation oil detoxification processing equipment 1 which is one Embodiment of this invention. 図１のＰＣＢ混入絶縁油無害化処理設備１の油浄化装置５０の概略的構成を示す図である。It is a figure which shows schematic structure of the oil purification apparatus 50 of the PCB mixing insulation oil detoxification processing equipment 1 of FIG. 紙木類乾留物を含む絶縁油と紙木類乾留物を含まない絶縁油をフーリエ変換赤外分光法ＦＴＩＲで分析した結果を示す図である。It is a figure which shows the result of having analyzed the insulating oil containing paper wood dry matter and the insulating oil which does not contain paper wood dry matter by Fourier-transform infrared spectroscopy FTIR. 酸化変質油の有無による金属ナトリウム注入量とＰＣＢ分解後の油中のＰＣＢ濃度との関係を示す図である。It is a figure which shows the relationship between the metal sodium injection amount by the presence or absence of oxidation alteration oil, and the PCB density | concentration in the oil after PCB decomposition | disassembly.

図１は、本発明の実施の一形態であるＰＣＢ混入絶縁油無害化処理設備１の概略的構成を示す図である。図２は、ＰＣＢ混入絶縁油無害化処理設備１の油浄化装置５０の概略的構成を示す図である。   FIG. 1 is a diagram showing a schematic configuration of a PCB-mixed insulating oil detoxification treatment facility 1 according to an embodiment of the present invention. FIG. 2 is a diagram showing a schematic configuration of the oil purifying device 50 of the PCB-mixed insulating oil detoxification processing facility 1.

ＰＣＢ混入絶縁油無害化処理設備１は、ＰＣＢ混入絶縁油、さらにはＰＣＢ汚染物に付着するＰＣＢ混入絶縁油を回収し、これらを金属ナトリウムで無害化する設備であり、ＰＣＢ汚染物を真空加熱し汚染物に付着する絶縁油を回収する絶縁油回収装置２と、絶縁油回収装置２で回収される回収絶縁油及び柱上変圧器から抜き出されたＰＣＢ混入絶縁油等を無害化する無害化処理装置３と、回収絶縁油を浄化する油浄化装置５０とを含み構成される。油浄化装置５０を除いた他の装置は、従来から使用されているＰＣＢ混入絶縁油無害化処理設備と基本的に同じ構成である。柱上変圧器に充填されたＰＣＢ微量混入絶縁油及び柱上変圧器に付着するＰＣＢ微量混入絶縁油を回収し、これらを無害化処理する場合を例に採り、まず油浄化装置５０を除いたＰＣＢ混入絶縁油無害化処理設備の構成、無害化処理プロセス、従来、酸化変質油を含むＰＣＢ混入絶縁油を処理するとき発生していたトラブル、悪影響について説明し、続いて油浄化装置５０の構成及び作用効果について説明する。   The PCB-mixed insulating oil detoxification treatment facility 1 is a facility that collects PCB-mixed insulating oil and further PCB-mixed insulating oil adhering to PCB contaminants and detoxifies them with metal sodium. Insulating oil recovery device 2 that recovers the insulating oil adhering to the contaminants, harmlessness that makes the insulating oil recovered by the insulating oil recovery device 2 and PCB mixed insulating oil extracted from the pole transformer harmless It comprises the chemical treatment device 3 and an oil purification device 50 for purifying the recovered insulating oil. The other devices except the oil purifying device 50 have basically the same configuration as the conventional PCB-mixed insulating oil detoxification treatment facility. In this example, the PCB trace mixed insulating oil filled in the pole transformer and the PCB trace mixed insulating oil adhering to the pole transformer are collected and detoxified, and the oil purifier 50 is first removed. Configuration of detoxification treatment facility for PCB-mixed insulating oil, detoxification process, troubles and adverse effects that have conventionally occurred when processing PCB-mixed insulating oil containing oxidized and denatured oil, and then configuration of oil purification device 50 The operation and effect will be described.

絶縁油回収装置２は、ＰＣＢ汚染物を真空加熱し汚染物に付着する絶縁油を回収する装置であり、ＰＣＢ汚染物を真空加熱する真空加熱炉１１、真空加熱炉１１で蒸発させた絶縁油等を凝縮させる凝縮器１３、凝縮器１３で凝縮回収した凝縮液に含まれる水を分離する油水分離器１５及び回収絶縁油を貯蔵する回収油貯蔵タンク１７を含む。   The insulating oil recovery device 2 is a device that recovers the insulating oil attached to the contaminant by vacuum heating the PCB contaminant. The insulating oil evaporated in the vacuum heating furnace 11 and the vacuum heating furnace 11 that vacuum heats the PCB contaminant. The condenser 13 which condenses etc., the oil-water separator 15 which isolate | separates the water contained in the condensate condensed and collect | recovered with the condenser 13, and the collection | recovery oil storage tank 17 which stores collection | recovery insulating oil are included.

