JP2009011848A - Detoxifying treatment method for apparatus including organic halogen compound - Google Patents
Detoxifying treatment method for apparatus including organic halogen compound Download PDFInfo
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- JP2009011848A JP2009011848A JP2008225808A JP2008225808A JP2009011848A JP 2009011848 A JP2009011848 A JP 2009011848A JP 2008225808 A JP2008225808 A JP 2008225808A JP 2008225808 A JP2008225808 A JP 2008225808A JP 2009011848 A JP2009011848 A JP 2009011848A
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- organic halogen
- halogen compound
- compound
- oil
- treatment liquid
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- 150000002896 organic halogen compounds Chemical class 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 238000011049 filling Methods 0.000 claims abstract description 47
- 238000004140 cleaning Methods 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 238000001784 detoxification Methods 0.000 claims abstract description 35
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 32
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000012544 monitoring process Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000123 paper Substances 0.000 claims description 16
- 239000002023 wood Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001722 carbon compounds Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000012212 insulator Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 6
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002013 dioxins Chemical class 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 94
- 239000000243 solution Substances 0.000 description 27
- 239000000523 sample Substances 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000001678 irradiating effect Effects 0.000 description 6
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005695 dehalogenation reaction Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RZNAUCXHYSSBOQ-UHFFFAOYSA-N 1,1'-biphenyl dihydrochloride Chemical compound Cl.Cl.C1(=CC=CC=C1)C1=CC=CC=C1 RZNAUCXHYSSBOQ-UHFFFAOYSA-N 0.000 description 1
- YSKHYETWIGVGRJ-UHFFFAOYSA-N 1,1'-biphenyl tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.c1ccc(cc1)-c1ccccc1 YSKHYETWIGVGRJ-UHFFFAOYSA-N 0.000 description 1
- OGBQILNBLMPPDP-UHFFFAOYSA-N 2,3,4,7,8-Pentachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C=C2C2=C1C=C(Cl)C(Cl)=C2 OGBQILNBLMPPDP-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- HZGJTATYGAJRAL-UHFFFAOYSA-N 3,4,4a,5,6,7,8,8a-octahydro-2h-naphthalene-1,1-diol Chemical compound C1CCCC2C(O)(O)CCCC21 HZGJTATYGAJRAL-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LKNJXAOGEUWHBW-UHFFFAOYSA-N Cl.Cl.Cl.C1=CC=CC=C1C1=CC=CC=C1 Chemical compound Cl.Cl.Cl.C1=CC=CC=C1C1=CC=CC=C1 LKNJXAOGEUWHBW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 239000010735 electrical insulating oil Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/78—Recycling of wood or furniture waste
Landscapes
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、有機ハロゲン化合物を含む絶縁油が充填又は保存された電気機器（変圧器、油絶縁ケーブルの油槽等）を解体前に無害化する方法に関し、特に高濃度または低濃度のＰＣＢを含有する絶縁油が充填又は保存された電気機器（柱上変圧器等）を解体前に無害化する方法に関する。 The present invention relates to a method for detoxifying an electrical device (transformer, oil tank of oil insulated cable, etc.) filled or stored with an insulating oil containing an organic halogen compound before disassembling, and particularly contains a high or low concentration PCB. The present invention relates to a method for detoxifying an electric device (such as a pole transformer) filled or stored with insulating oil before disassembly.
各種有機ハロゲン化合物のなかでも、ポリ塩化ビフェニール（以下ＰＣＢと略称する。）は人体を含む生体に極めて有害であることから、１９７３年に特定化学物質に指定され、その製造、輸入、使用が禁止されている。しかし、その後適切な廃棄方法が決まらないまま数万トンのＰＣＢが未処理の状態で放置されている。ＰＣＢは、高温（３０〜７５０℃）分解では強毒性のダイオキシン類である塩素化ジベンゾ−ｐ−ダイオキシン（ＰＣＤＤ）とジベンゾフラン（ＰＣＤＦ）が副生することから、技術的にＰＣＢを安全に分解することが難しく、永年にわたりＰＣＢの安全で効率的な各種分解法が検討されている。 Among various organic halogen compounds, polychlorinated biphenyl (hereinafter abbreviated as “PCB”) is extremely harmful to living organisms including the human body. Therefore, it was designated as a specified chemical substance in 1973 and its manufacture, import and use are prohibited. Has been. However, after that, tens of thousands of tons of PCBs are left untreated without determining an appropriate disposal method. PCB decomposes PCB safely technically because chlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF), which are highly toxic dioxins, are by-produced at high temperature (30 to 750 ° C) decomposition. This is difficult, and various safe and efficient decomposition methods for PCBs have been studied for many years.
また、有機ハロゲン化合物を絶縁油中に含む、変圧器、油絶縁ケーブルの油槽、コンデンサ、蛍光灯用安定器については、洗浄等による機器の無害化も併せて検討されている。 In addition, transformers, oil-insulated cable oil tanks, capacitors, and fluorescent lamp ballasts that contain organic halogen compounds in the insulating oil are also being considered to make the equipment harmless by washing or the like.
特許文献１には、ＰＣＢを含有する機器を、電器絶縁油からなる粗洗浄液で洗浄する工程と、仕上げ洗浄液で洗浄する工程又は過熱処理をする工程と、洗浄液を金属ナトリウムで脱塩素化する工程を有する無害化方法が提案されている。 Patent Document 1 includes a step of cleaning a device containing PCB with a rough cleaning solution made of electrical insulating oil, a step of cleaning with a finish cleaning solution or a step of overheating, and a step of dechlorinating the cleaning solution with metallic sodium. A detoxification method having the following has been proposed.
特許文献２には、有機ハロゲン化合物を含有する静止誘導機を水及び酸化剤とともに圧力容器中に設置し、加圧及び加熱により圧力容器中の水を超臨界状態にして、有機ハロゲン化合物を分解するという、無害化方法が提案されている。 In Patent Document 2, a stationary induction machine containing an organic halogen compound is installed in a pressure vessel together with water and an oxidizing agent, and the water in the pressure vessel is brought into a supercritical state by pressurization and heating to decompose the organic halogen compound. A detoxifying method has been proposed.
特許文献３には、本発明者等が提案した方法として、柱上変圧器に充填されているＰＣＢ含有絶縁油にイソプロピルアルコールとＫＯＨを混合し、Ｐｄ／Ｃ触媒存在下にマイクロ波を照射することによりＰＣＢを分解する方法が記載されている。
しかしながら、特許文献１記載の方法では新たに生じる洗浄廃液を処理する工程が必要になるという問題があり、また、特許文献２に記載されている方法は高温（４３０℃）及び高圧（２５ＭＰａ）で反応させるため、装置が大掛かりになり設置場所が制限されるとともに経済性に劣る。 However, the method described in Patent Document 1 has a problem that a process for treating newly generated cleaning waste liquid is required, and the method described in Patent Document 2 has a high temperature (430 ° C.) and a high pressure (25 MPa). In order to make it react, an apparatus becomes large, an installation place is restricted and it is inferior to economical efficiency.
一方で、複雑な内部構造を有する機器では、絶縁油をすべて抽出することは事実上不可能であり、ＰＣＢを含む絶縁油を抜き取って別処理をした場合の、有機ハロゲン化合物を含む絶縁油の残留した機器の処理が懸念されており、低コストで簡便に機器に残留する絶縁油中の有機ハロゲン化合物を分解し機器を無害化する技術が求められている。 On the other hand, it is virtually impossible to extract all of the insulating oil in a device having a complicated internal structure. When the insulating oil containing PCB is extracted and processed separately, the insulating oil containing the organic halogen compound is removed. There is concern about the treatment of the remaining equipment, and there is a need for a technique for detoxifying the equipment by decomposing the organic halogen compound in the insulating oil remaining in the equipment at low cost.
その点、本発明者等が提案した特許文献３記載の方法は、液処理と同時に内部部材中に存在するＰＣＢも溶出、分解処理することが可能であるが、万一、機器内に残ってしまう場合にはＰＣＢ含有機器を処理するために特許文献１、２であげた問題点があった。 In that respect, the method described in Patent Document 3 proposed by the present inventors can also elute and decompose PCB present in the internal member simultaneously with the liquid treatment, but should remain in the device by any chance. In such a case, there are problems mentioned in Patent Documents 1 and 2 for processing a PCB-containing device.
本発明は、前記従来の課題に鑑みてなされたものであり、抜油後或いは分解処理後に、変圧器（柱上、大型）、油絶縁ケーブルの油槽等の機器に残留する絶縁油に含まれる有機ハロゲン化合物を、特別な分解処理装置を使用することなく簡易に短期間で、有害なダイオキシン類を副生することなく洗浄でき、機器を解体前に無害化処理することができる、有機ハロゲン化合物内蔵機器の無害化処理方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional problems, and is an organic material contained in insulating oil remaining in devices such as transformers (posts and large-sized) and oil tanks of oil-insulated cables after oil removal or decomposition processing. Built-in organic halogen compounds that can easily and easily clean halogen compounds without using any special decomposition treatment equipment in a short period of time and without producing harmful dioxins as a by-product. An object is to provide a detoxification method for equipment.
本発明者らは、前記課題を解決するため鋭意検討した結果、有機ハロゲン化合物を含む絶縁油を内蔵する機器に、水素供与体とアルカリ化合物の混合溶液を充填して処理液を調製し、その処理液を触媒充填装置に流通させ卒業基準を満たすまで循環させ、適宜処理液中の有機ハロゲン化合物濃度をモニタリングし、有機ハロゲン化合物濃度が所定の基準値以下に保たれ、かつ減少していくことを確認しながら、反応の進行状況を確認することにより、内蔵機器を機器付属のコイル、絶縁紙、木片等に残存する有機ハロゲン化合物も含め、短期間で簡易に無害化処理できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention prepared a treatment liquid by filling a mixed solution of a hydrogen donor and an alkali compound into a device containing an insulating oil containing an organic halogen compound. Circulate the treatment liquid through the catalyst filling equipment and circulate it until it meets the graduation standard, monitor the organic halogen compound concentration in the treatment liquid as appropriate, and keep the organic halogen compound concentration below the specified reference value and decrease it. By confirming the progress of the reaction while confirming the above, it was found that the built-in equipment can be easily detoxified in a short period of time, including organic halogen compounds remaining on the coil attached to the equipment, insulating paper, wood chips, etc. The invention has been completed.
