JP2008272594A - Electrolytic reduction dehalogenation method for activated carbon adsorbed organic halide - Google Patents
Electrolytic reduction dehalogenation method for activated carbon adsorbed organic halide Download PDFInfo
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- JP2008272594A JP2008272594A JP2007060952A JP2007060952A JP2008272594A JP 2008272594 A JP2008272594 A JP 2008272594A JP 2007060952 A JP2007060952 A JP 2007060952A JP 2007060952 A JP2007060952 A JP 2007060952A JP 2008272594 A JP2008272594 A JP 2008272594A
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- Prior art keywords
- activated carbon
- organic halide
- reductive dehalogenation
- organic
- dehalogenation
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Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 150000004820 halides Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 23
- 230000002829 reductive effect Effects 0.000 claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- -1 aromatic halide Chemical class 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 150000002013 dioxins Chemical class 0.000 claims description 4
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 2
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000003053 immunization Effects 0.000 abstract 2
- 238000002649 immunization Methods 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- NHRQHXRDQZDFIO-UHFFFAOYSA-N 1-chloro-4-hexoxybenzene Chemical compound CCCCCCOC1=CC=C(Cl)C=C1 NHRQHXRDQZDFIO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001784 detoxification Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- KNRQFACTBMDELK-UHFFFAOYSA-N hexoxybenzene Chemical compound CCCCCCOC1=CC=CC=C1 KNRQFACTBMDELK-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GKLMJONYGGTHHM-UHFFFAOYSA-N 1-bromo-4-hexoxybenzene Chemical compound CCCCCCOC1=CC=C(Br)C=C1 GKLMJONYGGTHHM-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007256 debromination reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006042 reductive dechlorination reaction Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NPALUNJGWGOZQN-UHFFFAOYSA-N 1-hexoxy-4-(4-hexoxyphenyl)benzene Chemical group C1=CC(OCCCCCC)=CC=C1C1=CC=C(OCCCCCC)C=C1 NPALUNJGWGOZQN-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229920000557 Nafion® Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 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
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、活性炭に吸着した有害な有機ハロゲン化物を、電解還元により還元的脱塩素化を行って簡便且つ安全に無害化処理する方法に関する。 The present invention relates to a method for easily and safely detoxifying harmful organic halides adsorbed on activated carbon by performing reductive dechlorination by electrolytic reduction.
焼却炉などの排ガス、大気中の汚染物質、あるいは河川、湖沼、さらには工業排水などの汚水の浄化に於いて、活性炭吸着法は最も汎用的且つ有力な方法として多用されている。これに伴って、汚染物質を吸着した大量の活性炭が生成する。特に、ダイオキシン類や残留農薬などの各種有害有機塩素化物を吸着した活性炭は、通常、焼却処理、熱分解処理や埋め立て処理などが行われているが、排ガスと共に排出、あるいは埋立地からの溶出など、いずれも処理に伴う二次的な環境汚染を引き起こすことが懸念され、安全且つ簡便な無害化処理法あるいは賦活再生法が求められてきた。従来の有害有機塩素化物を吸着した活性炭の無害化処理法としては、過酸化物を作用させる化学的方法[特許文献1、特許文献2]、触媒を含む処理水中での酸素酸化(空気酸化)[特許文献3]が報告されている。また、活性炭および金属触媒を担持した活性炭に有害有機塩素化物を吸着させた後、マイクロ波を照射して分解する方法が報告されている[特許文献4]。しかし、これらの方法は大量の活性炭の無害化処理法としては、操作の簡便性、コスト、あるいは安全性などの観点から、必ずしも満足いく方法ではなく、多くの解決すべき問題を残している。 In purifying exhaust gas from incinerators, pollutants in the atmosphere, or sewage from rivers, lakes, and industrial effluents, the activated carbon adsorption method is widely used as the most versatile and effective method. Along with this, a large amount of activated carbon adsorbing contaminants is generated. In particular, activated carbon that adsorbs various toxic organic chlorinated substances such as dioxins and residual pesticides is usually incinerated, pyrolyzed, and landfilled. However, it is discharged with exhaust gas or eluted from landfills. In any case, there is a concern about causing secondary environmental pollution associated with the treatment, and a safe and simple detoxification treatment method or activation regeneration method has been demanded. As a conventional detoxification treatment method for activated carbon adsorbing harmful organic chlorinated substances, a chemical method using a peroxide [Patent Document 1, Patent Document 2], oxygen oxidation in treated water containing a catalyst (air oxidation) [Patent Document 3] has been reported. In addition, a method has been reported in which harmful organic chlorinated products are adsorbed on activated carbon and activated carbon supporting a metal catalyst, and then decomposed by irradiation with microwaves [Patent Document 4]. However, these methods are not necessarily satisfactory as detoxification treatment methods for a large amount of activated carbon from the viewpoint of easy operation, cost, safety, etc., and many problems to be solved remain.