ＰＣＢ汚染物である柱上変圧器は、ＰＣＢ微量混入絶縁油を抜き出した後、解体、破砕されケース、銅線、金具、碍子、紙木などに分けられた後、各々真空加熱炉１１に投入される。真空加熱炉１１内は加熱され、さらに真空ポンプを含む減圧装置により減圧状態となっている。ケース等に付着するＰＣＢを含む絶縁油は、真空加熱炉１１内で蒸発し、凝縮器１３で冷却され凝縮した後、油水分離器１５に送られる。柱上変圧器は、銅線、金具などの金属のほか紙木を含むため、真空加熱炉１１で加熱されるとＰＣＢを含む絶縁油のほか、紙木が乾留されこれらが凝縮液となって油水分離器１５に送られる。このため凝縮液には、ＰＣＢを含む絶縁油のほか水、紙木類乾留物を含む。油水分離器１５では凝縮液が静置され比重差により油相と水相とに分離され、油相は、回収絶縁油として回収油貯蔵タンク１７に送られる。なお回収絶縁油にはＰＣＢを含む絶縁油の他、紙木類乾留物及び少量の水が含まれる。回収油貯蔵タンク１７の回収絶縁油は、タンクローリー１９で無害化処理装置３の処理タンク２１に送られる。   The pole transformer, which is a PCB contaminant, is extracted from PCB insulating oil, disassembled, crushed and separated into cases, copper wires, metal fittings, insulators, paper trees, etc., and then put into the vacuum heating furnace 11 Is done. The inside of the vacuum heating furnace 11 is heated and is in a reduced pressure state by a decompression device including a vacuum pump. The insulating oil containing PCB adhering to the case or the like is evaporated in the vacuum heating furnace 11, cooled and condensed by the condenser 13, and then sent to the oil / water separator 15. Since the pole transformer includes paper, in addition to metal such as copper wire and metal fittings, when heated in the vacuum heating furnace 11, the paper is dry-distilled in addition to insulating oil containing PCB, and these become condensate. It is sent to the oil / water separator 15. For this reason, the condensate contains water and paper wood distillate in addition to insulating oil containing PCB. In the oil / water separator 15, the condensate is allowed to stand and is separated into an oil phase and an aqueous phase due to a difference in specific gravity, and the oil phase is sent to the recovered oil storage tank 17 as recovered insulating oil. In addition, the recovered insulating oil includes paper and wood distillate and a small amount of water in addition to the insulating oil containing PCB. The recovered insulating oil in the recovered oil storage tank 17 is sent to the processing tank 21 of the detoxification processing apparatus 3 by the tank lorry 19.

無害化処理装置３は、ＳＰプロセス（soduim pulverulent dispersion）法を用いてＰＣＢ混入絶縁油を無害化する装置であり、金属ナトリウムとＰＣＢとを反応させＰＣＢを脱塩素化する。無害化処理装置３は、被処理油を貯蔵する処理タンク２１、被処理油に含まれる水を除去する減圧蒸留槽２３、ＰＣＢを金属ナトリウムと反応させ脱塩素化する反応槽２５、ＰＣＢの脱塩素化を確認するための分解確認槽２７、処理済油に含まれる残存金属ナトリウムを水和させ、さらに中和する抽出中和槽３１、処理済油と水とを分離する油水分離槽３３、水を回収する洗浄水再生設備３５を備える。   The detoxification treatment device 3 is a device for detoxifying PCB-containing insulating oil using an SP process (soduim pulverulent dispersion) method, and reacts metallic sodium with PCB to dechlorinate PCB. The detoxification treatment apparatus 3 includes a treatment tank 21 for storing the oil to be treated, a vacuum distillation tank 23 for removing water contained in the oil to be treated, a reaction tank 25 for reacting the PCB with metal sodium and dechlorinating, and a removal of the PCB. Decomposition confirmation tank 27 for confirming chlorination, extraction neutralization tank 31 for hydrating and neutralizing residual metallic sodium contained in the treated oil, oil / water separation tank 33 for separating the treated oil and water, A washing water recycling facility 35 for collecting water is provided.

被処理油は、柱上変圧器から抜き出されたＰＣＢ微量混入絶縁油、又は柱上変圧器から抜き出されたＰＣＢ微量混入絶縁油と絶縁油回収装置２で回収される回収絶縁油との混合物であり、これらは処理タンク２１に貯蔵された後、減圧蒸留槽２３に送られる。   The to-be-treated oil is composed of the PCB trace mixed insulating oil extracted from the pole transformer, or the PCB trace mixed insulating oil extracted from the pole transformer and the recovered insulating oil recovered by the insulating oil recovery device 2. The mixture is stored in the processing tank 21 and then sent to the vacuum distillation tank 23.

減圧蒸留槽２３は、ジャケット付き攪拌槽であり、ジャケットに加熱した熱媒を供給することで被処理油を加熱する。また減圧蒸留槽２３は、槽内を減圧し被処理油に含まれる水を蒸発させ凝縮し回収する減圧装置（図示を省略）を備え、処理タンク２１から送られた被処理油は、ここで９０℃程度に加熱、０．０１４２Ｍｐａ程度に減圧され、被処理油に含まれる水が除去される。減圧蒸留槽２３で水分が除去された被処理油は反応槽２５に送られる。   The vacuum distillation tank 23 is a jacketed stirring tank, and heats the oil to be treated by supplying a heated heat medium to the jacket. The vacuum distillation tank 23 is equipped with a decompression device (not shown) that depressurizes the inside of the tank and evaporates, condenses, and recovers water contained in the oil to be treated, and the oil to be treated sent from the treatment tank 21 is here. It is heated to about 90 ° C. and depressurized to about 0.0142 Mpa to remove water contained in the oil to be treated. The treated oil from which moisture has been removed in the vacuum distillation tank 23 is sent to the reaction tank 25.

反応槽２５は、ジャケット付き攪拌槽であり、ここで減圧蒸留槽２３で水分が除去された被処理油に金属ナトリウムが添加される。金属ナトリウムは、絶縁油中に金属ナトリウムの微粒子を分散させた金属ナトリウム分散体（ＳＤ：soduim dispersion）として反応槽２５に添加される。被処理油と金属ナトリウムとは、攪拌されながらジャケットに供給される加熱した熱媒により９０℃程度まで加熱され、ＰＣＢは金属ナトリウムと反応し脱塩素化し、被処理油は無害化される。なお、金属ナトリウム分散体を添加し所定の時間経過後に、反応促進剤として所定量の水が添加される。反応槽２５の気相部には窒素ガスが供給されている。   The reaction tank 25 is a jacketed stirring tank, in which metal sodium is added to the oil to be treated from which water has been removed in the vacuum distillation tank 23. The metallic sodium is added to the reaction vessel 25 as a metallic sodium dispersion (SD: soduim dispersion) in which fine particles of metallic sodium are dispersed in insulating oil. The oil to be treated and the metal sodium are heated to about 90 ° C. by a heated heating medium supplied to the jacket while being stirred, and the PCB reacts with the metal sodium to dechlorinate, so that the oil to be treated is rendered harmless. A predetermined amount of water is added as a reaction accelerator after the metal sodium dispersion is added and a predetermined time elapses. Nitrogen gas is supplied to the gas phase portion of the reaction tank 25.

