WO1995028993A1 - Procede de decomposition d'un compose aromatique halogene par une substance alcaline - Google Patents

Procede de decomposition d'un compose aromatique halogene par une substance alcaline Download PDF

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Publication number
WO1995028993A1
WO1995028993A1 PCT/JP1995/000785 JP9500785W WO9528993A1 WO 1995028993 A1 WO1995028993 A1 WO 1995028993A1 JP 9500785 W JP9500785 W JP 9500785W WO 9528993 A1 WO9528993 A1 WO 9528993A1
Authority
WO
WIPO (PCT)
Prior art keywords
halogenated aromatic
aromatic compound
pcb
alkaline
group
Prior art date
Application number
PCT/JP1995/000785
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Fumio Tanimoto
Kiyohiko Tsukumo
Atsuhiko Nakamura
Tsuneo Yano
Nobuhiro Suzuki
Toshinori Toma
Koichi Furuhashi
Nobuyuki Nakayama
Original Assignee
Research Institute For Production Development
Mitsui & Co., Ltd.
Neos Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Research Institute For Production Development, Mitsui & Co., Ltd., Neos Co., Ltd. filed Critical Research Institute For Production Development
Priority to EP95916026A priority Critical patent/EP0711580A1/en
Priority to AU22672/95A priority patent/AU2267295A/en
Publication of WO1995028993A1 publication Critical patent/WO1995028993A1/ja