一方、活性炭を電極とする有機ハロゲン化物の電解酸化・還元がいくつか報告されている。予めハロゲン化脂肪族炭化水素化合物を活性炭に吸着しこれを陽極として電解質水溶液中で光照射下に電解を行い分解する方法が開示されている[特許文献5]。汚染土壌内の有機塩素化物を分解除去する方法として有機塩素化物を含む汚染水を活性炭を陽陰極として電解することにより有機塩素化物を分解処理する方法が報告されている[特許文献6]。また、パラジウムや亜鉛などの金属を担持した活性炭布を陰極とする有機塩素化物の電解還元も報告されている[非特許文献1]。しかし、いずれも電流効率や操作の簡便性などの観点から、実用的な活性炭の無害化処理法としては十分満足できるものではない。 On the other hand, some electrolytic oxidation / reduction of organic halides using activated carbon as an electrode have been reported. A method is disclosed in which a halogenated aliphatic hydrocarbon compound is adsorbed on activated carbon in advance, and this is used as an anode for electrolysis in an aqueous electrolyte solution under light irradiation to decompose [Patent Document 5]. As a method for decomposing and removing organic chlorinated substances in contaminated soil, a method for decomposing organic chlorinated substances by electrolyzing contaminated water containing organic chlorinated substances using activated carbon as a cathode is reported [Patent Document 6]. In addition, electrolytic reduction of an organic chlorinated product using an activated carbon cloth carrying a metal such as palladium or zinc as a cathode has been reported [Non-patent Document 1]. However, none of them is sufficiently satisfactory as a practical method for detoxifying activated carbon from the viewpoint of current efficiency and ease of operation.
本発明は上記課題を解決するためになされたものであり、活性炭に吸着した有害な有機ハロゲン化物を、安価で安全に、且つ簡便な操作で、還元的脱ハロゲン化して無害化処理する方法を提供することを目的とするものである。 The present invention has been made to solve the above-mentioned problems, and provides a method for detoxifying a harmful organic halide adsorbed on activated carbon by reductive dehalogenation at a low cost, safely and with a simple operation. It is intended to provide.
上記課題は、活性炭に吸着した有害有機ハロゲン化物の電解還元による還元的脱ハロゲン化に於いて、陰極と陽極との間に活性炭層とセパレーターとを積層した電解装置を用いることを特徴とする有機ハロゲン化物の還元的脱ハロゲン化法を提供することによって解決される。 An object of the present invention is to employ an organic electrolysis apparatus in which an activated carbon layer and a separator are laminated between a cathode and an anode in reductive dehalogenation by electrolytic reduction of harmful organic halides adsorbed on activated carbon. It is solved by providing a method for reductive dehalogenation of halides.
また、上記課題は、活性炭に吸着した有機ハロゲン化物の電解還元による還元的脱ハロゲン化に於いて、陰極と陽極との間に活性炭層とセパレーターとを積層したフロー型電解装置を用いて電解液を流しながら電解を行うことを特徴とする有機ハロゲン化物の還元的脱ハロゲン化法を提供することによっても解決される。 Further, the above-mentioned problem is that in reductive dehalogenation by electrolytic reduction of organic halide adsorbed on activated carbon, an electrolytic solution using a flow type electrolyzer in which an activated carbon layer and a separator are laminated between a cathode and an anode. This can also be solved by providing a method for reductive dehalogenation of an organic halide characterized in that electrolysis is carried out while flowing.