反応槽２５でＰＣＢが脱塩素化された被処理油（処理済油）は、分解確認槽２７に送られ、サンプリングライン２９を介してサンプリングされ、処理済油中のＰＣＢ濃度が所定の濃度以下になっているか確認される。ここでＰＣＢが所定濃度以下に達していないことが確認されると、処理済液を反応槽２５に返送し再度、ＰＣＢの脱塩素化を行う。処理済油は、ＰＣＢ濃度が所定の濃度以下であることが確認されると冷却され、その後に抽出中和槽３１に送られる。   The treated oil (treated oil) from which PCB has been dechlorinated in the reaction tank 25 is sent to the decomposition confirmation tank 27 and sampled through the sampling line 29, and the PCB concentration in the treated oil is below a predetermined concentration. Is confirmed. Here, when it is confirmed that the PCB does not reach the predetermined concentration or less, the treated liquid is returned to the reaction tank 25 and the PCB is dechlorinated again. The treated oil is cooled when it is confirmed that the PCB concentration is equal to or lower than a predetermined concentration, and then sent to the extraction neutralization tank 31.

分解確認槽２７から送られる処理済油は、抽出中和槽３１で多量の水と混合され、処理済油中に残存する金属ナトリウムが水和される。さらに金属ナトリウムが水和され生成した水酸化ナトリウムを中和させるための炭酸ガスが吹き込まれ所定のｐＨに調整された後、油水分離槽３３に送られる。   The treated oil sent from the decomposition confirmation tank 27 is mixed with a large amount of water in the extraction neutralization tank 31, and the metallic sodium remaining in the treated oil is hydrated. Further, carbon dioxide gas for neutralizing sodium hydroxide produced by hydration of metallic sodium is blown and adjusted to a predetermined pH, and then sent to the oil / water separation tank 33.

油水分離槽３３に送られる多量の水を含む処理済油は、油水分離槽３３で静置され比重差により油相３７と水相３９とに分離される。上層の油相３７は、処理済油タンク４１に送られ貯蔵される。一方、下層の水相３９は、水を回収する洗浄水再生設備３５に送られる。   The treated oil containing a large amount of water sent to the oil / water separation tank 33 is left in the oil / water separation tank 33 and separated into an oil phase 37 and an aqueous phase 39 due to a difference in specific gravity. The upper oil phase 37 is sent to the treated oil tank 41 and stored. On the other hand, the lower aqueous phase 39 is sent to a washing water recycling facility 35 that collects water.

洗浄水再生設備３５は、乾燥機４３を備え、水を蒸発させ回収すると共に水に含まれる塩化ナトリウム等を蒸発乾固させる。油水分離槽３３から送られる水は静置分離水受槽４５に一度、貯留された後、乾燥機４３に送られ加熱される。蒸発した水は、凝縮器４７で凝縮し凝縮水槽４９に貯留される。この水は抽出中和槽３１に送られ、金属ナトリウムを水和させるための水として使用される。一方、水に溶解していた塩化ナトリウム等は乾燥汚泥として回収される。このように無害化設備３は、水を系外に排出しないクローズドシステムとなっている。   The washing water regeneration facility 35 includes a dryer 43, which evaporates and collects water and evaporates and drys sodium chloride contained in the water. The water sent from the oil / water separation tank 33 is once stored in the stationary separation water receiving tank 45 and then sent to the dryer 43 and heated. The evaporated water is condensed by the condenser 47 and stored in the condensed water tank 49. This water is sent to the extraction neutralization tank 31 and used as water for hydrating metallic sodium. On the other hand, sodium chloride or the like dissolved in water is recovered as dry sludge. In this way, the detoxification facility 3 is a closed system that does not discharge water out of the system.

ＰＣＢ微量混入絶縁油を抜き出した後の柱上変圧器を破砕しこれを真空加熱し回収される回収絶縁油が含まれるＰＣＢ微量混入絶縁油を被処理油とする場合、被処理油には、Ｃ＝Ｏ結合及びＣ−Ｏ結合を含む酸化変質油が含まれる。Ｃ＝Ｏ結合及びＣ−Ｏ結合を含む酸化変質油が含まれるのは、柱上変圧器に紙、木が含まれ、これらの乾留物が回収絶縁油に含まれることによる。図３は、紙木類乾留物を含む絶縁油と紙木類乾留物を含まない絶縁油をフーリエ変換赤外分光法ＦＴＩＲで分析した結果を示す図である。紙木類乾留物を含む絶縁油にはＣ＝Ｏのピーク１７５０ｃｍ−１が強く表れている。Ｃ＝Ｏ結合を含む油酸化変質物としては、カルボン酸、エステル、アルデヒド、ケトンがある。酸化変質油はカルボン酸、アルコール類など水溶性の酸化変質油、非水溶性の酸化変質油を含み、極性が強いため、一部の酸化変質油は時間経過と共に酸化変質油同士が凝集、合体しスラッジとなり析出する。 When the PCB transformer mixed oil containing the recovered insulating oil is recovered by crushing the pole transformer after extracting the PCB trace insulating oil and vacuum heating it, Oxidized modified oils containing C═O bonds and C—O bonds are included. The reason why the oxidized modified oil containing C═O bond and C—O bond is included is that the pole transformer includes paper and wood, and these dry-distilled products are included in the recovered insulating oil. FIG. 3 is a diagram showing the results of analysis by Fourier transform infrared spectroscopy FTIR of insulating oil containing paper-wood dry matter and insulating oil not containing paper-wood dry matter. A peak of 1750 cm −1 of C═O appears strongly in the insulating oil containing the paper tree dry matter. Examples of the oil-oxidized alteration product containing a C═O bond include carboxylic acid, ester, aldehyde, and ketone. Oxidized and modified oils include water-soluble oxidized and modified oils such as carboxylic acids and alcohols, and water-insoluble oxidized and modified oils. Because of their strong polarity, some oxidized and modified oils aggregate and coalesce with each other over time. Sludge becomes sludge and precipitates.

