JP7440031B2 - Treatment method for cyanide-containing wastewater - Google Patents
Treatment method for cyanide-containing wastewater Download PDFInfo
- Publication number
- JP7440031B2 JP7440031B2 JP2019206379A JP2019206379A JP7440031B2 JP 7440031 B2 JP7440031 B2 JP 7440031B2 JP 2019206379 A JP2019206379 A JP 2019206379A JP 2019206379 A JP2019206379 A JP 2019206379A JP 7440031 B2 JP7440031 B2 JP 7440031B2
- Authority
- JP
- Japan
- Prior art keywords
- cyanide
- wastewater
- containing wastewater
- concentration
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims description 155
- 239000002351 wastewater Substances 0.000 title claims description 132
- 238000000034 method Methods 0.000 title claims description 52
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000004155 Chlorine dioxide Substances 0.000 claims description 37
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 37
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 26
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 claims description 20
- -1 ammonium ions Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 14
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 4
- 150000003868 ammonium compounds Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 238000012360 testing method Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000010802 sludge Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 10
- 150000002825 nitriles Chemical class 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000015278 beef Nutrition 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000001477 organic nitrogen group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 229960000686 benzalkonium chloride Drugs 0.000 description 3
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 3
- VWPXUKSDWYXLKV-UHFFFAOYSA-N bromosulfamic acid Chemical compound OS(=O)(=O)NBr VWPXUKSDWYXLKV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical class CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical group OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 2
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
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- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Chemical group CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- HIWVFNVUJDPDKS-UHFFFAOYSA-N 1-octadecylpyridin-1-ium Chemical class CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 HIWVFNVUJDPDKS-UHFFFAOYSA-N 0.000 description 1
- MINQXBMDXRYZDW-UHFFFAOYSA-N 2-hydroxydodecyl(trimethyl)azanium Chemical class CCCCCCCCCCC(O)C[N+](C)(C)C MINQXBMDXRYZDW-UHFFFAOYSA-N 0.000 description 1
- OCJOIFHALFZTMB-UHFFFAOYSA-N 2-hydroxyhexadecyl(trimethyl)azanium Chemical class CCCCCCCCCCCCCCC(O)C[N+](C)(C)C OCJOIFHALFZTMB-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Chemical group CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical group CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical group NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Chemical group CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KVWKDIMORVBAKI-UHFFFAOYSA-N OC(C[N+](CC)(CC)CC)CCCCCCCCCC Chemical class OC(C[N+](CC)(CC)CC)CCCCCCCCCC KVWKDIMORVBAKI-UHFFFAOYSA-N 0.000 description 1
- VPYGZGCVMSAJMJ-UHFFFAOYSA-N OC(C[N+](CC)(CC)CC)CCCCCCCCCCCCCC Chemical class OC(C[N+](CC)(CC)CC)CCCCCCCCCCCCCC VPYGZGCVMSAJMJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Chemical group 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Chemical group CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- 239000001361 adipic acid Chemical group 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
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- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- VHHTZMNPCWGDHG-UHFFFAOYSA-N chlorosulfamic acid Chemical compound ClNS(O)(=O)=O.ClNS(O)(=O)=O VHHTZMNPCWGDHG-UHFFFAOYSA-N 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OQUVWFIKPIVFNX-UHFFFAOYSA-N decyl-dimethyl-tetradecylazanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCC OQUVWFIKPIVFNX-UHFFFAOYSA-N 0.000 description 1
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical class CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SWSFKKWJEHRFFP-UHFFFAOYSA-N dihexadecyl(dimethyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC SWSFKKWJEHRFFP-UHFFFAOYSA-N 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- MELGLHXCBHKVJG-UHFFFAOYSA-N dimethyl(dioctyl)azanium Chemical class CCCCCCCC[N+](C)(C)CCCCCCCC MELGLHXCBHKVJG-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- DGJUONISEWDPFO-UHFFFAOYSA-N dodecyl(triethyl)azanium Chemical class CCCCCCCCCCCC[N+](CC)(CC)CC DGJUONISEWDPFO-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 235000014655 lactic acid Nutrition 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005645 linoleyl group Chemical group 0.000 description 1
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- VIVMUYLVKOXORD-UHFFFAOYSA-N magnesium dihypobromite Chemical compound [Mg+2].Br[O-].Br[O-] VIVMUYLVKOXORD-UHFFFAOYSA-N 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical group CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 1
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- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 1
- CENIAFYRIODGSU-UHFFFAOYSA-N triethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CC CENIAFYRIODGSU-UHFFFAOYSA-N 0.000 description 1
- JXCCIZBMTUFJKN-UHFFFAOYSA-N triethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](CC)(CC)CC JXCCIZBMTUFJKN-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
本発明は、従来よりも薬剤添加量を極力抑え、二酸化塩素ガスの発生およびそれによる設備への腐食などの作業環境の悪化を軽減し、従来よりも処理水におけるスラッジの発生量を低減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法に関する。 The present invention minimizes the amount of chemicals added than before, reduces deterioration of the working environment such as generation of chlorine dioxide gas and corrosion of equipment, and reduces the amount of sludge generated in treated water than before. The present invention relates to a method for treating cyanide-containing wastewater that can reliably remove cyanide from wastewater safely and inexpensively with simple operations.