このとき、活性炭として粉状活性炭あるいは布状活性炭のいずれかを用いることが好適であり、活性炭として予め遷移金属触媒を担持した粉状活性炭あるいは布状活性炭のいずれかを用いることが好適である。遷移金属触媒がパラジウム触媒であることが好適であり、電解液が支持塩を含む水、メタノール、あるいは水とメタノール混合溶液のいずれかであることが好適である。有機ハロゲン化物が、ポリクロロジベンゾ−パラ−ジオキシン(PCDDs)、ポリクロロジベンゾフラン(PCDFs)、コプラナ−ポリクロロビフェニル(コプラナ−PCB) などのダイオキシン類あるいはベンゼンヘキサクロリド(BHC)やポリクロロナフタレン(PCN)のいずれかであることが好適である。 At this time, it is preferable to use either powdered activated carbon or cloth-like activated carbon as the activated carbon, and it is preferable to use either powdered activated carbon or a cloth-like activated carbon on which a transition metal catalyst is previously supported as the activated carbon. The transition metal catalyst is preferably a palladium catalyst, and the electrolyte is preferably water containing a supporting salt, methanol, or a mixed solution of water and methanol. Organic halides are dioxins such as polychlorodibenzo-para-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), coplanar polychlorinated biphenyls (coplana-PCB), benzenehexachloride (BHC) and polychloronaphthalene (PCN). ) Is preferred.
また、このとき、有機ハロゲン化物が下記一般式(1)で示されるDDT誘導体のいずれかであることが好適である。
さらに、このとき、有機ハロゲン化物が下記一般式(2)で示される芳香族ハロゲン化物のいずれかであることも好適である。
本発明は、活性炭に吸着した有害な有機ハロゲン化物を、電解還元により直接還元的脱ハロゲン化して無害化処理するもので、活性炭と適当なセパレーターを陰極と陽極間に積層した電解槽を用いることにより、あるいは同様の積層構造を持つフローセルを用い電解液を流しながら通電を行うことにより、格段に電流効率を向上させることができ、低コストで安全に、且つ簡便な操作で効率よい還元的脱ハロゲン化が実現した。これにより、ダイオキシン類や残留農薬などの各種有害有機ハロゲン化物を吸着した活性炭の無害化処理に有効な方法を提供できる。さらには処理後の活性炭は有害ハロゲン化物を含まないので通常の賦活操作により、活性炭を再生することも可能である。 In the present invention, harmful organic halide adsorbed on activated carbon is detoxified by direct reductive dehalogenation by electrolytic reduction, and an electrolytic cell in which activated carbon and an appropriate separator are laminated between a cathode and an anode is used. Or by using a flow cell having a similar layered structure while flowing the electrolyte, the current efficiency can be greatly improved, and the reductive removal can be performed safely and easily with low cost. Halogenation was realized. Thereby, it is possible to provide an effective method for detoxifying activated carbon adsorbing various harmful organic halides such as dioxins and residual agricultural chemicals. Furthermore, since the activated carbon after treatment does not contain harmful halides, it is possible to regenerate the activated carbon by a normal activation operation.
本発明では、活性炭に吸着した有機ハロゲン化物の電解還元による還元的脱ハロゲン化に於いて、図1に示す陰極と陽極との間に活性炭層とセパレーターとを積層した電解装置を用いる。陽極上に、電解液は通すが活性炭は通さない非導電性セパレーターを配置し、その上に活性炭層を積層し、さらにその上に陰極を配置する。この積層構造を含んでいれば、装置の大きさや形状に特に限定はなく、電解液を含浸させたのち、直流電源を接続し電解する。 In the present invention, in reductive dehalogenation by electrolytic reduction of an organic halide adsorbed on activated carbon, an electrolysis apparatus in which an activated carbon layer and a separator are laminated between a cathode and an anode shown in FIG. 1 is used. On the anode, a non-conductive separator that allows the electrolyte to pass but not the activated carbon is disposed, an activated carbon layer is laminated thereon, and a cathode is further disposed thereon. If this laminated structure is included, the size and shape of the apparatus are not particularly limited, and after impregnating with an electrolytic solution, a direct current power source is connected for electrolysis.