油浄化装置５０を備えない従来のＰＣＢ混入絶縁油無害化処理設備を用いて酸化変質油を含むＰＣＢ混入絶縁油を処理する場合、析出するスラッジはタール状で粘性が高いため、例えば回収油貯蔵タンク１７から回収絶縁油を払出すラインに設けられたストレーナ（図示を省略）を閉塞させる。また酸化変質油に含まれる酸性成分又はスラッジは被処理油中の水と交わり酸性を呈するため、例えば回収油貯蔵タンク１７から回収絶縁油を払出すラインの配管等を腐食させる。さらに減圧蒸留槽２３で水分を除去すると水溶性の酸化変質油もスラッジとなって析出し、減圧蒸留槽２３と反応槽２５を結ぶラインに設けられたストレーナ（図示を省略）を閉塞させる。また酸化変質油を含むＰＣＢ微量混入絶縁油を被処理油とし、これを金属ナトリウムさらに反応促進剤である水と反応させると、酸化変質油も金属ナトリウムと反応するため、図４に示すように金属ナトリウムの消費量が多くなる。酸化変質油を含むＰＣＢ微量混入絶縁油と金属ナトリウム、反応促進剤である水との代表的な反応は、次式で示される。さらに酸化変質油が金属ナトリウム、反応促進剤と反応し生成する鹸化物、炭酸塩、有機酸塩等は、絶縁油には溶解せずかつ極性が強いため金属面に付着し易く、これらが壁面に付着、成長しスケールとなることで種々のトラブルが発生する。   When processing PCB mixed insulating oil containing oxidized and denatured oil using conventional PCB mixed insulating oil detoxification processing equipment that does not include the oil purification device 50, the sludge that precipitates is tar-like and highly viscous. A strainer (not shown) provided in a line for discharging the recovered insulating oil from the tank 17 is closed. In addition, since the acidic component or sludge contained in the oxidized modified oil is mixed with the water in the oil to be treated and exhibits acidity, for example, the piping of the line for discharging the recovered insulating oil from the recovered oil storage tank 17 is corroded. Further, when water is removed in the vacuum distillation tank 23, water-soluble oxidized and denatured oil is also precipitated as sludge, and a strainer (not shown) provided in a line connecting the vacuum distillation tank 23 and the reaction tank 25 is closed. In addition, if PCB insulating oil containing oxidized modified oil is treated oil, and this is reacted with water, which is metal sodium and further a reaction accelerator, oxidized modified oil also reacts with metal sodium, as shown in FIG. The consumption of metallic sodium increases. A typical reaction between a PCB trace-mixed insulating oil containing oxidized denatured oil, metallic sodium, and water as a reaction accelerator is represented by the following formula. Furthermore, saponified products, carbonates, organic acid salts, etc. produced by the reaction of oxidized modified oil with metallic sodium and reaction accelerators do not dissolve in insulating oil and are strong in polarity, so they easily adhere to the metal surface. Various troubles occur due to adhesion and growth to the scale.

Figure 0005383595
Figure 0005383595

本実施形態に示すＰＣＢ混入絶縁油無害化処理設備１は、油浄化装置５０が回収絶縁油に含まれる酸化変質油を除去又は低減させ、従来のＰＣＢ混入絶縁油無害化処理で見られたトラブルを防止する。   In the PCB-mixed insulating oil detoxification treatment facility 1 shown in the present embodiment, the oil purification apparatus 50 removes or reduces the oxidized denatured oil contained in the recovered insulating oil, and the trouble seen in the conventional PCB-mixed insulating oil detoxification treatment To prevent.

油浄化装置５０は、回収油貯蔵タンク１７に貯蔵する回収絶縁油を浄化するための装置であり、回収絶縁油に含まれる酸化変質油を吸着する吸着剤５２が充填された吸着塔５４（５４ａ、５４ｂ）と、酸化変質油を吸着し吸着能力が低下した吸着剤５２を再生する再生装置５６を備える。   The oil purification device 50 is a device for purifying the recovered insulating oil stored in the recovered oil storage tank 17, and is an adsorption tower 54 (54a) filled with an adsorbent 52 that adsorbs oxidized denatured oil contained in the recovered insulating oil. , 54b), and a regenerator 56 that regenerates the adsorbent 52 that has adsorbed oxidized denatured oil and has reduced adsorption capacity.

吸着塔５４は２塔設けられ、油循環ポンプ５８が介装された油循環ライン６０を通じて、回収油貯蔵タンク１７と結ばれる。また吸着塔５４は、回収油貯蔵タンク１７に比べ高い位置に設置されており、吸着塔５４内の回収絶縁油を全て抜き出し回収油貯蔵タンク１７に返送することができる油回収ライン６２（６２ａ、６２ｂ）が設けられている。油循環ライン６０には２塔の吸着塔５４ａ、５４ｂのそれぞれに回収絶縁油を単独に供給できるようにバルブが設けられている。油回収ライン６２（６２ａ、６２ｂ）もそれぞれの吸着塔５４ａ、５４ｂ内の回収絶縁油を回収可能に設けられている。   Two adsorption towers 54 are provided, and are connected to the recovered oil storage tank 17 through an oil circulation line 60 in which an oil circulation pump 58 is interposed. Further, the adsorption tower 54 is installed at a higher position than the recovered oil storage tank 17, and an oil recovery line 62 (62 a, 62 a) that can extract all the recovered insulating oil in the adsorption tower 54 and return it to the recovered oil storage tank 17. 62b) is provided. The oil circulation line 60 is provided with a valve so that the recovered insulating oil can be supplied independently to each of the two adsorption towers 54a and 54b. The oil recovery lines 62 (62a, 62b) are also provided so as to recover the recovered insulating oil in the respective adsorption towers 54a, 54b.