すなわち、本発明は以下のとおりである。
１）有機ハロゲン化合物を含む絶縁油を内蔵する機器から絶縁油が抜き出された抜油後の該機器内に、
水素供与体とアルカリ化合物の混合溶液を充填する充填工程と、
該機器内に残存する有機ハロゲン化合物を前記混合溶液に溶解もしくは溶出させた処理液を触媒充填装置に流通させながら循環させることにより機器及びその内部の付属部材に残存する有機ハロゲン化合物を溶出分解し、
該循環を、機器及びその内部の付属部材に残存する有機ハロゲン化合物が卒業基準を満たすまで実施する洗浄工程と、を有し、
洗浄工程において、適宜処理液中の有機ハロゲン化合物濃度をモニタリングし、有機ハロゲン化合物濃度が所定の基準値以下に保たれ、かつ減少していくことを確認しながら、反応の進行状況を確認し、
洗浄工程終了後に処理液を抜き出すことを特徴とする有機ハロゲン化合物内蔵機器の無害化処理方法。
２）前記充填工程の後に、機器に残存する有機ハロゲン化合物を、前記混合溶液に溶解もしくは溶出させる処理液調製工程を有することを特徴とする、前記１）に記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
３）前記有機ハロゲン化合物を含む絶縁油が、少量（１〜１０，０００ｐｐｍ）の有機ハロゲン化合物を含む絶縁油であることを特徴とする、前記１）又は２）に記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
４）前記有機ハロゲン化合物を含む絶縁油が、高濃度の有機ハロゲン化合物を含む絶縁油であることを特徴とする、前記１）又は２）に記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
５）少量の有機ハロゲン化合物を含む絶縁油を内蔵する機器内に、水素供与体とアルカリ化合物を添加して処理油を調製し、該処理油を触媒充填装置に流通させながら循環させることにより有機ハロゲン化合物を分解する分解工程と、
前記機器から処理油を抜き取る抜油工程と、
抜油後の機器内に水素供与体とアルカリ化合物の混合溶液を充填する充填工程と、
該機器内に残存する有機ハロゲン化合物を前記混合溶液に溶解もしくは溶出させた処理液を触媒充填装置に流通させながら循環させることにより機器及びその内部の付属部材に残存する有機ハロゲン化合物を溶出分解し、該循環を、機器及びその内部の付属部材に残存する有機ハロゲン化合物が卒業基準を満たすまで実施する洗浄工程と、を有し、
洗浄工程において、適宜処理液中の有機ハロゲン化合物濃度をモニタリングし、有機ハロゲン化合物濃度が所定の基準値以下に保たれ、かつは減少していくことを確認しながら、反応の進行状況を確認し、
洗浄工程終了後に処理液を抜き出すことを特徴とする有機ハロゲン化合物内蔵機器の無害化処理方法。
６）前記洗浄工程における処理液温度が常温以上６０℃以下であることを特徴とする、前記１）〜５）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
７）前記有機ハロゲン化合物の分解に際し、触媒充填装置内の処理液へマイクロ波を照射することを特徴とする、前記１）〜６）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
８）前記機器が、柱上変圧器、大型変圧器又は油絶縁ケーブルの油槽のいずれかであることを特徴とする、前記１）〜７）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
９）前記機器及びその内部の付属部材の材料が、鉄、銅、碍子、紙又は木であることを特徴とする、前記１）〜８）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
１０）前記有機ハロゲン化合物がＰＣＢであることを特徴とする、前記１）〜９）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
１１）前記水素供与体が、複素環式化合物、アミン系化合物、アルコール系化合物、ケトン系化合物及び脂環式化合物からなる群から選ばれた少なくとも一つの化合物であることを特徴とする、前記１）〜１０）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
１２）前記アルカリ化合物が、苛性ソーダ、苛性カリ、ナトリウムアルコキシド、カリウムアルコキシド及び水酸化カルシウムからなる群から選ばれた少なくとも一つの化合物であることを特徴とする、前記１）〜１１）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
１３）前記触媒が、炭素結晶化合物、金属担持炭素化合物、金属担持酸化物及び金属担持複合酸化物からなる群から選ばれた少なくとも一つの化合物であることを特徴とする、前記１）〜１２）のいずれかに記載の有機ハロゲン化合物内蔵機器の無害化処理方法。
That is, the present invention is as follows.
1) In the device after the oil is extracted, the insulating oil is extracted from the device containing the insulating oil containing the organic halogen compound.
A filling step of filling a mixed solution of a hydrogen donor and an alkali compound;
The organic halogen compound remaining in the device and its accessory members is dissolved and dissolved by circulating a treatment liquid in which the organic halogen compound remaining in the device is dissolved or eluted in the mixed solution while circulating it through the catalyst filling device. ,
A cleaning step for performing the circulation until the organohalogen compound remaining in the equipment and the accessory member therein satisfies the graduation standard,
In the washing process, the organic halogen compound concentration in the treatment liquid is monitored as appropriate, and the progress of the reaction is confirmed while confirming that the organic halogen compound concentration is kept below the predetermined reference value and decreases.
A method for detoxifying a device having a built-in organic halogen compound, wherein the treatment liquid is extracted after completion of the cleaning process.
2) Harmless to the organic halogen compound-containing device according to the above 1), comprising a treatment liquid preparation step of dissolving or eluting the organic halogen compound remaining in the device in the mixed solution after the filling step. Processing method.
3) The organic halogen compound-containing device according to 1) or 2) above, wherein the insulating oil containing the organic halogen compound is an insulating oil containing a small amount (1 to 10,000 ppm) of the organic halogen compound. Detoxification treatment method.
4) The detoxifying treatment method for an organic halogen compound-containing device according to 1) or 2) above, wherein the insulating oil containing the organic halogen compound is an insulating oil containing a high concentration organic halogen compound.
5) A processing oil is prepared by adding a hydrogen donor and an alkali compound in an apparatus containing an insulating oil containing a small amount of an organic halogen compound, and the processing oil is circulated while circulating through the catalyst filling device. A decomposition step for decomposing a halogen compound;
An oil extraction step of extracting the processing oil from the device;
A filling step of filling a mixed solution of a hydrogen donor and an alkali compound in the device after oil removal;
The organic halogen compound remaining in the device and its accessory members is dissolved and dissolved by circulating a treatment liquid in which the organic halogen compound remaining in the device is dissolved or eluted in the mixed solution while circulating it through the catalyst filling device. A cleaning step for performing the circulation until the organohalogen compound remaining in the equipment and the accessory member therein satisfies the graduation standard,
In the cleaning process, monitor the progress of the reaction by monitoring the concentration of the organic halogen compound in the treatment solution as appropriate and confirming that the concentration of the organic halogen compound is kept below the specified reference value and decreasing. ,
A method for detoxifying a device having a built-in organic halogen compound, wherein the treatment liquid is extracted after completion of the cleaning process.
6) The detoxifying treatment method for an organic halogen compound-containing device according to any one of 1) to 5) above, wherein the treatment liquid temperature in the cleaning step is from room temperature to 60 ° C.
7) When the organic halogen compound is decomposed, the treatment liquid in the catalyst filling apparatus is irradiated with microwaves, and the detoxification treatment for the organic halogen compound-containing device according to any one of 1) to 6) above Method.
8) The non-hazardous organic halogen compound-containing device according to any one of 1) to 7) above, wherein the device is a pole transformer, a large transformer, or an oil tank of an oil-insulated cable. Processing method.
9) The harmless organic halogen compound-containing device according to any one of 1) to 8) above, wherein the material of the device and the accessory member therein is iron, copper, insulator, paper, or wood. Processing method.
10) The method for detoxifying an organic halogen compound-containing device according to any one of 1) to 9) above, wherein the organic halogen compound is PCB.
11) The hydrogen donor is at least one compound selected from the group consisting of a heterocyclic compound, an amine compound, an alcohol compound, a ketone compound and an alicyclic compound. 10) A detoxification method for an organic halogen compound-containing device according to any one of 10) to 10).
12) The alkali compound is at least one compound selected from the group consisting of caustic soda, caustic potash, sodium alkoxide, potassium alkoxide, and calcium hydroxide, according to any one of 1) to 11) above Detoxification treatment method for organic halogen compound built-in equipment.
13) The catalyst is at least one compound selected from the group consisting of a carbon crystal compound, a metal-supported carbon compound, a metal-supported oxide, and a metal-supported composite oxide, 1) to 12) above The method for detoxifying an organic halogen compound-containing device according to any of the above
本発明の有機ハロゲン化合物内蔵機器の無害化処理方法によれば、機器に残留している有機ハロゲン化合物含有絶縁油が水素供与体とアルカリ化合物との混合溶液に混ざるとともに、機器本体の表面に付着、コイル等の付属部材の表面や内部に付着、或いは、紙、木片等の付属部材に染み込んだ有機ハロゲン化合物が、混合溶液中に溶解もしくは溶出されてくるので、該溶液を触媒充填装置を流通させながら循環させることにより、前記絶縁油中の有機ハロゲン化合物を短期間で洗浄することができる。また、処理時に有害なダイオキシン類が副生しないので安全である。また、常圧下でも簡易に無害化処理できるので、工場や変圧器貯蔵所などの現場で洗浄処理を実施することができる。従って、実用的な規模で大量の機器を無害化処理することが可能になる。 According to the detoxification treatment method for an organic halogen compound built-in device of the present invention, the organic halogen compound-containing insulating oil remaining in the device is mixed with a mixed solution of a hydrogen donor and an alkali compound and adhered to the surface of the device body. The organic halogen compounds adhering to the surface and the inside of the accessory member such as a coil or soaking into the accessory member such as paper and wood chips are dissolved or eluted in the mixed solution, and the solution is circulated through the catalyst filling device. The organic halogen compound in the insulating oil can be washed in a short period of time by circulating while it is allowed to circulate. In addition, it is safe because harmful dioxins are not by-produced during processing. In addition, since the detoxification process can be easily performed even under normal pressure, the cleaning process can be performed at a site such as a factory or a transformer storage. Accordingly, it is possible to detoxify a large amount of devices on a practical scale.