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to a method for safely decomposing a halogenated aromatic compound such as polychlorinated biphenyl (hereinafter abbreviated as PCB) by using an alkaline substance in a polar solvent.
  • a halogenated aromatic compound such as polychlorinated biphenyl (hereinafter abbreviated as PCB)
  • No. 54 discloses the alumina-alkaline method.
  • U.S. Pat. No. 4,532,028 also discloses that in a mixture of an alkyl or alkylene sulfoxide and a polyol, an alkali and a PCB having a concentration of 50,000 ppm or less are used. A method is described in which the reaction is carried out at 0 ° C or less to obtain a few ppm.
  • Each of these conventional techniques has excellent features, but it further removes halogenated aromatic compounds from low-concentration levels of samples, and consequently contains substantially 25 halogenated aromatic compounds. At present, it has not been reduced to such an extent that it is less than 1 ppm. Removal to the bottom has not yet been realized.
  • the solvent used in the conventional method is heated to a high temperature of 150 ° C or more in the presence of an alkaline substance or an alkaline metal, the solvent loses chemical stability. As a result, decomposition and polymerization proceed, so that there is a problem that it cannot be carried out industrially.
  • the inventors of the present invention have made various studies to solve the above-mentioned problems, and as a result, have a high boiling point polar solvent and have excellent stability against alcohol even at high temperatures.
  • Select a non-proton polar solvent, and in this non-proton polar solvent heat a halogenated aromatic compound and an amount of an alkali substance that significantly exceeds the amount dissolved in the non-proton polar solvent at a high temperature. It has been found that the contacting method below is very effective in decomposing the halogenated aromatic compound.
  • the present invention provides a method for decomposing a halogenated aromatic compound by bringing the halogenated aromatic compound into contact with the alkali substance in a non-proton polar solvent.
  • the contact temperature ranges from about 150 ° C to about 300 ° C, and the contact time ranges from 1 hour to 10 hours.
  • a special feature is that the mixing ratio at the start is 5,000 mg Z kg or more.
  • the mixing ratio of the alkali substance to the whole reaction system at the start of the reaction is 7, OOOOmgZkg or more.
  • halogenated aromatic compounds to be decomposed A halogenated aromatic compound selected from the group consisting of polychlorinated biphenyls, polychlorinated terphenyls, polybrominated biphenyls, and analogs thereof, or two or more halogens selected from this group There are mixtures of fluorinated aromatic compounds.
  • a method of adding an inexpensive chemical in excess of the reacting chemicals is generally used, but in the present invention, the amount of the non-proton polar solvent as a solvent is reduced. Set the amount of alkaline substance corresponding to. That is, in the present invention, rather than excess of the alkali substance with respect to the halogenated aromatic compound, excess of the alkali substance with respect to the non-proton polar solvent is used.
  • IS enhances the action of non-proton polar solvents.
  • the content of the halogenated aromatic compound is not limited to 100%, and for example, the content of the halogenated aromatic compound may be reduced from 2 ppm by a hydrocarbon oil whose main component is a non-aromatic hydrocarbon. Those diluted to a concentration range of up to 80% can also be treated.
  • calcium hydroxide (Ca (OH) 2) and the like may be added to the reaction system in the form of calcium oxide (Ca0) and an oxide.
  • the effective non-proton polar solvent is 1, 3 under any conditions.
  • These non-proton polar solvents are readily available because they are commercially available because they are used relatively industrially. Of particular note is that these non-proton polar solvents, in addition to being less toxic and less dangerous, also better dissolve halogenated aromatics.
  • the reaction rate between the halogenated aromatic compound and the alkali substance may be significantly reduced.
  • the halogenated aromatic compound was decomposed from a concentration of several ppm to a value lower than the detection limit (less than 0.5 ppb). However, it was confirmed that they were substantially eliminated.
  • non-proton polar solvents include 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), tetramethylethylene sulfone, and 1.3— Dimethyl-1 2—Imidazolidinone and tetramethylene sulfonate, the main component of which is a solvent selected from the group consisting of a mixture of dimethyl sulfoxide, N-methylpyrrolidone, Is it possible to use methyl urea, methyl blend liquor, and polyethylene glycol dimethyl ether?
  • the halogenated aromatic compound can be effectively decomposed even when one polar solvent selected from the above or a mixture containing two or more polar solvents selected from this group at a concentration of 35% or less is used.
  • Table 1 shows the processing conditions and the amount of residual PCB after the processing for the examples and comparative examples of the present invention.
  • the column of residual PCB is indicated as ND.
  • the initial compounding ratio of the alkaline substance to the entire reaction system is equivalent to 17,000 mg / kg, and the alkaline ratio to the chlorine amount in PCB is equivalent to 90 molar ratio.
  • the PCB concentration in the oil reservoir was reduced to 80 ppb even if the treatment was performed for about 2 hours under the same conditions.
  • the initial compounding ratio of the alkaline substance to the entire reaction system is equivalent to 48,000 mg / kg, and the alkaline ratio to the chlorine amount in the PCB is equivalent to 16 in molar ratio.
  • the PCB concentration in the oil reservoir was reduced to 40 ppb even after the treatment was performed for about 3 hours under the same conditions.