ここで使用する吸着剤５２は、酸化変質油を化学吸着及び／又は物理吸着できるものであればよく、特定の吸着剤に限定されるものではない。吸着性能に優れる吸着剤が好ましいことは言うまでもない。酸化変質油は極性を有するため化学吸着及び／又は物理吸着が容易であり、化学吸着剤としてＣａＯ、ＭｇＯ、Ａｌ２Ｏ３、Ｃａ（ＯＨ）２、Ｍｇ（ＯＨ）２、Ａｌ（ＯＨ）３などが、物理吸着剤としてゼオライト、シリカゲル、活性炭等が例示される。 The adsorbent 52 used here is not limited to a specific adsorbent, as long as it can chemically adsorb and / or physically adsorb oxidized oxidized oil. Needless to say, an adsorbent having excellent adsorption performance is preferable. Oxidized and denatured oil has polarity, and thus is easily chemisorbed and / or physically adsorbed. As a chemical adsorbent, CaO, MgO, Al 2 O 3 , Ca (OH) 2 , Mg (OH) 2 , Al (OH) 3 Examples of the physical adsorbent include zeolite, silica gel, activated carbon and the like.

吸着塔５４の大きさは、酸化変質油の濃度、回収絶縁油の量に基づき適宜設定すればよく、吸着塔５４の構造も回収絶縁油がショートパスすることなく、また充填する吸着剤５２全体と均一に接触可能なものであれば特定の構造のものに限定されない。また吸着塔５４内を上下２段に区切り、各々の段に化学吸着剤、物理吸着剤を分けて充填するようにしてもよい。   The size of the adsorption tower 54 may be set as appropriate based on the concentration of oxidized denatured oil and the amount of recovered insulating oil. The structure of the adsorption tower 54 does not cause a short path of the recovered insulating oil, and the entire adsorbent 52 to be filled. As long as it can be contacted uniformly, it is not limited to a specific structure. Alternatively, the inside of the adsorption tower 54 may be divided into two upper and lower stages, and each stage may be filled with a chemical adsorbent and a physical adsorbent.

再生装置５６は、吸着塔５４に洗浄（再生）水を送る洗浄水供給手段と、吸着剤５２を洗浄した酸化変質油を含む洗浄後の水を電気分解する電解装置６４と、洗浄後の吸着剤５２に付着する水を蒸発させ乾燥させる減圧装置６８を備える。   The regenerator 56 includes a washing water supply means for sending the washing (regeneration) water to the adsorption tower 54, an electrolysis device 64 for electrolyzing the washed water containing the oxidized denatured oil that has washed the adsorbent 52, and the adsorption after the washing. A pressure reducing device 68 that evaporates and dries the water adhering to the agent 52 is provided.

電解装置６４と再生用水タンク６６と吸着塔５４とは、水循環ポンプ７０が介装された水循環ライン７２で結ばれ、水循環ポンプ７０が介装された水循環ライン７２が洗浄水供給手段として機能する。電解装置６４で電気分解された水を貯蔵する再生用水タンク６６は、吸着塔５４に比べ低い位置に設置されており、洗浄に使用した吸着塔５４内の水を全て抜き出し再生用水タンク６６に返送することができる水回収ライン７４（７４ａ、７４ｂ）が設けられている。水循環ライン７２にはそれぞれの吸着塔５４ａ、５４ｂに洗浄用の水を単独に供給できるようにバルブが設けられている。水回収ライン７４（７４ａ、７４ｂ）もそれぞれの吸着塔５４ａ、５４ｂ内の水を回収可能に設けられている。   The electrolyzer 64, the regeneration water tank 66, and the adsorption tower 54 are connected by a water circulation line 72 in which a water circulation pump 70 is interposed, and the water circulation line 72 in which the water circulation pump 70 is interposed functions as washing water supply means. A regeneration water tank 66 for storing water electrolyzed by the electrolyzer 64 is installed at a lower position than the adsorption tower 54, and all the water in the adsorption tower 54 used for washing is extracted and returned to the regeneration water tank 66. Water recovery lines 74 (74a, 74b) are provided. The water circulation line 72 is provided with a valve so that cleaning water can be independently supplied to the respective adsorption towers 54a and 54b. The water recovery lines 74 (74a, 74b) are also provided so as to recover the water in the respective adsorption towers 54a, 54b.

洗浄に使用する水には、電気分解により過酸化物が生成する電解質を含む水を使用する。このような電解質としてＮａ２ＳＯ４，Ｋ２ＳＯ４などの硫酸塩、Ｎａ２ＣＯ３，Ｋ２ＣＯ３などの炭酸塩、ＮａＣｌなどが例示され、水に溶解したとき中性を示すものが好ましい。Ｎａ２ＳＯ４，Ｋ２ＳＯ４などの硫酸塩、Ｎａ２ＣＯ３，Ｋ２ＣＯ３などの炭酸塩、ＮａＣｌなどを含む水を電解することで、ペルオキソ一硫酸（Ｈ２ＳＯ５）、過炭酸（Ｈ２ＣＯ３・３／２Ｈ２Ｏ２）、次亜塩素酸（ＨＯＣｌ）などの過酸化物が生成する。これら過酸化物は、強い酸化作用を有するので、水に溶解した酸化変質油を酸化分解することができる。電解質として硫酸塩、炭酸塩等を添加せず、水に溶解した酸化変質油に含まれるカルボン酸等を利用することもできるが分解速度が遅いため、硫酸塩、炭酸塩等の電気分解により過酸化物が生成する電解質を添加することが好ましい。 As the water used for washing, water containing an electrolyte that generates a peroxide by electrolysis is used. Examples of such an electrolyte include sulfates such as Na 2 SO 4 and K 2 SO 4 , carbonates such as Na 2 CO 3 and K 2 CO 3 , NaCl, and the like, and those that show neutrality when dissolved in water. preferable. By electrolyzing water containing sulfates such as Na 2 SO 4 and K 2 SO 4 , carbonates such as Na 2 CO 3 and K 2 CO 3 , NaCl, etc., peroxomonosulfuric acid (H 2 SO 5 ) carbonate (H 2 CO 3 · 3 / 2H 2 O 2), peroxides such as hypochlorous acid (HOCl) is produced. Since these peroxides have a strong oxidizing action, it is possible to oxidatively decompose oxidized denatured oil dissolved in water. Carboxylic acid contained in oxidized modified oil dissolved in water can be used without adding sulfate, carbonate, etc. as the electrolyte. However, since the decomposition rate is slow, it is excessive by electrolysis of sulfate, carbonate, etc. It is preferable to add an electrolyte that generates an oxide.