機器内に少量の有機ハロゲン化合物を含む絶縁油が内蔵されている場合は、この中で絶縁油中の有機ハロゲン化合物の分解処理を行った後、絶縁油を抜き取り、抜油後の機器に上記の洗浄処理を施すことが出来るので、これにより、絶縁油の無害化処理から容器の無害化処理までを一貫して実施することができる。 When insulation oil containing a small amount of organic halogen compound is built in the equipment, the organic halogen compound in the insulation oil is decomposed in the oil, and then the insulation oil is extracted, and the above equipment is removed from the equipment. Since the cleaning process can be performed, the process from the detoxification process of the insulating oil to the detoxification process of the container can be performed consistently.
機器内に高濃度の有機ハロゲン化合物を含む絶縁油が内蔵されている場合は、この絶縁油を抜き取り、別の反応槽において分解処理を行った後、抜油後の機器に上記の洗浄処理を施すことが出来るので、これにより、絶縁油の無害化処理から容器の無害化処理までを一貫して実施することができる。 If the equipment contains insulating oil containing high-concentration organic halogen compounds, remove this insulating oil, perform the decomposition treatment in another reaction tank, and then perform the above cleaning treatment on the equipment after oil removal. As a result, it is possible to consistently carry out from the detoxification treatment of the insulating oil to the detoxification treatment of the container.
また、前記の触媒充填装置において、触媒槽を流通する処理液にマイクロ波を照射することにより、分解を促進することができる。 Further, in the catalyst filling device, the decomposition can be promoted by irradiating the processing liquid flowing through the catalyst tank with microwaves.
また、無害化処理に用いる水素供与体及び／又はアルカリ化合物を選択することにより、有機ハロゲン化合物の分解を高い効率で行うことができ、さらに、それらの使用量を規定することにより、有機ハロゲン化合物の分解をより高い効率で行うことができる。また、予めアルカリ化合物を水素供与体に溶解しておいた溶液を機器へ充填することにより、有機ハロゲン化合物の初期分解速度を高めることができる。 Moreover, by selecting a hydrogen donor and / or an alkali compound used for the detoxification treatment, the organic halogen compound can be decomposed with high efficiency, and further, by defining the amount of use thereof, the organic halogen compound Can be decomposed with higher efficiency. In addition, the initial decomposition rate of the organic halogen compound can be increased by filling a device with a solution in which an alkali compound is previously dissolved in a hydrogen donor.
また、分解に用いる触媒として、炭素結晶化合物、金属担持炭素化合物、金属担持酸化物及び金属担持複合酸化物から選ばれた少なくとも一つの化合物を用いることにより、有機ハロゲン化合物の分解を高い効率で行うことができ、処理コストを低減することができる。 Further, by using at least one compound selected from a carbon crystal compound, a metal-supported carbon compound, a metal-supported oxide, and a metal-supported composite oxide as a catalyst used for decomposition, the organic halogen compound is decomposed with high efficiency. And the processing cost can be reduced.
以下、本発明に係る有機ハロゲン化合物内蔵機器の無害化処理方法について、図面を参照しつつ詳細に説明する。 Hereinafter, the harmless treatment method for an organic halogen compound-containing device according to the present invention will be described in detail with reference to the drawings.
図１及び図２は、本発明の一実施形態である、有機ハロゲン化合物を含有する絶縁油が付着した機器の無害化処理フローの説明図である。図１は、低濃度の有機ハロゲン化合物を含有する絶縁油を内蔵する機器の無害化処理フロー、図２は高濃度の有機ハロゲン化合物を含有する絶縁油を内蔵する機器の無害化処理フローである。 1 and 2 are explanatory diagrams of a detoxification process flow of a device to which an insulating oil containing an organic halogen compound is attached according to an embodiment of the present invention. FIG. 1 is a detoxification process flow for a device incorporating an insulating oil containing a low concentration organic halogen compound, and FIG. 2 is a detoxification process flow for a device containing an insulation oil containing a high concentration organic halogen compound. .
図１の無害化処理フローでは、有機ハロゲン化合物を含む絶縁油（好ましくは、少量のＰＣＢを含む絶縁油）が充填された柱上変圧器等の機器内に、水素供与体とアルカリ化合物を添加して処理油を調製した後、該処理油を触媒充填装置に流通させながら循環させることによって有機ハロゲン化合物を分解する（分解工程）。分解処理後の絶縁油は、機器から抜き取る（抜油工程）。 In the detoxification process flow of FIG. 1, a hydrogen donor and an alkali compound are added into a device such as a pole transformer filled with an insulating oil containing an organic halogen compound (preferably an insulating oil containing a small amount of PCB). Then, after preparing the treated oil, the organohalogen compound is decomposed by circulating the treated oil through the catalyst filling device (decomposition step). The insulating oil after the decomposition treatment is extracted from the equipment (oil removal process).
図２の無害化処理フローでは、有機ハロゲン化合物を含む絶縁油（好ましくは、高濃度のＰＣＢを含む絶縁油）が充填された大型変圧器等の機器から絶縁油を抜き取り、別の反応槽で、抜き取った絶縁油に水素供与体とアルカリ化合物を添加して処理油を調製した後、該処理油を触媒充填装置に流通させながら循環させることによって有機ハロゲン化合物を分解する（分解工程）。 In the detoxification process flow of FIG. 2, the insulating oil is extracted from a device such as a large transformer filled with an insulating oil containing an organic halogen compound (preferably an insulating oil containing a high concentration of PCB), and is separated in another reaction tank. Then, a hydrogen donor and an alkali compound are added to the extracted insulating oil to prepare a treated oil, and then the organic halogen compound is decomposed by circulating the treated oil through the catalyst filling device (decomposing step).
次いで、抜油後の機器内に、水素供与体とアルカリ化合物の混合溶液を充填する（充填工程）。次に、機器本体及び機器内部に存在する付属部材（コイル、絶縁紙等）に残存する有機ハロゲン化合物を、前記混合溶液に溶解もしくは溶出させ、処理液を調製する（処理液調製工程）。この処理液を、別途設置する触媒充填装置に流通させ、処理液に混ざり込んだ残留有機ハロゲン化合物を触媒に接触させることにより分解し、機器本体及び付属部材に残存する有機ハロゲン化合物が卒業基準を満たすまで循環させる（洗浄工程）。洗浄工程終了後、処理液を抜き出し、機器を解体する。解体後の部材を材料ごとに選別し、リサイクルする。前記の分解工程において、有機ハロゲン化合物の分解を促進するために、触媒部分の溶液にマイクロ波を照射してもよい。 Next, the device after the oil removal is filled with a mixed solution of a hydrogen donor and an alkali compound (filling step). Next, the organic halogen compound remaining in the device main body and the attached members (coil, insulating paper, etc.) present in the device is dissolved or eluted in the mixed solution to prepare a treatment solution (treatment solution preparation step). This treatment liquid is circulated through a separately installed catalyst filling device, and the residual organic halogen compound mixed in the treatment liquid is decomposed by bringing it into contact with the catalyst. Circulate until full (cleaning process). After completion of the cleaning process, the processing solution is extracted and the equipment is disassembled. After dismantling, sort the materials by material and recycle. In the decomposition step, the catalyst portion solution may be irradiated with microwaves in order to promote decomposition of the organic halogen compound.
上記方法が適用可能な機器としては、例えば、変圧器（柱上、大型）、油絶縁ケーブルの油槽等が挙げられる。特に、機器内部に細部に入り込んだ種々の付属部材が存在し、かつ紙や木等に有機ハロゲン化合物が染み込んでいる可能性がある、柱上変圧器の処理に適用するのが好ましい。ここで、大型変圧器とは、絶縁油容量が１００Ｌ〜３０万Ｌのものを言う。 Examples of the equipment to which the above method can be applied include transformers (on poles, large size), oil tanks for oil-insulated cables, and the like. In particular, the present invention is preferably applied to the treatment of a pole transformer in which there are various accessory members that have entered the details inside the device, and there is a possibility that an organic halogen compound is infiltrated into paper or wood. Here, the large transformer refers to a transformer having an insulating oil capacity of 100L to 300,000L.
本発明において、無害化処理対象である有機ハロゲン化合物を含む絶縁油には、高濃度の有機ハロゲン化合物を含む絶縁油（即ち、含有量１０，０００ｐｐｍ超の有機ハロゲン化合物を含む絶縁油や、ＰＣＢを５０質量％以上含有する有機ハロゲン化合物（ＰＣＢ１００％品からなるものを含む）からなる絶縁油）、及び、少量の有機ハロゲン化合物を含む鉱油等をベースにした絶縁油（含有量：１ｐｐｍ〜１０，０００ｐｐｍ、好ましくは１ｐｐｍ〜５００ｐｐｍ）、の双方が含まれる。絶縁油に含まれる有機ハロゲン化合物としては、ＰＣＢ、ダイオキシン類等を挙げることができ、その種類は特に限定されるものではない。 In the present invention, the insulating oil containing an organic halogen compound to be detoxified is an insulating oil containing a high concentration of an organic halogen compound (that is, an insulating oil containing an organic halogen compound with a content exceeding 10,000 ppm, PCB, Insulating oil (content: 1 ppm to 10 ppm) based on an organic halogen compound containing 50% by mass or more (including an insulating oil made of 100% PCB) and mineral oil containing a small amount of an organic halogen compound 1,000 ppm, preferably 1 ppm to 500 ppm). Examples of the organic halogen compound contained in the insulating oil include PCBs and dioxins, and the kind thereof is not particularly limited.
ＰＣＢ市販品としては、例えば、鐘淵化学（株）のＫＣ−２００（主成分：２塩化ビフェニール）、ＫＣ−３００（主成分：３塩化ビフェニール）、ＫＣ−４００（主成分：４塩化ビフェニール）、ＫＣ−５００（主成分：５塩化ビフェニール）、ＫＣ−６００（主成分：６塩化ビフェニール）や、三菱モンサイト（株）のアロクロール１２５４（５４％ Ｃｈｌｏｒｉｎｅ）等を挙げることができる。 Examples of commercially available PCBs include KC-200 (main component: biphenyl dichloride), KC-300 (main component: biphenyl trichloride), KC-400 (main component: biphenyl tetrachloride) manufactured by Kaneka Chemical Co., Ltd. KC-500 (main component: biphenyl bichloride), KC-600 (main component: biphenyl bichloride), Arrochlor 1254 (54% Chlorine) manufactured by Mitsubishi Monsite Corporation, and the like.