  • the alkali ratio to the chlorine amount in the PCB is 120 in molar ratio, which is higher than or equal to that of Examples 1 to 7, but high concentration of PCB remains.
  • the initial compounding ratio of the alkaline substance to the whole reaction system was 2, 000 mg / day despite the excess of NaOH relative to the PCB. kg.
  • Examples 1 to 7 the case where 50 g of insulating oil containing PCB was added to the reaction system was explained.
  • the insulating oil containing PCB was added to the reaction system.
  • the case where a very small amount is added to the above is described. In this case, since the amount of insulating oil is small, the insulating oil itself dissolves into the DMI layer. After the reaction, the PCB concentration in the DMI layer is analyzed by GC-MS.
  • Example 9 3 g of insulating oil containing PCB, 90 g of DMl, and 13 g of powdered NaOH were mixed in a flask. As in Example 1. Keep them at a temperature of 200 ° C for about 5 hours, stirring them well. Next, after cooling to room temperature, the PCB of the DMI layer is analyzed by GC-MS. As a result, it was confirmed that the concentration of PCB, which was initially 70, OOO ppm in the entire reaction system, decreased to below the detection limit of GC-MS. Under these conditions, the initial blending ratio of the alkaline substance is equivalent to 130,000 mg / kg, and the alkaline ratio to the chlorine amount in the PCB is equivalent to 3 in molar ratio. In addition, it was confirmed that the PCB was reduced to 70 ppb even when the treatment was performed for about 2 hours under the same conditions.
  • Example 9 3 g of insulating oil containing PCB, 90 g of DMl, and 13 g of powdered NaOH were mixed in
  • the initial blending ratio of the alkaline substance is equivalent to 25,000 mg / kg, and the alkaline ratio to the chlorine amount in PCB is equivalent to 4 in molar ratio.
  • PCB was reduced to 60 ppb even when the treatment was performed for about 2 hours under the same conditions.
  • Example 11 to Example 14 described the case where insulating oil was not added instead of adding PCB directly to the reaction system. In these cases, too, after the reaction, the concentration of the PCB in the DMI layer is analyzed by GC-MS.
  • Example 12 First, as shown in Table 1, 0 ⁇ 11 of 1002, 1.9 g of powdery NaOH, and an amount of PCB with a concentration of 100,000 ppm in total reaction system After mixing them in a flask, they are kept at a temperature of 200 for about 5 hours, with good stirring, as in Example 8. Next, after cooling to room temperature, the PCB of the DMI layer is analyzed by GC-MS. As a result, it was confirmed that PCB decreased to below the detection limit of GC-MS. Under these conditions, the initial blending ratio of the alkaline substance is 19, OOOmgZkg, and the alkaline ratio to the chlorine amount in PCB is 3 in molar ratio. In addition, it was confirmed that PCB was reduced to 35 ppb even when the treatment was performed for about 2 hours under the same conditions, Example 12
  • the initial compounding ratio of the alkali substance is equivalent to 20, OOO mggZkg, and the alkali ratio to the chlorine amount in the PCB is equivalent to 2.8 in molar ratio.
  • the PCB was reduced to 40 ppb even if the treatment was performed for about 2 hours under the same condition> 0 cases.
  • the conditions for decomposing the PCB by bringing the PCB and the alkaline substance into contact with each other in a non-proton polar solvent are, in addition to the above examples, the amount of the alkaline substance added at the start of the reaction.
  • the contact temperature between the PCB and the alkaline substance is set in a range from about 150 ° C to about 300 ° C
  • the contact time is set in a range from about 1 hour to about 10 hours.
  • the mixing ratio of the alkaline substance to the entire reaction system at the start of the reaction was 5,000 mg / kg or more, the PCB could be reliably decomposed to below the detection limit.
  • the mixing ratio of the alkaline substance to the entire reaction system at the start of the reaction was set to 7.0000 mg kg or more. By doing so, it was confirmed that the PCB could be more reliably decomposed to below the detection limit.
  • PCB halogenated aromatic compounds
  • PCB polychlorinated terphenyls
  • NaOH, KOH, CaOH, and CaO NaO, Mg (OH) 2, and the like can be used as the alkaline substance.
  • a mixture with lenglycol dimethyl ether may be used.
  • dimethyl sulfoxide, N-methylpyrrolidone, and tetramethyl are preferred from the viewpoint of alkali resistance at high temperatures. It is preferable that the blending ratio of tyl urea, polyethylene glycol, or polyethylene glycol dimethyl ether is 35% or less.
  • PCB-containing non-proton Aluminium re-treatment Treatment Insulation oil amount under remaining conditions Polar soluble matter amount [g] vs. temperature control PCB
  • the halogenated aromatic compound and the alkali substance are mixed in a non-proton polar solvent at a temperature of about 150 ° C. to about 300 ° C. for about 1 hour. It is characterized in that it is brought into contact for about 10 hours and the mixing ratio of the alkaline substance to the whole reaction system at the start of the reaction is set to 5,000 mg / kg or more. Therefore, according to the present invention, even small amounts of halogenated aromatic compounds such as PCBs that directly harm the human body can be reliably and safely removed to a substantially harmless state. It is. Therefore, it is possible to treat hydrocarbon oil containing PCB to a substantially harmless state.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
PCT/JP1995/000785 1994-04-22 1995-04-20 Procede de decomposition d'un compose aromatique halogene par une substance alcaline WO1995028993A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95916026A EP0711580A1 (en) 1994-04-22 1995-04-20 Method of decomposing halogenated aromatic compound with alkaline substance
AU22672/95A AU2267295A (en) 1994-04-22 1995-04-20 Method of decomposing halogenated aromatic compound with alkaline substance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12169094A JP3247543B2 (ja) 1994-04-22 1994-04-22 ハロゲン化芳香族化合物のアルカリ分解方法
JP6/121690 1994-04-22