電解装置６４は、電解電極７６と電解電極７６に電源を供給する電源供給装置（図示を省略）とを備える。電解電極７６は、電食防止のためのシールド型の電解電極であり、電源供給装置から所定の電圧が印加され、電解質を含む水を電気分解し過酸化物を生成させ、生成する過酸化物で水に溶解する酸化変質油を酸化分解する。   The electrolysis device 64 includes an electrolysis electrode 76 and a power supply device (not shown) that supplies power to the electrolysis electrode 76. The electrolytic electrode 76 is a shield-type electrolytic electrode for preventing electrolytic corrosion. A predetermined voltage is applied from a power supply device, and water containing the electrolyte is electrolyzed to generate a peroxide. Oxidative degradation of oxidatively modified oil that dissolves in water.

減圧装置６８は、真空ポンプ（図示を省略）及び蒸発した水を凝縮させる凝縮器（図示を省略）を備え、各吸着塔５４ａ、５４ｂとガスライン７８を介して結ばれる。ガスライン７８は、ライン途中にバルブが設けられ、吸着塔５４ａ、５４ｂを個別に減圧可能に構成されている。   The decompression device 68 includes a vacuum pump (not shown) and a condenser (not shown) for condensing evaporated water, and is connected to the adsorption towers 54 a and 54 b via the gas line 78. The gas line 78 is provided with a valve in the middle of the line so that the adsorption towers 54a and 54b can be individually decompressed.

油浄化装置５０の運転要領の一例を示す。吸着塔５４ａが吸着工程、吸着塔５４ｂが再生工程であるとする。   An example of the operating procedure of the oil purification apparatus 50 is shown. It is assumed that the adsorption tower 54a is an adsorption process and the adsorption tower 54b is a regeneration process.

回収油貯蔵タンク１７に貯蔵する回収絶縁油は、油循環ライン６０を通じて吸着塔５４ａにのみ供給される。回収絶縁油は、吸着塔５４ａ内を上昇する過程で吸着剤５２と接触し、回収絶縁油に含まれる酸化変質油が吸着剤５２に吸着され、浄化された回収絶縁油が油循環ライン６０を通じて回収油貯蔵タンク１７に返送される。油循環ライン６０を介して回収油貯蔵タンク１７と吸着塔５４ａとの間を回収絶縁油を循環させながら回収絶縁油を浄化する。   The recovered insulating oil stored in the recovered oil storage tank 17 is supplied only to the adsorption tower 54 a through the oil circulation line 60. The recovered insulating oil comes into contact with the adsorbent 52 in the process of rising in the adsorption tower 54 a, the oxidized altered oil contained in the recovered insulating oil is adsorbed by the adsorbent 52, and the purified recovered insulating oil passes through the oil circulation line 60. It is returned to the recovered oil storage tank 17. The recovered insulating oil is purified while circulating the recovered insulating oil between the recovered oil storage tank 17 and the adsorption tower 54a via the oil circulation line 60.

吸着塔５４ｂには、水循環ライン７２を通じて再生用水タンク６６から洗浄用の水が供給される。吸着塔５４ｂに供給された水は、吸着塔５４ｂ内を降下する過程で吸着剤５２と接触し吸着剤５２を洗浄する。吸着剤５２を洗浄した酸化変質油を含む水は、電解装置６４に送られ、ここで電気分解される。水には電解質が含まれ電気分解されることで過酸化物が生成し、水に溶解した酸化変質油は過酸化物で酸化分解される。電気分解後の水は、再生用水タンク６４に送られ循環使用される。   Washing water is supplied from the regeneration water tank 66 to the adsorption tower 54 b through the water circulation line 72. The water supplied to the adsorption tower 54b comes into contact with the adsorbent 52 and cleans the adsorbent 52 in the process of descending the adsorption tower 54b. The water containing the oxidized modified oil that has washed the adsorbent 52 is sent to the electrolyzer 64 where it is electrolyzed. Water contains an electrolyte and is electrolyzed to produce a peroxide, and the oxidized modified oil dissolved in water is oxidized and decomposed with the peroxide. The electrolyzed water is sent to the regeneration water tank 64 for circulation.

洗浄が終了した吸着塔５４ｂは、水循環ライン７２が閉止され、続いて水回収ライン７４ｂを通じて、吸着塔５４ｂ内の全ての水が再生用水タンク６６へ送られる。吸着塔５４ｂ内の全ての水が排出された後、水回収ライン７４ｂが閉止され、続いて減圧装置６８と吸着塔５４ｂとが連通され、吸着塔５４ｂが減圧される。これにより吸着剤５２に付着又は吸着した水が蒸発し吸着剤５２が乾燥する。吸着剤５２の洗浄、乾燥により吸着剤５２の再生が終了する。   In the adsorption tower 54b that has been cleaned, the water circulation line 72 is closed, and then all the water in the adsorption tower 54b is sent to the regeneration water tank 66 through the water recovery line 74b. After all the water in the adsorption tower 54b is discharged, the water recovery line 74b is closed, and then the decompression device 68 and the adsorption tower 54b are communicated to depressurize the adsorption tower 54b. Thereby, the water adhering or adsorbing to the adsorbent 52 evaporates and the adsorbent 52 is dried. The regeneration of the adsorbent 52 is completed by washing and drying the adsorbent 52.