次に、本発明の有機ハロゲン化合物内蔵機器の無害化処理方法を、工程ごとに順に説明する。 Next, the detoxification method for the organic halogen compound-containing device of the present invention will be described in order for each step.
（分解工程）
図１に示す機器の無害化処理フローにおいては、絶縁油を内蔵する機器に、水素供与体とアルカリ化合物を添加して処理油を調製した後、該処理油を触媒充填装置に流通させながら循環させることにより、有機ハロゲン化合物を分解する。分解操作は後述する洗浄操作と同様の方法にて実施すればよく、分解工程では主に絶縁油が無害化される。
(Disassembly process)
In the detoxification process flow of the apparatus shown in FIG. 1, after preparing a process oil by adding a hydrogen donor and an alkali compound to an apparatus incorporating an insulating oil, the process oil is circulated while circulating through the catalyst filling apparatus. To decompose the organic halogen compound. The decomposition operation may be performed by the same method as the cleaning operation described later, and the insulating oil is mainly rendered harmless in the decomposition step.
図２に示す機器の無害化処理フローにおいては、絶縁油を内蔵する機器から絶縁油を抜き取り、別の反応槽に移送する。抜き取った絶縁油に水素供与体とアルカリ化合物を添加して処理油を調製した後、該処理油を触媒充填装置に流通させながら循環させることにより、有機ハロゲン化合物を分解する。 In the detoxification process flow of the equipment shown in FIG. 2, the insulating oil is extracted from the equipment containing the insulating oil and transferred to another reaction tank. A hydrogen donor and an alkali compound are added to the extracted insulating oil to prepare a treated oil, and then the treated halogen is circulated through the catalyst filling device to decompose the organic halogen compound.
（抜油工程）
次に、機器の開口部を通じて絶縁油の抜き取りを行う。絶縁油の抜き取りは、開口部から流下させてもよく、また、ポンプ等で吸い出しても良い。なお、すでに絶縁油が抜き取られている機器については、分解工程、抜油工程は省略することができる。
(Oil removal process)
Next, the insulating oil is extracted through the opening of the device. The insulating oil can be drawn out from the opening or sucked out by a pump or the like. In addition, about the apparatus from which insulation oil was already extracted, a decomposition process and an oil extraction process can be skipped.
（充填工程）
次に、機器に水素供与体とアルカリ化合物の混合溶液を充填する。図３及び図４は充填工程、及び、前記溶液を触媒充填装置に流通させながら循環させることにより有機ハロゲン化合物を分解する洗浄工程の概略を示す図である。図３及び図４において、有機ハロゲン化合物を含有する絶縁油が付着した機器の本体１に、水素供与体とアルカリ化合物の混合溶液２を充填する。
(Filling process)
Next, the device is filled with a mixed solution of a hydrogen donor and an alkali compound. 3 and 4 are diagrams showing an outline of a filling step and a cleaning step for decomposing the organic halogen compound by circulating the solution through the catalyst filling device. 3 and 4, a main body 1 of an apparatus to which an insulating oil containing an organic halogen compound is attached is filled with a mixed solution 2 of a hydrogen donor and an alkali compound.
（処理液調製工程）
充填開始直後より、前記混合溶液に機器本体及び機器内部に存在する付属部材に残存する有機ハロゲン化合物を溶解もしくは溶出させる。なお、充填開始から充填終了までの間に処理液調製工程が終了する場合もしくは溶出と分解を同時に進める場合は、改めて、処理液調製工程を設ける必要はない。
(Processing solution preparation process)
Immediately after the start of filling, the organic halogen compound remaining in the device main body and the accessory members present in the device is dissolved or eluted in the mixed solution. When the treatment liquid preparation process is completed between the start of filling and the end of filling, or when elution and decomposition are simultaneously performed, it is not necessary to provide the treatment liquid preparation process again.
充填開始から次の洗浄工程開始までの所要時間は、特に限定されないが、処理効果を損なわない時間であれば短時間でも良く、通常、０．０１分〜６０日間の範囲で適宜選択される。拡散シミュレーションによって所要時間を求めても良い。前記の所要時間は短い方が無害化処理時間の短縮という点からは好ましいが、一昼夜ないし数週間浸漬しておくことにより、機器細部（コイル３等）に入り込んでいる絶縁油を溶液中に浸出させることが可能である。溶液２の液温は特に限定されないが、通常、０〜６０℃の範囲で選択するのが好ましい。 Although the time required from the start of filling to the start of the next cleaning step is not particularly limited, it may be a short time as long as it does not impair the treatment effect, and is usually selected appropriately within a range of 0.01 minutes to 60 days. The required time may be obtained by diffusion simulation. Although the shorter required time is preferable from the viewpoint of shortening the detoxification processing time, the insulating oil that has entered the device details (such as the coil 3) is leached into the solution by being immersed for a whole day or several weeks. It is possible to make it. Although the liquid temperature of the solution 2 is not specifically limited, Usually, it is preferable to select in the range of 0-60 degreeC.
また、溶液２を調製する場合、水素供与体とアルカリ化合物の割合は任意であるが、アルカリ化合物濃度が低すぎると有機ハロゲン化合物の分解が進みにくくなり、高すぎても分解速度が平衡に達し経済性が悪くなることから、水素供与体とアルカリ化合物の合計（質量）に対するアルカリ化合物の濃度が０．１〜２０質量％となる範囲で選択するのが好ましい。水素供与体とアルカリ化合物の混合方式は、アルカリ化合物と水素供与体の添加順序、例えば同時添加、分割添加、水素供与体を機器に入れてからアルカリ化合物を添加する方法又はその逆添加などいずれの方法であってもよく、特に限定されるものではない。混合時間は、特に限定されないが処理効果を損なわない時間であれば短時間でも良く、通常５〜９０分が好ましい。また、アルカリ化合物を水素供与体に添加し高速攪拌等することにより溶解させ、予め混液にしたものを使用してもよい。 Further, when preparing the solution 2, the ratio of the hydrogen donor and the alkali compound is arbitrary, but if the alkali compound concentration is too low, the decomposition of the organic halogen compound is difficult to proceed, and if it is too high, the decomposition rate reaches equilibrium. It is preferable to select the concentration within a range of 0.1 to 20% by mass of the alkali compound with respect to the total (mass) of the hydrogen donor and the alkali compound, because the economy becomes worse. The mixing method of the hydrogen donor and the alkali compound may be any addition order of the alkali compound and the hydrogen donor, such as simultaneous addition, divided addition, a method of adding the alkali compound after putting the hydrogen donor into the apparatus, or the reverse addition thereof. It may be a method and is not particularly limited. The mixing time is not particularly limited, but may be a short time as long as it does not impair the treatment effect, and is usually preferably 5 to 90 minutes. Alternatively, an alkali compound may be added to a hydrogen donor and dissolved by high-speed stirring or the like and mixed in advance.
（洗浄工程）
次に、処理液２をポンプ１１によりマイクロ波装置１０内に設置された触媒充填装置１５へ供給する。機器には、処理液２をポンプ１１を介して触媒充填装置１５に供給するための供給ライン１２と、触媒充填装置から処理液を回収する回収ライン１３が備えられている。これにより、機器内の処理液を触媒充填装置に供給し、有機ハロゲン化合物を触媒と接触させる。
(Washing process)
Next, the treatment liquid 2 is supplied by a pump 11 to a catalyst filling device 15 installed in the microwave device 10. The apparatus is provided with a supply line 12 for supplying the treatment liquid 2 to the catalyst filling device 15 via the pump 11 and a recovery line 13 for collecting the treatment liquid from the catalyst filling device. Thereby, the process liquid in an apparatus is supplied to a catalyst filling apparatus, and an organic halogen compound is made to contact with a catalyst.
図３及び図４に示す触媒充填装置１５には、一部図示を省略しているが、有機ハロゲン化合物を分解しうる後述する触媒が充填された触媒充填層が形成されている。処理液２は、図中の矢印で示すようにポンプ１１、供給ライン１２を介して触媒充填装置１５に導入され、導入された処理液は、触媒充填層２０を流通し、触媒充填層流通後の処理液２は、回収ライン１３により機器本体１内へ戻される。かくして、処理液が触媒と接触することにより、処理液中の有機ハロゲン化合物は分解する。洗浄工程で有機ハロゲン化合物の分解に用いた触媒は、再生処理を施した後、他の油の処理に再使用することもでき、再生処理は公知の方法、或いは水や有機溶剤を用いて触媒を洗浄する方法等を採用すればよい。 3 and 4, a catalyst packed layer filled with a catalyst to be described later capable of decomposing an organic halogen compound is formed, although a part of the illustration is omitted. The treatment liquid 2 is introduced into the catalyst filling device 15 via the pump 11 and the supply line 12 as indicated by the arrows in the figure, and the introduced treatment liquid circulates through the catalyst packed bed 20 and after the catalyst packed bed flows. The treatment liquid 2 is returned into the apparatus main body 1 by the recovery line 13. Thus, when the treatment liquid comes into contact with the catalyst, the organic halogen compound in the treatment liquid is decomposed. The catalyst used for the decomposition of the organic halogen compound in the washing step can be reused for the treatment of other oils after the regeneration treatment. The regeneration treatment can be performed by a known method or by using water or an organic solvent. What is necessary is just to employ | adopt the method etc. which wash | clean.
処理液２が触媒充填装置１５を流通する際に、マイクロ波装置１０からマイクロ波を処理液２に照射することもでき、連続的又は断続的にマイクロ波を照射することによって、有機ハロゲン化合物の分解を促進することができる。この場合、マイクロ波の出力、周波数は、設定する洗浄条件に応じて適宜決定することができるが、周波数１〜３００ＧＨｚのマイクロ波を電気的に制御しながら１０Ｗ〜２０ｋＷの範囲で照射するのが好ましい。 When the treatment liquid 2 flows through the catalyst filling device 15, the microwave can be irradiated to the treatment liquid 2 from the microwave device 10, and by continuously or intermittently irradiating the microwave, Degradation can be accelerated. In this case, the output and frequency of the microwave can be appropriately determined according to the cleaning conditions to be set. However, the microwave of frequency 1 to 300 GHz is irradiated in the range of 10 W to 20 kW while being electrically controlled. preferable.