また、本発明では、図2に示す陰極と陽極との間に活性炭層とセパレーターとを積層したフロー型電解装置を用いる。陽極上に、電解液は通すが活性炭は通さない非導電性セパレーターを置き、その上に活性炭層を積層し、さらにその上に陰極を配置する。電解液を陽極側の電解液導入口から導入し、セパレーター、活性炭層を通って陰極側の電解液排出口から流出させながら電解を行う。このように電解液をフローセル中に流すことにより、安定した電流を効率よく流すことができる。フローセルの大きさや形状は、上記積層構造を含んでいれば特に限定はない。 Moreover, in this invention, the flow type electrolyzer which laminated | stacked the activated carbon layer and the separator between the cathode and anode shown in FIG. 2 is used. On the anode, a non-conductive separator that allows the electrolytic solution to pass but not the activated carbon passes, and an activated carbon layer is laminated thereon, and a cathode is further disposed thereon. The electrolytic solution is introduced from the electrolytic solution inlet on the anode side, and electrolysis is performed while flowing out from the electrolytic solution outlet on the cathode side through the separator and the activated carbon layer. In this way, by flowing the electrolytic solution into the flow cell, a stable current can be efficiently flowed. The size or shape of the flow cell is not particularly limited as long as it includes the above laminated structure.
活性炭としては通常市販されている粉状活性炭(直径1〜500μm)、顆粒状活性炭、破砕状活性炭、ガス吸着等に用いる成型活性炭、あるいはフェルト状活性炭、布状活性炭などが用いられるが、好ましくは粉状活性炭もしくは布状活性炭のいずれかが用いられる。また、活性炭として予め遷移金属触媒を担持した粉状活性炭あるいは布状活性炭のいずれかを好適に用いることができる。 As the activated carbon, commercially available powdered activated carbon (1 to 500 μm in diameter), granular activated carbon, crushed activated carbon, molded activated carbon used for gas adsorption, etc., felt activated carbon, cloth activated carbon, etc. are preferably used. Either powdered activated carbon or cloth-like activated carbon is used. Moreover, either powdered activated carbon or cloth-like activated carbon in which a transition metal catalyst is supported in advance can be suitably used as the activated carbon.
活性炭上に担持される遷移金属触媒としては、通常の水添反応で用いられる白金、パラジウム、ロジウムあるいはニッケルを含む触媒が例示できるが、好ましくは、硝酸パラジウム、塩化パラジウム、酢酸パラジウム、塩化パラジウムビス(ベンゾニトリル)、塩化パラジウムビス(アセトニトリル)などのパラジウム触媒が用いられる。 Examples of the transition metal catalyst supported on activated carbon include catalysts containing platinum, palladium, rhodium or nickel used in ordinary hydrogenation reactions, but preferably palladium nitrate, palladium chloride, palladium acetate, palladium chloride bis A palladium catalyst such as (benzonitrile) or palladium chloride bis (acetonitrile) is used.
電解装置(図1、図2)に用いられるセパレーターとしては、電解液は通すが活性炭は通さない非導電性の多孔質材料であれば特に限定はない。具体的には、セルロース、ガラス繊維、シリカゲル、ポリ(テトラフルオロエチレン)製のろ紙や、セルロースやポリエステルなどの合成高分子からできた布や、有機溶媒で変性しないナフィオン(登録商標)やテフロン(登録商標)などの多孔質高分子からなる膜や、ガラスフィルターなどを例示できる。 The separator used in the electrolyzer (FIGS. 1 and 2) is not particularly limited as long as it is a non-conductive porous material that allows the electrolytic solution to pass but does not allow the activated carbon to pass. Specifically, cellulose, glass fiber, silica gel, poly (tetrafluoroethylene) filter paper, cloth made of synthetic polymers such as cellulose and polyester, Nafion (registered trademark) and Teflon (not modified with organic solvents) Examples thereof include a film made of a porous polymer such as a registered trademark and a glass filter.
陽極及び陰極の電極材料としては、市販の金属電極あるいは炭素電極を用いることができる。具体的には、ステンレス、鉄、ニッケル、チタン、銅、アルミニウム、白金被覆各種金属などの金属電極、あるいはグラッシーカーボンやグラファイトなどの炭素電極が例示できる。 Commercially available metal electrodes or carbon electrodes can be used as the anode and cathode electrode materials. Specific examples include metal electrodes such as stainless steel, iron, nickel, titanium, copper, aluminum, and various metals covered with platinum, or carbon electrodes such as glassy carbon and graphite.