再生が終了した吸着塔５４ｂを吸着工程するには、油循環ライン６０を通じて吸着塔５４ｂに回収絶縁油を供給すればよい。一方、吸着塔５４ａの吸着剤５２を再生するには、油循環ライン６０を閉止した後、油回収ライン６２ａを通じて、吸着塔５４ａ内の全ての回収絶縁油を回収油貯蔵タンク１７に送る。吸着塔５４ａ内の全ての回収絶縁油が排出された後、油回収ライン６２ａを閉止し、水循環ライン７２を通じて再生用水タンク６６から洗浄用の水を供給すればよい。   In order to adsorb the adsorption tower 54b after the regeneration, the recovered insulating oil may be supplied to the adsorption tower 54b through the oil circulation line 60. On the other hand, in order to regenerate the adsorbent 52 of the adsorption tower 54a, after the oil circulation line 60 is closed, all the recovered insulating oil in the adsorption tower 54a is sent to the recovered oil storage tank 17 through the oil recovery line 62a. After all the recovered insulating oil in the adsorption tower 54a is discharged, the oil recovery line 62a is closed, and cleaning water is supplied from the regeneration water tank 66 through the water circulation line 72.

以上のように油浄化装置５０は、２塔の吸着塔５４ａ、５４ｂを備えるので、一方の吸着塔５４ａ（５４ｂ）が吸着工程の間、他方の吸着塔５４ｂ（５４ａ）を再生工程としこれを交互に繰り返すことで連続的に油浄化を行うことができる。   As described above, since the oil purification apparatus 50 includes the two adsorption towers 54a and 54b, the one adsorption tower 54a (54b) is used as the regeneration process while the other adsorption tower 54b (54a) is used as the regeneration process. Oil purification can be performed continuously by repeating alternately.

基礎実験において、酸化変質油を含むＰＣＢ微量混入絶縁油を吸着剤と長時間接触させた後、この油をロータリーエバポレータで減圧蒸留したところ、フラスコ内には殆ど残渣が見られなかった。一方、酸化変質油を含むＰＣＢ微量混入絶縁油をそのままロータリーエバポレータで減圧蒸留したところ、フラスコ内に比較的多くの褐色の残渣が認められた。また酸化変質油を含むＰＣＢ微量混入絶縁油を吸着剤と長時間接触させた後、この油を金属ナトリウムと反応させたところ、ＰＣＢの分解に必要な金属ナトリウム量は、酸化変質油を含まないＰＣＢ微量混入絶縁油とほぼ同等であった。また酸化変質油を吸着した吸着剤を水で洗浄可能なことも基礎実験で確認済みである。   In a basic experiment, a PCB trace-mixed insulating oil containing an oxidized modified oil was contacted with an adsorbent for a long time, and then this oil was distilled under reduced pressure using a rotary evaporator. As a result, almost no residue was found in the flask. On the other hand, when a PCB trace-mixed insulating oil containing oxidation-modified oil was distilled as it was under reduced pressure with a rotary evaporator, a relatively large amount of brown residue was observed in the flask. Further, after contacting PCB with a trace amount of insulating oil containing oxidized modified oil with adsorbent for a long time and then reacting this oil with metallic sodium, the amount of metallic sodium required for PCB decomposition does not include oxidized modified oil. It was almost the same as PCB trace mixed insulating oil. In addition, it has been confirmed in basic experiments that the adsorbent adsorbing oxidized denatured oil can be washed with water.

上記基礎実験から分かるように油浄化装置５０で酸化変質油を含むＰＣＢ混入絶縁油を浄化することで、酸化変質油が低減され、従来、問題となっていたストレーナの閉塞を防止することができる。また酸化変質油に含まれる酸性成分も低減されるため従来、問題となっていた回収絶縁油を払出すラインの配管等の腐食を防止することができる。さらに金属ナトリウムの消費量を低減することができる。また従来問題となっていた反応槽２５の壁面に付着するスケールも酸化変質油が低減されるので抑制することができる。上記のように油浄化装置５０を備えるＰＣＢ混入絶縁油無害化処理設備１は、従来、酸化変質油を含むＰＣＢ混入絶縁油を処理するとき発生していたトラブル、設備及び運転上の悪影響を防止又は抑制することができるので、ＰＣＢ混入絶縁油の無害化処理を安定的に行うことができる。   As can be seen from the above basic experiment, by purifying the PCB-mixed insulating oil containing the oxidized modified oil with the oil purification device 50, the oxidized modified oil is reduced, and the strainer clogging which has been a problem in the past can be prevented. . In addition, since acidic components contained in the oxidized modified oil are also reduced, it is possible to prevent corrosion of piping and the like of a line from which the recovered insulating oil that has been a problem in the past has been hit. Furthermore, consumption of metallic sodium can be reduced. Further, the scale adhering to the wall surface of the reaction tank 25, which has been a problem in the past, can be suppressed because the oxidized and deteriorated oil is reduced. As described above, the PCB-mixed insulating oil detoxification treatment facility 1 provided with the oil purifier 50 prevents the troubles, facilities, and adverse effects on the operation that have occurred when processing the PCB-mixed insulating oil including the oxidized denatured oil. Or since it can suppress, the detoxification process of PCB mixing insulating oil can be performed stably.

また油浄化装置５０は、吸着剤５２を再生しながら使用するので廃棄物とならない。また吸着剤５２の洗浄に使用した水も、水に含まれる酸化変質油を酸化分解し循環使用するので、酸化変質油を含むＰＣＢ混入絶縁油を浄化した後も廃棄物、廃液及び排水が排出されない。ＰＣＢを取り扱う装置、設備の場合、系外に排出される物にＰＣＢが付着していないか又はＰＣＢで汚染されていないかが問題となるが、油浄化装置５０は、廃棄物、廃液及び排水を排出しないのでこのような心配は不要である。   Moreover, since the oil purification apparatus 50 is used while regenerating the adsorbent 52, it does not become waste. Also, the water used for cleaning the adsorbent 52 is oxidatively decomposed and circulated through oxidation-degraded oil contained in the water, so waste, waste liquid and wastewater are discharged even after the PCB-mixed insulating oil containing the oxidized and denatured oil is purified. Not. In the case of equipment and facilities that handle PCBs, there is a problem whether PCBs are not attached to or are not contaminated with PCBs that are discharged outside the system. Such a worry is unnecessary because it is not discharged.