処理液を触媒充填装置に流通させながら循環させる状態で、しばらく放置するが、適宜処理液中の有機ハロゲン化合物濃度を測定することで、反応の進行状況を確認できる。前記循環は、機器本体及び付属部材に残存する有機ハロゲン化合物が、それぞれ所定の卒業基準を満たすまで実施する。処理液を洗浄する際の処理液の液温は、常温以上６０℃以下が好ましい。常温以下ではＰＣＢの分解が遅いため処理時間が長くなり、６０℃を超えると副生物が生成しやすくなる。 While the treatment liquid is circulated while being circulated through the catalyst filling device, it is left for a while, but the progress of the reaction can be confirmed by appropriately measuring the concentration of the organic halogen compound in the treatment liquid. The circulation is carried out until the organohalogen compounds remaining in the device main body and the accessory members satisfy predetermined graduation standards. The liquid temperature of the treatment liquid when washing the treatment liquid is preferably from room temperature to 60 ° C. Below normal temperature, PCB decomposition is slow, so the processing time is long, and when it exceeds 60 ° C., by-products are easily generated.
測定の結果、有機ハロゲン化合物濃度が所定の卒業基準値以下の場合は処理を終了する。一方、有機ハロゲン化合物濃度が所定の卒業基準値を超える場合は処理操作を継続する。洗浄処理終了後、機器から処理液を抜き出し、機器を解体する。解体後の機器は、鉄製の機器本体、鉄製のコイル、銅、絶縁紙等の紙、木等に分別し、それぞれリサイクルする。 As a result of the measurement, if the organic halogen compound concentration is less than or equal to a predetermined graduation reference value, the process is terminated. On the other hand, when the organic halogen compound concentration exceeds a predetermined graduation reference value, the processing operation is continued. After the cleaning process is completed, the processing solution is extracted from the equipment and the equipment is disassembled. After dismantling, the equipment is sorted into iron equipment body, iron coils, copper, paper such as insulating paper, wood, etc., and recycled.
本発明において油に添加する「水素供与体」としては、例えば、複素環式化合物、アミン系化合物、アルコール系化合物、ケトン系化合物、及び脂環式化合物等の有機系水素供与体等が挙げられる。これらの化合物の中でも、安全性の観点より、アルコール系化合物、ケトン系化合物、脂環式化合物が好ましく、特に、安全性が高く、低コストで入手可能であり、しかも反応制御が容易で、有機ハロゲン化合物分解効率が高い点より、アルコール系化合物が好ましい。これらの水素供与体は、単独で又は二種以上を任意に組合わせて使用することができる。 Examples of the “hydrogen donor” added to the oil in the present invention include organic hydrogen donors such as heterocyclic compounds, amine compounds, alcohol compounds, ketone compounds, and alicyclic compounds. . Among these compounds, alcohol compounds, ketone compounds, and alicyclic compounds are preferable from the viewpoint of safety. In particular, they are highly safe, can be obtained at low cost, and are easy to control reaction. Alcohol compounds are preferred from the viewpoint of high halogen compound decomposition efficiency. These hydrogen donors can be used alone or in any combination of two or more.
ここで、前記のアルコール系化合物としては、脂肪族アルコール、芳香族アルコールのいずれであってもよく、直鎖又は分岐鎖を有する一価アルコールや多価アルコールを用いることができる。アルコール系化合物の炭素数は１〜１２の範囲が好ましく、より好ましくは２〜９の範囲、さらに好ましくは３〜６の範囲である。前記アルコール系化合物の具体例としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、ｓ−ブタノール、ｔ−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、１−オクタノール、２−オクタノール等の脂肪族アルコール、シクロプロピルアルコール、シクロブチルアルコール、シクロペンチルアルコール、シクロヘキシルアルコール、シクロヘプチルアルコール、シクロオクチルアルコール等の脂環式アルコール、エチレングリコール、プロピレングリコール、デカリンジオール等の多価アルコール等が挙げられる。これらの中でも、分解効率の点から２−プロパノール、シクロヘキサノールが特に好ましい。 Here, the alcohol compound may be either an aliphatic alcohol or an aromatic alcohol, and a monohydric alcohol or polyhydric alcohol having a linear or branched chain can be used. The carbon number of the alcohol compound is preferably in the range of 1 to 12, more preferably in the range of 2 to 9, and still more preferably in the range of 3 to 6. Specific examples of the alcohol compound include, for example, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, s-butanol, t-butanol, 1-pentanol, 2-pentanol, and 3-pentanol. 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol and other aliphatic alcohols, cyclopropyl alcohol, cyclobutyl alcohol, cyclopentyl alcohol, cyclohexyl Examples thereof include alicyclic alcohols such as alcohol, cycloheptyl alcohol and cyclooctyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol and decalin diol. Among these, 2-propanol and cyclohexanol are particularly preferable from the viewpoint of decomposition efficiency.
また、アルカリ化合物としては、有機ハロゲン化合物の脱ハロゲン化反応を促進しうるものであれば限定されないが、脱ハロゲン化効率を高める観点より、苛性ソーダ、苛性カリ、ナトリウムアルコキシド、カリウムアルコキシド、水酸化カルシウム等が好ましく用いられる。中でも、コストやハンドリング性の観点より、苛性ソーダ、苛性カリが特に好ましい。アルカリ化合物は、単独で又は二種以上を任意に組合わせて使用することができる。アルカリ化合物は有機ハロゲン化合物に対し、１．０〜１．５倍当量用いるのがよい。 The alkali compound is not limited as long as it can accelerate the dehalogenation reaction of the organic halogen compound, but from the viewpoint of increasing the dehalogenation efficiency, caustic soda, caustic potash, sodium alkoxide, potassium alkoxide, calcium hydroxide, etc. Is preferably used. Among these, caustic soda and caustic potash are particularly preferable from the viewpoint of cost and handling properties. An alkali compound can be used individually or in combination of 2 or more types. The alkali compound is preferably used in an amount of 1.0 to 1.5 times the amount of the organic halogen compound.
本発明の無害化処理方法においては、機器内に付着した絶縁油を水素供与体とアルカリ化合物の混合溶液へ混ぜ合わせるために、振とうによる外部からの攪拌、攪拌子による内部からの攪拌、超音波によるミクロ的な攪拌など、いずれの方法を用いてもよい。振とうによる外部からの攪拌としては、例えば、柱上変圧器などの容器を、振動式攪拌機、振動台、振とう機等を用いて加振する方法（例えば、垂直及び／又は水平方向へ平行振動させる方法、回旋振動させる方法など）などが挙げられる。攪拌子による内部からの攪拌としては、例えば、攪拌羽根やマグネチックスターラー等の攪拌子を用いて処理液を攪拌する方法などが挙げられる。攪拌する場合は、連続攪拌、間欠攪拌のいずれの方法を採用してもよい。 In the detoxification treatment method of the present invention, in order to mix the insulating oil adhering in the apparatus into the mixed solution of the hydrogen donor and the alkali compound, stirring from the outside by shaking, stirring from the inside by a stirrer, Any method such as microscopic stirring by sound waves may be used. As agitation from the outside by shaking, for example, a method of vibrating a container such as a pole transformer using a vibrating stirrer, a shaking table, a shaker, etc. (for example, parallel in the vertical and / or horizontal direction) A method of vibrating, a method of rotating and the like) and the like. Examples of the stirring from the inside by the stirring bar include a method of stirring the treatment liquid using a stirring bar such as a stirring blade or a magnetic stirrer. In the case of stirring, either continuous stirring or intermittent stirring may be employed.
本発明の触媒充填装置に充填する触媒としては、有機ハロゲン化合物（特に、ＰＣＢ）の脱ハロゲン化反応を促進しうるものであれば限定されないが、無機系触媒は触媒寿命が長く、かつ、アルカリ化合物存在下でも安定であるため、有機系触媒よりも好ましい。無機系触媒の好ましい具体例としては、脱ハロゲン化効率を高める観点より、複合金属酸化物、炭素結晶化合物、金属担持炭素化合物、金属担持酸化物、金属担持複合金属酸化物及び金属酸化物等が好ましく用いられる。中でも、アルカリ性雰囲気で安定性が高い点より、炭素結晶化合物、金属担持炭素化合物、金属担持酸化物及び金属担持複合酸化物が好ましく、特に金属担持炭素化合物が好ましい。これらの触媒は、単独で又は二種以上を任意に組合せて使用することができる。また、上記の方法で再生された再生触媒を使用してもよい。 The catalyst filled in the catalyst filling apparatus of the present invention is not limited as long as it can accelerate the dehalogenation reaction of an organic halogen compound (particularly PCB), but an inorganic catalyst has a long catalyst life and is alkaline. Since it is stable even in the presence of a compound, it is preferable to an organic catalyst. Preferred specific examples of the inorganic catalyst include composite metal oxides, carbon crystal compounds, metal-supported carbon compounds, metal-supported oxides, metal-supported composite metal oxides and metal oxides from the viewpoint of increasing the dehalogenation efficiency. Preferably used. Among these, from the viewpoint of high stability in an alkaline atmosphere, a carbon crystal compound, a metal-supported carbon compound, a metal-supported oxide, and a metal-supported composite oxide are preferable, and a metal-supported carbon compound is particularly preferable. These catalysts can be used individually or in combination of 2 or more types. Further, a regenerated catalyst regenerated by the above method may be used.
ここで、前記の炭素結晶化合物としては、グラファイト、カーボンナノチューブ（金属を含むものと含まないものの双方が含まれる）、フラーレン等が挙げられる。 Here, examples of the carbon crystal compound include graphite, carbon nanotubes (both including and not including metal), fullerene, and the like.