電流は電解装置の形状や活性炭の種類と量、さらには電解液の種類によって一定しないが、概ね活性炭層1gあたり1〜1000mA、より好ましくは10〜100mAの電流を流す。 The current is not constant depending on the shape of the electrolysis apparatus, the type and amount of the activated carbon, and the type of the electrolytic solution, but a current of about 1 to 1000 mA, more preferably 10 to 100 mA is applied per 1 g of the activated carbon layer.
電解液の溶媒としては、水あるいはメタノール、エタノール、プロパノールなどの低級アルコールが用いられるが、好ましくは、水あるいはメタノールあるいはそれらの1:100ないし100:1の混合溶媒が用いられる。 As the solvent of the electrolytic solution, water or a lower alcohol such as methanol, ethanol, propanol or the like is used, but preferably water, methanol, or a mixed solvent thereof of 1: 100 to 100: 1 is used.
電解液には必要な電流を流すために0.001〜5mol/L、好ましくは0.01〜1mol/Lの支持電解質を加える。支持電解質としては、硫酸、塩酸、リン酸、酢酸、蟻酸などの酸、水酸化ナトリウム、水酸化カリウム、水酸化テトラアルキルアンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸テトラアルキルアンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素テトラアルキルアンモニウムなどのアルカリ、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸カリウム、過塩素酸テトラアルキルアンモニウム、過塩素酸N,N’−ジアルキルイミダゾリウム、テトラフルオロホウ酸リチウム、テトラフルオロホウ酸ナトリウム、テトラフルオロホウ酸カリウム、テトラフルオロホウ酸テトラアルキルアンモニウム、テトラフルオロホウ酸N,N’−ジアルキルイミダゾリウム、ヘキサフルオロリン酸リチウム、ヘキサフルオロリン酸ナトリウム、ヘキサフルオロリン酸カリウム、ヘキサフルオロリン酸テトラアルキルアンモニウム、ヘキサフルオロリン酸N,N’−ジアルキルイミダゾリウム、硫酸ナトリウム、硫酸カリウム、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化テトラアルキルアンモニウム、塩化N,N’−ジアルキルイミダゾリウム、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化テトラアルキルアンモニウム、臭化N,N’−ジアルキルイミダゾリウム、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、パラトルエンスルホン酸リチウム、パラトルエンスルホン酸ナトリウム、パラトルエンスルホン酸カリウム、ビス(トリフリミド)酸リチウム、ビス(トリフリミド)酸ナトリウム、ビス(トリフリミド)酸カリウムなどの塩を例示することができる。 In order to pass a necessary current to the electrolytic solution, 0.001 to 5 mol / L, preferably 0.01 to 1 mol / L of a supporting electrolyte is added. Supporting electrolytes include acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid, sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxide, sodium carbonate, potassium carbonate, tetraalkylammonium carbonate, sodium bicarbonate, hydrogen carbonate Alkali such as potassium and tetraalkylammonium hydrogen carbonate, lithium perchlorate, sodium perchlorate, potassium perchlorate, tetraalkylammonium perchlorate, N, N'-dialkylimidazolium perchlorate, lithium tetrafluoroborate Sodium tetrafluoroborate, potassium tetrafluoroborate, tetraalkylammonium tetrafluoroborate, N, N′-dialkylimidazolium tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate , Potassium hexafluorophosphate, tetraalkylammonium hexafluorophosphate, N, N′-dialkylimidazolium hexafluorophosphate, sodium sulfate, potassium sulfate, lithium chloride, sodium chloride, potassium chloride, tetraalkylammonium chloride, chloride N, N′-dialkylimidazolium, lithium bromide, sodium bromide, potassium bromide, tetraalkylammonium bromide, N, N′-dialkylimidazolium bromide, lithium acetate, sodium acetate, potassium acetate, paratoluenesulfone Examples of the salt include lithium acid, sodium paratoluenesulfonate, potassium paratoluenesulfonate, lithium bis (triflimide), sodium bis (triflimide), and potassium bis (triflimide). That.