なお本発明は上記実施形態に限定されるものではなく、要旨を変更しない範囲で上記実施形態を変更してもよい。例えば、吸着塔５４にヒータを取付け、再生時の吸着剤５２の乾燥を促進するようにしてもよい。また吸着剤の種類に応じた吸着温度を設定し、吸着性を高めるようにしてもよい。また吸着塔５４へ供給する洗浄用の水は、吸着塔５４の下方から供給し上方から排出するようにしてもよい。   In addition, this invention is not limited to the said embodiment, You may change the said embodiment in the range which does not change a summary. For example, a heater may be attached to the adsorption tower 54 to promote drying of the adsorbent 52 during regeneration. Further, an adsorption temperature may be set according to the type of adsorbent to enhance the adsorptivity. The washing water supplied to the adsorption tower 54 may be supplied from below the adsorption tower 54 and discharged from above.

１ ＰＣＢ混入絶縁油無害化処理設備
２ 絶縁油回収設備
３ 無害化設備
１１ 真空加熱炉
１３ 凝縮器
１５ 油水分離器
１７ 回収油貯蔵タンク
１９ タンクローリー
２１ 処理タンク
２３ 減圧蒸留槽
２５ 反応槽
２７ 分解確認槽
２９ サンプリングライン
３１ 抽出中和槽
３３ 油水分離槽
３５ 洗浄水再生設備
３７ 油相
３９ 水相
４１ 処理済油タンク
４３ 乾燥機
４５ 静置分離水受槽
４７ 凝縮器
４９ 凝縮水槽
５０ 油浄化装置
５２ 吸着剤
５４、５４ａ、５４ｂ 吸着塔
５６ 再生装置
５８ 油循環ポンプ
６０ 油循環ライン
６２、６２ａ、６２ｂ 油回収ライン
６４ 電解装置
６６ 再生用水タンク
６８ 減圧装置
７０ 水循環ポンプ
７２ 水循環ライン
７４、７４ａ、７４ｂ 水回収ライン
７６ 電解電極
７８ ガスライン DESCRIPTION OF SYMBOLS 1 PCB mixing insulation oil detoxification processing equipment 2 Insulation oil recovery equipment 3 Detoxification equipment 11 Vacuum heating furnace 13 Condenser 15 Oil-water separator 17 Recovery oil storage tank 19 Tank lorry 21 Processing tank 23 Vacuum distillation tank 25 Reaction tank 27 Decomposition confirmation tank 29 Sampling Line 31 Extraction Neutralization Tank 33 Oil Water Separation Tank 35 Wash Water Recycling Equipment 37 Oil Phase 39 Water Phase 41 Treated Oil Tank 43 Dryer 45 Stationary Separated Water Receiving Tank 47 Condenser 49 Condensed Water Tank 50 Oil Purifier 52 Adsorbent 54, 54a, 54b Adsorption tower 56 Regeneration device 58 Oil circulation pump 60 Oil circulation line 62, 62a, 62b Oil recovery line 64 Electrolyzer 66 Regeneration water tank 68 Decompression device 70 Water circulation pump 72 Water circulation line 74, 74a, 74b Water recovery line 76 Electrode electrode 78 Gas line

Claims (4)

ＰＣＢ混入絶縁油に含まれる酸化変質油を化学吸着及び／又は物理吸着する吸着剤と、前記吸着剤を洗浄する水を供給する洗浄水供給手段と、酸化変質油を含む洗浄後の水を電気分解する電解装置と、洗浄後の吸着剤を乾燥させる乾燥手段とを含む油浄化装置と、
ＰＣＢ混入絶縁油中のＰＣＢを金属ナトリウムで脱塩素化する無害化処理装置と、を備え、
前記吸着剤を洗浄する水は、酸化変質油を含む洗浄後の水を前記電解装置で電気分解した水であり、水を循環使用し系外に排出しないことを特徴とするＰＣＢ混入絶縁油の無害化処理設備。 The adsorbent that chemically and / or physically adsorbs the oxidized modified oil contained in the PCB mixed insulating oil, the washing water supply means for supplying water for washing the adsorbent, and the washed water containing the oxidized modified oil are electrically An oil purifier including an electrolytic device for decomposing, and a drying means for drying the adsorbent after washing ;
The PCB of P CB contamination insulating oil and a detoxification apparatus for dechlorination with metallic sodium,
The water for washing the adsorbent is water obtained by electrolyzing the washed water containing oxidized and denatured oil with the electrolyzer, and is used for circulating the water and not discharging it outside the system . Detoxification processing equipment. 前記水は、硫酸塩、炭酸塩、塩化ナトリウムのうち１種以上の電解質を含み、前記電気分解で過酸化物が生成し、該過酸化物が前記酸化変質油を酸化分解することを特徴とする請求項１に記載のＰＣＢ混入絶縁油の無害化処理設備。 The water contains one or more electrolytes of sulfate, carbonate, and sodium chloride, a peroxide is generated by the electrolysis, and the peroxide oxidizes and decomposes the oxidized modified oil. The detoxification processing facility for PCB-mixed insulating oil according to claim 1 . 前記酸化変質油は、Ｃ＝Ｏ結合及びＣ−Ｏ結合を含むことを特徴とする請求項１又は２に記載のＰＣＢ混入絶縁油の無害化処理設備。 The said oxidation-modified oil contains a C = O bond and a C-O bond, The detoxification processing equipment for PCB-mixed insulating oil according to claim 1 or 2 . 前記酸化変質油は、ＰＣＢ汚染物を真空加熱し回収される回収絶縁油に含まれることを特徴とする請求項１から３のいずれか１項に記載のＰＣＢ混入絶縁油の無害化処理設備。 The oxidation deterioration oils, PCB contaminants detoxification treatment facilities PCB contamination insulating oil according to any one of claims 1 to 3, characterized in that contained in the recovered insulating oil is vacuum heated recovered.
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