また前記の金属担持炭素化合物としては、金属を担持した炭素化合物であればよく、その金属担持量は、触媒全量に対して０．１〜２０ｗｔ％、より好ましくは０．１〜１０ｗｔ％である。担持される金属としては、例えば、鉄、銀、白金、ルテニウム、パラジウム、ロジウム等が挙げられ、脱ハロゲン化効率を高める観点より、パラジウム、ルテニウム、白金が好ましい。金属担持炭素化合物の具体例としては、例えば、Ｐｄ／Ｃ（パラジウム担持炭素化合物）、Ｒｕ／Ｃ（ルテニウム担持炭素化合物）、Ｐｔ／Ｃ（白金担持炭素化合物）等が挙げられる。 The metal-supported carbon compound may be a carbon compound supporting a metal, and the amount of the metal supported is 0.1 to 20 wt%, more preferably 0.1 to 10 wt% with respect to the total amount of the catalyst. . Examples of the supported metal include iron, silver, platinum, ruthenium, palladium, rhodium and the like, and palladium, ruthenium, and platinum are preferable from the viewpoint of increasing the dehalogenation efficiency. Specific examples of the metal-supported carbon compound include Pd / C (palladium-supported carbon compound), Ru / C (ruthenium-supported carbon compound), and Pt / C (platinum-supported carbon compound).
前記の金属担持酸化物及び金属担持複合酸化物は、金属を担持した酸化物、複合酸化物であれば限定されないが、その金属担持量及び金属の種類は、上記の金属担持炭素化合物と同様である。金属担持酸化物の具体例としては 例えば、Ｐｄ／ＴｉＯ２（パラジウム担持２酸化チタン）等が挙げられる。金属担持複合酸化物の具体例としては、例えば、Ｐｄ／ＳｉＯ２・Ａｌ２Ｏ３（パラジウム担持シリカ−アルミナ）等が挙げられる。 The metal-supported oxide and the metal-supported composite oxide are not limited as long as they are metal-supported oxides and composite oxides, but the amount of metal supported and the type of metal are the same as those of the metal-supported carbon compound. is there. Specific examples of the metal-supported oxide include Pd / TiO 2 (palladium-supported titanium dioxide). Specific examples of the metal-supported composite oxide include Pd / SiO 2 .Al 2 O 3 (palladium-supported silica-alumina).
なお、アルカリ化合物存在下で安定なものであれば、ポリエチレン等の樹脂に金属を担持した触媒も使用することができる In addition, as long as it is stable in the presence of an alkali compound, a catalyst in which a metal is supported on a resin such as polyethylene can also be used.
触媒の形状は、粒状のものでもハニカム状のものでもよい。粒状の場合はカラムの上下をメッシュ等で固定する必要があり、その場合の粒子径は７５μｍ〜１０ｍｍが好ましい。１０ｍｍを超える場合は比表面積が不足し、７５μｍ未満の場合はメッシュが詰まり差圧が高くなる。より好ましくは１５０μｍ〜５ｍｍが望ましい。触媒粒子は、できるだけ粒子径のそろったものがよい。 The shape of the catalyst may be granular or honeycomb. In the case of granular, it is necessary to fix the upper and lower sides of the column with a mesh or the like, and the particle diameter in that case is preferably 75 μm to 10 mm. When it exceeds 10 mm, the specific surface area is insufficient, and when it is less than 75 μm, the mesh is clogged and the differential pressure becomes high. More preferably, it is 150 μm to 5 mm. The catalyst particles should have the same particle size as possible.
本発明の無害化処理方法によれば、機器本体に付着する有機ハロゲン化合物や、付属部材に残存する有機ハロゲン化合物も分解されるので、機器を解体処理することにより、各部材を再利用することもできる。 According to the detoxification treatment method of the present invention, the organic halogen compound adhering to the device main body and the organic halogen compound remaining in the accessory member are also decomposed, so that each member can be reused by disassembling the device. You can also.
また本発明により、抜油後の機器の効率的な無害化処理が可能となる。特に、柱上変圧器等の機器に保存又は充填された絶縁油の無害化処理工程の後、引き続き機器中に残留した絶縁油を無害化処理する際に、機器内に有機ハロゲン化合物が染み込んだ絶縁紙や木片等が存在する場合にも、染み込んだ有機ハロゲン化合物が溶液中に溶出するので、機器を丸ごと無害化処理できる。 Further, according to the present invention, it is possible to perform an efficient detoxification process for equipment after oil removal. In particular, after detoxifying treatment of insulating oil stored or filled in equipment such as pole transformers, organic halogen compounds were infiltrated into the equipment when detoxifying the remaining insulating oil in the equipment. Even when insulating paper or wood chips are present, the soaked organic halogen compound is eluted in the solution, so that the entire device can be rendered harmless.
次に、本発明を実施例により具体的に説明するが、本発明は以下の実施例にのみ限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited only to a following example.
（拡散シミュレーションによる処理時間の設定）
下記拡散モデルから誘導される近似式（１）式を用いて、処理時間を決定した。なお、液処理８日間中は固体内ＰＣＢ濃度２０ｐｐｍ変化なしと想定し、次の９日間で液中のＰＣＢ濃度０ｐｐｍと仮定し、液温は平均２５〜４０℃と仮定し、固体内濃度が０．５ｐｐｍ以下になる日数を算出した。その結果を表１に示す。液温平均３０℃と仮定し容器の無害化処理所要時間１４日間を設定した。
(Processing time setting by diffusion simulation)
The processing time was determined using the approximate expression (1) derived from the following diffusion model. It is assumed that the PCB concentration in the solid does not change 20 ppm during the liquid treatment for 8 days, the PCB concentration in the liquid is assumed to be 0 ppm in the next 9 days, the liquid temperature is assumed to be 25 to 40 ° C. on average, and the concentration in the solid is The number of days to be 0.5 ppm or less was calculated. The results are shown in Table 1. Assuming an average liquid temperature of 30 ° C., a detoxification time of 14 days was set for the container.
［実施例１］
（ＰＣＢ分解処理）
ＰＣＢ２４．０７ｐｐｍを含む４５Ｌ容柱上変圧器に、水素供与体としてイソプロピルアルコール９Ｌ（対試験油２０ｖｏｌ％）、及びアルカリとしてＫＯＨ４７３．６８ｇ（対絶縁油１％）を添加し、攪拌した。
[Example 1]
(PCB decomposition process)
To a 45 L column transformer containing 24.07 ppm of PCB, 9 L of isopropyl alcohol (20 vol% of test oil) as a hydrogen donor and 473.68 g of KOH (1% of insulating oil) as an alkali were added and stirred.
一方、粒状活性炭（商品名：ダイヤホープ００８）にパラジウム（Ｐｄ）を５％担持させた触媒（平均粒径１ｍｍ程度）を用意し、７０℃で４８時間乾燥した。この触媒２ｋｇを触媒充填装置に入れ、上下を１００メッシュの網で挟み込み、触媒を充填した。柱上変圧器の外側に、ＥＦＮＩＣ（株）製ギヤポンプ（ＭｏｄｅｌＧＰＥ−０３１、１２Ｖ ＤＣ）を、合計２個取り付け、各ポンプに内径６ｍｍのテフロン（登録商標）チューブを取り付け、各ポンプ共に、それぞれ片方の端を処理液底部に浸漬し、他の端を触媒充填装置の上部に取り付けた。 On the other hand, a catalyst (average particle diameter of about 1 mm) in which 5% palladium (Pd) was supported on granular activated carbon (trade name: Diahop 008) was prepared and dried at 70 ° C. for 48 hours. 2 kg of this catalyst was put into a catalyst filling device, and the upper and lower sides were sandwiched between 100 mesh nets to fill the catalyst. A total of two gear pumps (Model GPE-031, 12V DC) manufactured by EFNIC Co., Ltd. are attached to the outside of the pole transformer, and a Teflon (registered trademark) tube with an inner diameter of 6 mm is attached to each pump. The other end was immersed in the bottom of the treatment liquid, and the other end was attached to the upper part of the catalyst filling apparatus.
柱上変圧器から処理油をポンプで抜き出し、触媒充填装置の触媒層に、８００ｍｌ／分の速度で連続的に通液しながら、触媒充填装置と柱上変圧器の間を８時間循環させた。その間、周波数２．５４ＧＨｚ、最大出力６５０Ｗのマイクロ波を電気的に制御しながら照射し、反応温度を６０℃に維持した。その後１６時間はマイクロ波照射を停止し、常温にて液を循環させた。 The treated oil was pumped out from the pole transformer and circulated between the catalyst filler and the pole transformer for 8 hours while continuously passing through the catalyst layer of the catalyst filler at a rate of 800 ml / min. . Meanwhile, microwaves with a frequency of 2.54 GHz and a maximum output of 650 W were irradiated while being electrically controlled, and the reaction temperature was maintained at 60 ° C. Thereafter, microwave irradiation was stopped for 16 hours, and the liquid was circulated at room temperature.
定期的にサンプリングしながら、処理油中のＰＣＢ濃度が目標値（０．５ｐｐｍ）以下になるまで、前記操作を繰り返し行った。なお、サンプリングした処理油中のＰＣＢ濃度は、ＳＧＥ ＨＴ８（島津ＧＬＣ Ｌｔｄ．製）をキャピラリーカラムとするヒューレットパッカード製のガスクロマトグラフィー質量分析計ＨＰ６８９０（以下、「ＧＣ−ＭＳ」）を用いて分析した。 While periodically sampling, the above operation was repeated until the PCB concentration in the treated oil became the target value (0.5 ppm) or less. The PCB concentration in the sampled treated oil was analyzed using a gas chromatography mass spectrometer HP6890 (hereinafter referred to as “GC-MS”) manufactured by Hewlett-Packard using SGE HT8 (manufactured by Shimadzu GLC Ltd.) as a capillary column. .
（容器洗浄処理）
マイクロ波出力最大６５０Ｗ、循環ポンプ循環量０．８Ｌ／ｈ、処理槽容量２０Ｌの処理装置を、柱上変圧器外部に設置し、柱上変圧器より分解済絶縁油を抜き取り、新たに洗浄薬液（ＩＰＡ３５Ｌ（コイルが浸る量３０Ｌ＋触媒層吸収量５Ｌ）とＫＯＨ４２ｇ（残油量に対し約１％）の混合溶液）に入れ替えた。
(Container cleaning process)
A processing device with a maximum microwave output of 650 W, a circulation pump circulation rate of 0.8 L / h, and a processing tank capacity of 20 L is installed outside the pole transformer, and the decomposed insulating oil is extracted from the pole transformer, and a new cleaning chemical (IPA35L (coil immersion amount 30L + catalyst layer absorption amount 5L) and KOH 42g (mixed solution of about 1% with respect to residual oil amount)).