本発明の電解還元は通常の環境条件下で行うことができ、冷却や加温等は特に必要ではないが、5〜30℃で電解するのが好適である。 The electrolytic reduction of the present invention can be carried out under normal environmental conditions, and cooling or heating is not particularly required, but it is preferable to perform electrolysis at 5 to 30 ° C.
以下、実施例によって本発明を説明するが、この実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, it is not limited to this Example.
実施例1
市販の5重量%のパラジウムを担持した活性炭1gに4−クロロフェニルヘキシルエーテル(1a)200mgを吸着した。この活性炭に少量の0.5mol/L水酸化ナトリウム水溶液を含浸し、図3の装置に装填した。この装置に200mAの電流を流して20分間電解した。反応後の活性炭をトルエンで洗浄し、洗液をガスクロマトグラフィーで分析したところ、還元体生成物であるフェニルヘキシルエーテル(2a)が62%、ホモカップリング体である4,4’−ジヘキシルオキシビフェニル(3a)が10%得られ、原料1aが12%回収された。
Example 1
200 mg of 4-chlorophenyl hexyl ether (1a) was adsorbed on 1 g of commercially available activated carbon carrying 5% by weight of palladium. The activated carbon was impregnated with a small amount of a 0.5 mol / L sodium hydroxide aqueous solution and loaded into the apparatus shown in FIG. The apparatus was electrolyzed with a current of 200 mA for 20 minutes. After the reaction, the activated carbon was washed with toluene, and the washing solution was analyzed by gas chromatography. 10% of biphenyl (3a) was obtained, and 12% of raw material 1a was recovered.
実施例2〜6
基質として4−ヘキシルオキシブロモベンゼン(1b)を用い、下記の表1に示した支持電解質を用いる以外は実施例1と同様にして還元的脱臭素化を行った。
Examples 2-6
Reductive debromination was carried out in the same manner as in Example 1 except that 4-hexyloxybromobenzene (1b) was used as a substrate and the supporting electrolyte shown in Table 1 below was used.
実施例7〜14
5重量%の酢酸パラジウムを担持した粉状活性炭を用い、下記の表2に示す支持電解質を用いた以外は実施例1と同様にして還元的脱臭素化を行った。
Examples 7-14
Reductive debromination was carried out in the same manner as in Example 1 except that powdered activated carbon supporting 5% by weight of palladium acetate was used and the supporting electrolyte shown in Table 2 below was used.
実施例15
10mgのPCB(KC−500)を吸着した活性炭10gを用いて、200mAの電流を流して100分間電解した以外は実施例1と同様にして還元的脱塩素化を行い、JIS K0093に掲載のCB%を用いる方法により分析、計算した結果、凡そ77%のPCBが脱塩素化・無害化処理されたことがわかった。
Example 15
Reductive dechlorination was carried out in the same manner as in Example 1 except that 10 g of activated carbon adsorbed with 10 mg of PCB (KC-500) was used and electrolysis was performed for 100 minutes with a current of 200 mA, and CB described in JIS K0093. As a result of analysis and calculation by a method using%, it was found that about 77% of PCB was dechlorinated and detoxified.
実施例16〜18
下記の表3に示す芳香族ハロゲン化物(Ar−X)を用いる以外は実施例1と同様にして還元的脱ハロゲン化を行った。
Examples 16-18
Reductive dehalogenation was performed in the same manner as in Example 1 except that the aromatic halide (Ar-X) shown in Table 3 below was used.
実施例19
5重量%のPdを担持した布状の活性炭250mgに4−クロロフェニルヘキシルエーテル(1a)50mgを吸着させた。この布状の活性炭を少量の0.1mol/L水酸化ナトリウム水溶液に浸したのち、図4の装置に装填した。この装置に10mAの電流を流して定電流電解した。反応後の活性炭をトルエンで洗浄し、洗液をガスクロマトグラフィーで分析したところ、還元体生成物であるフェニルヘキシルエーテル(2a)が75%、ホモカップリング体である4,4’−ジヘキシルオキシビフェニル(3a)が13%得られた。
Example 19
50 mg of 4-chlorophenylhexyl ether (1a) was adsorbed on 250 mg of cloth-like activated carbon carrying 5% by weight of Pd. This cloth-like activated carbon was immersed in a small amount of a 0.1 mol / L sodium hydroxide aqueous solution and then loaded into the apparatus shown in FIG. This apparatus was subjected to constant current electrolysis by supplying a current of 10 mA. The activated carbon after the reaction was washed with toluene, and the washing solution was analyzed by gas chromatography. As a result, 75% of the reduced product, phenylhexyl ether (2a), and 4,4′-dihexyloxy, which was a homo-coupled product, were obtained. 13% of biphenyl (3a) was obtained.