Publications (1)

Publication Number Publication Date
WO1995028993A1 true WO1995028993A1 (fr) 1995-11-02

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PCT/JP1995/000785 WO1995028993A1 (fr) 1994-04-22 1995-04-20 Procede de decomposition d'un compose aromatique halogene par une substance alcaline

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EP (1) EP0711580A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JP3247543B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU2267295A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW288009B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1995028993A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2942856B2 (ja) * 1996-10-09 1999-08-30 財団法人生産開発科学研究所 難分解性有機塩素化合物の洗浄除去方法
JP4537539B2 (ja) * 2000-06-20 2010-09-01 利夫 半谷 有害物質の分解処理方法と処理設備
JP4913366B2 (ja) * 2005-06-21 2012-04-11 株式会社ネオス 難分解性有機ハロゲン化合物の処理方法
KR101377105B1 (ko) 2011-11-28 2014-03-28 안동대학교 산학협력단 폴리브롬화 디페닐 에테르(pbde)의 화학적 처리방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951804A (en) 1957-10-22 1960-09-06 Houdry Process Corp Purification of reformate charge stocks using activated alumina impregnated with alkali or alkaline earth metal hydroxides
JPS49126651A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1973-04-10 1974-12-04
CA1181771A (en) 1982-07-27 1985-01-29 Ontario Hydro Process for dehalogenation of organic halides
US4532028A (en) 1983-10-24 1985-07-30 Niagara Mohawk Power Corporation Method for reducing content of halogenated aromatics in hydrocarbon solutions
IT1206508B (it) 1983-07-22 1989-04-27 Sea Marconi Decontamin Srl Processo continuo per la decomposizione e decontaminazione di composti organici e agenti tossici alogenati.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910353A (en) 1983-02-07 1990-03-20 Transformer Service, Inc. Dehalogenation of polychlorinated biphenyls and other related compounds
JP2831869B2 (ja) * 1991-12-27 1998-12-02 日本ペイント株式会社 ハロゲン化炭化水素の分解処理方法
JP2611900B2 (ja) * 1992-06-05 1997-05-21 財団法人生産開発科学研究所 炭化水素油よりハロゲン化芳香族化合物を除去する方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951804A (en) 1957-10-22 1960-09-06 Houdry Process Corp Purification of reformate charge stocks using activated alumina impregnated with alkali or alkaline earth metal hydroxides
JPS49126651A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1973-04-10 1974-12-04
CA1181771A (en) 1982-07-27 1985-01-29 Ontario Hydro Process for dehalogenation of organic halides
IT1206508B (it) 1983-07-22 1989-04-27 Sea Marconi Decontamin Srl Processo continuo per la decomposizione e decontaminazione di composti organici e agenti tossici alogenati.
US4532028A (en) 1983-10-24 1985-07-30 Niagara Mohawk Power Corporation Method for reducing content of halogenated aromatics in hydrocarbon solutions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0711580A4 *

Also Published As

Publication number Publication date
EP0711580A4 (en) 1996-03-20
EP0711580A1 (en) 1996-05-15
JP3247543B2 (ja) 2002-01-15
TW288009B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1996-10-11
AU2267295A (en) 1995-11-16
JPH07289656A (ja) 1995-11-07

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