柱上変圧器内の薬液を、マイクロ波を照射させながらパラジウムを担持した活性炭触媒（２ｋｇ）層を通過させ、循環ポンプにて薬液を流量８００ｍｌ／分にて循環させ、容器洗浄処理を行った。洗浄処理においては処理温度を６０℃に保ちながらマイクロ波を８時間照射させながら液を循環させ、その後１６時間常温にて薬液を循環させた。このような状態にて１４日間洗浄処理を行った。洗浄薬液にて処理を行っている期間中、１日１回ＰＣＢ濃度を測定し、ＰＣＢ濃度が基準値（０．５ｐｐｍ）以下に保たれ、かつ減少していくことを確認した。柱上変圧器内のコイルを吊り上げ、薬液が垂れなくなるまで液切りをした。 The chemical solution in the pole transformer was passed through an activated carbon catalyst (2 kg) layer carrying palladium while irradiating microwaves, and the chemical solution was circulated at a flow rate of 800 ml / min with a circulation pump, and the container was washed. . In the cleaning treatment, the liquid was circulated while irradiating with microwaves for 8 hours while maintaining the treatment temperature at 60 ° C., and then the chemical liquid was circulated at room temperature for 16 hours. In such a state, a washing treatment was performed for 14 days. During the treatment with the cleaning chemical solution, the PCB concentration was measured once a day, and it was confirmed that the PCB concentration was kept below the reference value (0.5 ppm) and decreased. The coil in the pole transformer was lifted and drained until the chemical did not sag.
（卒業判定）
柱上変圧器内壁部を脱脂綿またはガラスウール（２０ｇ）を用いて５００ｃｍ２の範囲を拭取り、拭取り試験用試料とした（鉄（本体））。
(Graduation judgment)
The inner wall of the pole transformer was wiped over 500 cm 2 using absorbent cotton or glass wool (20 g) to obtain a sample for wiping test (iron (main body)).
コイル部を分解し、材料別に鉄、銅、碍子、紙、木に分別をした。 The coil part was disassembled and separated into iron, copper, insulators, paper, and wood by material.
鉄、銅、碍子については、有機溶剤（トルエン、ヘキサン、または第４石油類に属した有機溶剤）を用い、金属製容器に１回の液量を２０００ｍｌとし洗浄した。 About iron, copper, and an insulator, the organic solvent (Toluene, hexane, or the organic solvent which belongs to 4th petroleum) was used, and it wash | cleaned by making 2000 ml into a metal container.
各材料毎に、液に浸漬し振とう洗浄を行った。鉄（コイル他）は試料１つに対して５〜１０秒、銅および碍子等については洗浄容器に複数の試料を入れ１０秒間振とう洗浄を実施し、分析試料とした（平成４年厚生省告示第１９２号、改正平成１０年８月第２２２号；別表第２の第三に準拠）。 Each material was immersed in a solution and washed with shaking. Iron (coil, etc.) is 5-10 seconds for one sample, and copper, insulators, etc. are placed in a washing container and washed for 10 seconds with shaking, and used as an analysis sample (Notification by the Ministry of Health, Labor and Welfare in 1992) No. 192, amended August 1998 No. 222; according to Appendix No. 2 3).
紙材料は全ての部分を１０ｃｍ以下に裁断し、縮分にて試料５０ｇを採取した。５０ｇ採取した試料を３ｃｍ以下に裁断し、分析試料とした。 All parts of the paper material were cut to 10 cm or less, and 50 g of a sample was collected by shrinking. A sample collected by 50 g was cut to 3 cm or less and used as an analysis sample.
木材料は全ての部分を５ｃｍ以下に裁断し、縮分にて試料５０ｇを採取した。５０ｇ採取した試料を２ｍｍ目のふるいを通過した大きさに裁断し、分析試料とした。 All parts of the wood material were cut to 5 cm or less, and 50 g of a sample was collected by shrinking. A sample collected by 50 g was cut into a size passing through a 2 mm sieve and used as an analysis sample.
本体の拭取り試料、及び鉄、銅、碍子の有機溶剤抽出液については、ＰＣＢ濃度分析を行い、紙、木材については、溶出試験（平成１６年環境省告示第３１号に基づく）を行った。これらの分析結果を表２にまとめて示す。 PCB concentration analysis was performed on the wiping sample of the main body and organic solvent extracts of iron, copper, and insulator, and dissolution tests (based on the Ministry of the Environment Notification No. 31 of 2004) were performed on paper and wood. . The results of these analyzes are summarized in Table 2.
表２から明らかなように、柱上変圧器本体及び付属部材は、全て卒業基準を満たしていた。 As is clear from Table 2, the pole transformer main body and the attached members all satisfied the graduation standard.
容器洗浄処理に使用した薬液（処理液）中のＰＣＢ濃度は、処理開始から処理終了まで、表３に示すように０．５ｍｇ／ｋｇ以下で推移した。また、処理終了後の液中のダイオキシン類の濃度は、表４に示すが、ダイオキシン等の生成はなかった。なお、ダイオキシン類の測定法はＪＩＳ Ｋ ０３１１に準拠した。 As shown in Table 3, the PCB concentration in the chemical solution (treatment solution) used for the container cleaning treatment changed at 0.5 mg / kg or less as shown in Table 3. Moreover, although the density | concentration of the dioxins in the liquid after completion | finish of a process is shown in Table 4, there was no production | generation of a dioxin etc. In addition, the measuring method of dioxins was based on JISK0311.
［実施例２］
絶縁油中にＰＣＢ１７ｐｐｍを含む４５Ｌ容柱上変圧器から、絶縁油（１種２号）をポンプで抜き出し、各部材のＰＣＢ含有量を、実施例１の卒業判定と同様の方法にて確認した。
続いて、マイクロ波出力最大６５０Ｗ、循環ポンプ循環量４８Ｌ／ｈ、処理槽容量２０Ｌの処理装置を、柱上変圧器外部に設置し、絶縁油を抜き出した柱上変圧器に、洗浄薬液（ＩＰＡ３５Ｌ（コイルが浸る量３０Ｌ＋触媒層吸収量５Ｌ）とＫＯＨ４２ｇ（残油量に対し約１％）の混合溶液）を加えた。
[Example 2]
Insulating oil (Type 1 No. 2) was pumped out from a 45 L column transformer containing 17 ppm of PCB in the insulating oil, and the PCB content of each member was confirmed by the same method as the graduation judgment of Example 1. .
Subsequently, a processing apparatus having a maximum microwave output of 650 W, a circulation pump circulation rate of 48 L / h, and a processing tank capacity of 20 L was installed outside the pole transformer, and the cleaning chemical (IPA35L) was placed on the pole transformer from which the insulating oil was extracted. (A mixed solution of 30 L of coil soaking amount + 5 L of catalyst layer absorption) and 42 g of KOH (about 1% with respect to the residual oil amount) was added.
柱上変圧器内の薬液を、マイクロ波を照射させながらパラジウムを担持した活性炭触媒（２ｋｇ）層を通過させ、循環ポンプにて薬液を流量８００ｍｌ／分にて循環させ、容器洗浄処理を行った。洗浄処理においては処理温度を６０℃に保ちながらマイクロ波を８時間照射させながら液を循環させ、その後１６時間常温にて薬液を循環させた。このような状態にて２１日間洗浄処理を行った。洗浄薬液にて処理を行っている期間中、処理日数０日から４日までは、１日１回ＰＣＢ濃度を測定し、４日以降は８日目、１２日目、１６日目、２１日目にＰＣＢ濃度を測定し、ＰＣＢ濃度が基準値（０．５ｐｐｍ）以下に保たれ、かつ減少していくことを確認した。柱上変圧器内のコイルを吊り上げ、薬液が垂れなくなるまで液切りをしたのち、以下に記述する卒業判定方法にて、柱上変圧器内壁、コイル部の鉄、銅、碍子、紙、木に残留するＰＣＢ量を分析した。 The chemical solution in the pole transformer was passed through an activated carbon catalyst (2 kg) layer carrying palladium while irradiating microwaves, and the chemical solution was circulated at a flow rate of 800 ml / min with a circulation pump, and the container was washed. . In the cleaning treatment, the liquid was circulated while irradiating with microwaves for 8 hours while maintaining the treatment temperature at 60 ° C., and then the chemical liquid was circulated at room temperature for 16 hours. In this state, a cleaning process was performed for 21 days. During the treatment with the cleaning chemical, the PCB concentration is measured once a day from the 0th to the 4th, and after the 4th, the 8th, 12th, 16th, 21st The PCB concentration was measured by eye and it was confirmed that the PCB concentration was kept below the reference value (0.5 ppm) and decreased. After lifting the coil in the pole transformer and draining it until the chemical no longer hangs, use the graduation judgment method described below to apply iron, copper, insulator, paper, and wood to the pole transformer inner wall and coil. The amount of PCB remaining was analyzed.
（卒業判定）
柱上変圧器内壁部を有機溶剤（トルエン、ヘキサン、または第４石油類に属した有機溶剤）を浸した脱脂綿（１．５ｇ）またはガラスウール（２０ｇ）を用いて５００ｃｍ２の範囲を拭取り、拭取り試験用試料とした（鉄（本体））。
(Graduation judgment)
Wipe the area of 500 cm 2 using absorbent cotton (1.5 g) or glass wool (20 g) soaked with an organic solvent (toluene, hexane, or an organic solvent belonging to the 4th petroleum) on the inner wall of the pole transformer. A sample for wiping test was made (iron (main body)).
コイル部を分解し、材料別に鉄、銅、碍子、紙、木に分別をした。 The coil part was disassembled and separated into iron, copper, insulators, paper, and wood by material.
鉄（コイル部）については、巻いてある状態のものを広げ表面部を有機溶剤（トルエン、ヘキサン、または第４石油類に属した有機溶剤）を浸した脱脂綿（１．５ｇ）またはガラスウール（２０ｇ）を用いて約５００ｃｍ２の範囲を拭取り、拭取り試験用試料とした。 As for iron (coil part), cotton wool (1.5 g) or glass wool (surface coil part) is spread and the surface part is soaked with an organic solvent (toluene, hexane, or an organic solvent belonging to the fourth petroleum). 20 g) was used to wipe a range of about 500 cm 2 to obtain a sample for wiping test.