実施例20
5重量%のPdを担持した布状の活性炭250mgに4−クロロフェニルヘキシルエーテル(1a)50mgを吸着させた。この布状の活性炭を少量の0.1mol/L水酸化ナトリウム水溶液に浸したのち、図5の装置に装填した。この装置に0.1mol/L水酸化ナトリウム水溶液を毎分4mL流しながら、10mAの電流を一時間20分間流して定電流電解した。反応後の活性炭をトルエンで洗浄し、洗液をガスクロマトグラフィーで分析したところ、還元体生成物であるフェニルヘキシルエーテル(2a)が83%、ホモカップリング体である4,4’−ジヘキシルオキシビフェニル(3a)が11%,原料(1a)が3%回収された。
Example 20
50 mg of 4-chlorophenylhexyl ether (1a) was adsorbed on 250 mg of cloth-like activated carbon carrying 5% by weight of Pd. The cloth-like activated carbon was immersed in a small amount of a 0.1 mol / L sodium hydroxide aqueous solution and then loaded into the apparatus shown in FIG. The apparatus was subjected to constant current electrolysis by flowing a current of 10 mA for 1 hour and 20 minutes while flowing 4 mL of a 0.1 mol / L sodium hydroxide aqueous solution per minute. After the reaction, the activated carbon was washed with toluene, and the washing solution was analyzed by gas chromatography. 11% of biphenyl (3a) and 3% of raw material (1a) were recovered.
実施例21
電解中、水酸化ナトリウムメタノール溶液(0.1mol/L,20ml)を毎分4mLで循環させる以外は実施例20と同様に反応させたところ、還元体生成物であるフェニルヘキシルエーテル(2a)が78%、ホモカップリング体である4,4’−ジヘキシルオキシビフェニル(3a)が15%得られた。原料回収はなかった。
Example 21
During electrolysis, a reaction was conducted in the same manner as in Example 20 except that sodium hydroxide methanol solution (0.1 mol / L, 20 ml) was circulated at a rate of 4 mL per minute. As a result, phenylhexyl ether (2a) as a reduced product was obtained. 78% and 4,4′-dihexyloxybiphenyl (3a) which is a homo-coupled product was obtained 15%. There was no material recovery.
本発明は電力、エネルギー、各種化学産業に於いて、有害有機ハロゲン化物を含む排ガスあるいは排水や廃液水の浄化に用いられた使用済み活性炭の無害化処理さらには賦活再生処理に好適に利用できる。 INDUSTRIAL APPLICABILITY The present invention can be suitably used for detoxification treatment of used activated carbon used for purification of exhaust gas containing toxic organic halides, waste water or waste water, and activation regeneration treatment in the electric power, energy and various chemical industries.
1 陽極
2 陰極
3 電解液は通すが活性炭は通さない非導電性セパレーター
4 活性炭層(粉状活性炭あるいは布状活性炭)
5 電源装置
6 電解液導入口
7 電解液排出口
8 カバー
9 ポリ(テトラフルオロエチレン)製ろ紙
10 基質を吸着したパラジウム担持粉状活性炭層
11 基質を吸着したパラジウム担持布状活性炭層
1 Anode 2 Cathode 3 Non-conductive separator that allows electrolyte to pass but not activated carbon 4 Activated carbon layer (powder activated carbon or cloth activated carbon)
DESCRIPTION OF SYMBOLS 5 Power supply device 6 Electrolyte inlet 7 Electrolyte outlet 8 Cover 9 Poly (tetrafluoroethylene) filter paper 10 Palladium carrying powdery activated carbon layer which adsorbed substrate 11 Palladium carrying cloth activated carbon layer which adsorbed substrate
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