銅、碍子については、有機溶剤（トルエン、ヘキサン、または第４石油類に属した有機溶剤）を用い、金属製容器に１回の液量を洗浄する部材重量に対して等量とし洗浄した。 About copper and an insulator, the organic solvent (Toluene, hexane, or the organic solvent which belongs to 4th petroleum) was used, and it wash | cleaned by making it equal to the member weight which wash | cleans one liquid quantity to a metal container.
各材料毎に、液に浸漬し超音波洗浄を行った。銅、碍子は試料１つに対して洗浄容器に試料を入れ６時間超音波洗浄を実施し、分析試料とした（平成４年厚生省告示第１９２号、改正平成１０年８月第２２２号；別表第２の第三に準拠）。 Each material was immersed in a liquid and subjected to ultrasonic cleaning. For copper and insulator, put the sample into a washing container and perform ultrasonic cleaning for 6 hours to make an analytical sample (Ministry of Health and Welfare Notification No. 192, revised August 1998 No. 222; Appendix) According to the second third).
紙材料は、コイルの外側、中、内側の部分を採取し１０ｃｍ以下に裁断し、縮分にて試料１６０ｇを採取した。１６０ｇ採取した試料を３ｃｍ以下に裁断し、分析試料とした。 For the paper material, the outside, inside, and inside portions of the coil were sampled and cut to 10 cm or less, and 160 g of a sample was sampled by reduction. A sample collected from 160 g was cut to 3 cm or less and used as an analysis sample.
木材料はコイルの中間部の木材料およびコイル上部にあるプレスボードをそれぞれ採取し試料ととした。 As the wood material, a wood material in the middle part of the coil and a press board at the top of the coil were collected and used as samples.
コイルの中間部の木材は全ての部分を５ｃｍ以下に裁断し、縮分にて試料１６０ｇを採取した。５０ｇ採取した試料を２ｍｍ目のふるいを通過した大きさに裁断し、分析試料とした。 All parts of the wood in the middle part of the coil were cut to 5 cm or less, and 160 g of a sample was collected by shrinking. A sample collected by 50 g was cut into a size passing through a 2 mm sieve and used as an analysis sample.
コイル上部のプレスボードは５ｃｍ以下に裁断し、縮分にて試料１６０ｇを採取した。１５０ｇ採取した試料を２ｍｍ目のふるいを通過した大きさに裁断し、分析試料とした。 The press board on the top of the coil was cut to 5 cm or less, and 160 g of a sample was collected by shrinking. A sample collected of 150 g was cut into a size that passed through a 2 mm sieve and used as an analysis sample.
本体の拭取り試料、及び鉄、銅、碍子の有機溶剤抽出液については、ＰＣＢ濃度分析を行い、紙、木材については、溶出試験（平成１６年環境省告示第３１号に基づく）を行った。これらの分析結果を表５にまとめて示す。 PCB concentration analysis was performed on the wiping sample of the main body and organic solvent extracts of iron, copper, and insulator, and dissolution tests (based on the Ministry of the Environment Notification No. 31 of 2004) were performed on paper and wood. . The results of these analyzes are summarized in Table 5.
表５から明らかなように、柱上変圧器本体及び付属部材は、全て卒業基準を満たしてい
た。
As is clear from Table 5, the pole transformer main body and the attached members all satisfied the graduation standard.
容器洗浄処理に使用した薬液（処理液）中のＰＣＢ濃度は、処理開始から処理終了まで
表６に示すように０．５ｍｇ／ｋｇ以下で推移した。また、処理終了後の液中のダイオキ
シン類の濃度は、表７に示すが、ダイオキシン等の生成はなかった。
The PCB concentration in the chemical solution (treatment solution) used for the container cleaning process changed from 0.5 mg / kg or less as shown in Table 6 from the start of the process to the end of the process. Moreover, although the density | concentration of the dioxins in the liquid after completion | finish of a process is shown in Table 7, there was no production | generation of a dioxin.
１ 機器本体
２ 水素供与体とアルカリ化合物の混合溶液、処理液
３ コイル（鉄心）
１０ マイクロ波装置
１１ ポンプ
１２ 供給ライン
１３ 回収ライン
１５ 触媒充填装置
２０ 触媒層
DESCRIPTION OF SYMBOLS 1 Apparatus body 2 Hydrogen donor and alkali compound mixed solution, treatment liquid 3 Coil (iron core)
DESCRIPTION OF SYMBOLS 10 Microwave apparatus 11 Pump 12 Supply line 13 Recovery line 15 Catalyst filling apparatus 20 Catalyst layer
Claims (13)
水素供与体とアルカリ化合物の混合溶液を充填する充填工程と、
該機器内に残存する有機ハロゲン化合物を前記混合溶液に溶解もしくは溶出させた処理液を触媒充填装置に流通させながら循環させることにより機器及びその内部の付属部材に残存する有機ハロゲン化合物を溶出分解し、
該循環を、機器及びその内部の付属部材に残存する有機ハロゲン化合物が卒業基準を満たすまで実施する洗浄工程と、を有し、
洗浄工程において、適宜処理液中の有機ハロゲン化合物濃度をモニタリングし、有機ハロゲン化合物濃度が所定の基準値以下に保たれ、かつ減少していくことを確認しながら、反応の進行状況を確認し、
洗浄工程終了後に処理液を抜き出すことを特徴とする有機ハロゲン化合物内蔵機器の無害化処理方法。 In the equipment after the oil is extracted from the equipment containing the insulating oil containing the organic halogen compound,
A filling step of filling a mixed solution of a hydrogen donor and an alkali compound;
The organic halogen compound remaining in the device and its accessory members is dissolved and dissolved by circulating a treatment liquid in which the organic halogen compound remaining in the device is dissolved or eluted in the mixed solution while circulating it through the catalyst filling device. ,
A cleaning step for performing the circulation until the organohalogen compound remaining in the equipment and the accessory member therein satisfies the graduation standard,
In the washing process, the organic halogen compound concentration in the treatment liquid is monitored as appropriate, and the progress of the reaction is confirmed while confirming that the organic halogen compound concentration is kept below the predetermined reference value and decreases.
A method for detoxifying a device having a built-in organic halogen compound, wherein the treatment liquid is extracted after completion of the cleaning process.
前記機器から処理油を抜き取る抜油工程と、
抜油後の機器内に水素供与体とアルカリ化合物の混合溶液を充填する充填工程と、
該機器内に残存する有機ハロゲン化合物を前記混合溶液に溶解もしくは溶出させた処理液を触媒充填装置に流通させながら循環させることにより機器及びその内部の付属部材に残存する有機ハロゲン化合物を溶出分解し、該循環を、機器及びその内部の付属部材に残存する有機ハロゲン化合物が卒業基準を満たすまで実施する洗浄工程と、を有し、
洗浄工程において、適宜処理液中の有機ハロゲン化合物濃度をモニタリングし、有機ハロゲン化合物濃度が所定の基準値以下に保たれ、かつは減少していくことを確認しながら、反応の進行状況を確認し、
洗浄工程終了後に処理液を抜き出すことを特徴とする有機ハロゲン化合物内蔵機器の無害化処理方法。 Organohalogen compounds are prepared by adding a hydrogen donor and an alkali compound in a device containing an insulating oil containing a small amount of an organic halogen compound to prepare a treatment oil, and circulating the treatment oil through a catalyst filling device. A decomposition process for decomposing
An oil extraction step of extracting the processing oil from the device;
A filling step of filling a mixed solution of a hydrogen donor and an alkali compound in the device after oil removal;
The organic halogen compound remaining in the device and its accessory members is dissolved and dissolved by circulating a treatment liquid in which the organic halogen compound remaining in the device is dissolved or eluted in the mixed solution while circulating it through the catalyst filling device. A cleaning step for performing the circulation until the organohalogen compound remaining in the equipment and the accessory member therein satisfies the graduation standard,
In the cleaning process, monitor the progress of the reaction by monitoring the concentration of the organic halogen compound in the treatment liquid as appropriate and confirming that the organic halogen compound concentration is kept below the specified reference value and decreases. ,
A method for detoxifying a device having a built-in organic halogen compound, wherein the treatment liquid is extracted after completion of the cleaning process.
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| JP2010227390A (en) * | 2009-03-27 | 2010-10-14 | Tokyo Electric Power Co Inc:The | Detoxifying treatment method for apparatus incorporating organic halogen compound |
| JP2010269283A (en) * | 2009-05-25 | 2010-12-02 | Tokyo Electric Power Co Inc:The | Method and system for detoxifying apparatus using pcb |
| JP2010274170A (en) * | 2009-05-27 | 2010-12-09 | Tokyo Electric Power Co Inc:The | Detoxifying treatment method and apparatus for instrument with remaining organic halogen compound |
| JP2012005937A (en) * | 2010-06-23 | 2012-01-12 | Toshio Konuma | System for treating waste electrical equipment contaminated with pcb |
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| JP2010234194A (en) * | 2009-03-30 | 2010-10-21 | Tokyo Electric Power Co Inc:The | Pretreatment cleaning method for high concentration pcb contaminated equipment |
| JP5892474B2 (en) * | 2012-09-21 | 2016-03-23 | 東京電力株式会社 | Method for estimating the number of days to clean a transformer container contaminated with PCB |
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| JP2010227390A (en) * | 2009-03-27 | 2010-10-14 | Tokyo Electric Power Co Inc:The | Detoxifying treatment method for apparatus incorporating organic halogen compound |
| JP2010269283A (en) * | 2009-05-25 | 2010-12-02 | Tokyo Electric Power Co Inc:The | Method and system for detoxifying apparatus using pcb |
| JP2010274170A (en) * | 2009-05-27 | 2010-12-09 | Tokyo Electric Power Co Inc:The | Detoxifying treatment method and apparatus for instrument with remaining organic halogen compound |
| JP2012005937A (en) * | 2010-06-23 | 2012-01-12 | Toshio Konuma | System for treating waste electrical equipment contaminated with pcb |
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