シアンは生態系に強い悪影響を及ぼすため、シアン含有廃水（「シアン廃水」ともいう）を自然界にそのまま放出することはできない。水質汚濁防止法に基づきシアンの排水基準が定められ、この基準（１ｍｇ／Ｌ以下）を満たすようにシアン除去処理を行い、無害化した廃水でなければ下水などに排出できない。また、地域によっては、条例により、上記の排水基準値よりもさらに低い上乗せ排水基準が定められている。また、廃水中に含まれるシアンの一部はシアン化水素ガスとして周辺に拡散し、作業環境が著しく損なわれるという問題もあり、労働安全衛生法では、シアン化水素の作業環境濃度は３ｐｐｍ以下であることが規定されている。
シアンは、廃水の由来にも因り、含有量の多少はあるが、難分解性シアン錯体およびそのイオン、易分解性シアン錯体およびそのイオン、シアン化物イオンの３種の形態で廃水中に存在している。
Because cyanide has a strong negative impact on the ecosystem, cyanide-containing wastewater (also called "cyanide wastewater") cannot be directly released into the natural world. Wastewater standards for cyanide have been established based on the Water Pollution Control Law, and cyanide removal treatment is performed to meet these standards (1 mg/L or less), and wastewater must be rendered harmless before it can be discharged into a sewage system. Additionally, in some regions, additional wastewater standards that are lower than the above-mentioned wastewater standards are established by ordinance. Additionally, there is the problem that some of the cyanide contained in wastewater diffuses into the surrounding area as hydrogen cyanide gas, seriously impairing the working environment.The Industrial Safety and Health Act stipulates that the concentration of hydrogen cyanide in the working environment is 3 ppm or less. has been done.
Cyanide exists in three forms in wastewater: persistent cyanide complexes and their ions, easily decomposable cyanide complexes and their ions, and cyanide ions, although the content varies depending on the origin of the wastewater. ing.
従来からシアン含有廃水中のシアンの除去処理として様々な方法が提案され、実用化されているが、いずれも一長一短があり、廃水の状況に応じて使い分けられている。
例えば、（１）シアン含有廃水をアルカリ性に調整した後、塩素を注入してシアンを酸化分解するアルカリ塩素法、（２）強力なオゾンの酸化力でシアンを窒素ガスと炭酸水素塩に酸化分解するオゾン酸化法および（３）非溶解性の電極を用いてシアンを電気分解し、酸化反応を行なう電解酸化法（電解法）などの酸化分解法；（４）シアン含有廃水中に、鉄イオンの供給化合物として、例えば硫酸第一鉄を添加し、難溶性のフェリ／フェロシアン化物を生成させ、これを沈殿除去する紺青法、（５）塩化亜鉛と還元剤とを添加し、生成した不溶錯体を沈殿除去する亜鉛白法および（６）２価の銅塩と還元剤とを添加し、生成した不溶錯体を沈殿除去する還元銅塩法などの不溶錯体法；（７）シアンに対して馴養させた微生物（シアン分解菌）にシアンを分解させる生物処理法；（８）シアン含有廃水を高温に保持してシアン化合物をアンモニアと蟻酸に加水分解させ、共存する重金属類を単体または酸化物として析出させる熱加水分解法および（９）シアンの分解以外に有機汚濁物をも酸化分解させる湿式酸化法などの熱水反応などがある。
Various methods have been proposed and put into practical use to remove cyanide from cyanide-containing wastewater, but each method has advantages and disadvantages, and they are used depending on the situation of the wastewater.
For example, (1) an alkaline chlorine method in which cyanide-containing wastewater is adjusted to alkalinity and then chlorine is injected to oxidize and decompose cyanide; (2) cyanide is oxidized and decomposed into nitrogen gas and hydrogen carbonate using the powerful oxidizing power of ozone. and (3) oxidative decomposition methods such as electrolytic oxidation (electrolytic method) in which cyanide is electrolyzed using a non-dissolving electrode to perform an oxidation reaction; (4) iron ions are present in cyanide-containing wastewater. As a feed compound, for example, ferrous sulfate is added to produce poorly soluble ferri/ferrocyanide, which is then precipitated and removed using the Prussian method; (5) zinc chloride and a reducing agent are added to produce an insoluble Insoluble complex methods such as the zinc white method in which the complex is precipitated and removed; and (6) the reduced copper salt method in which a divalent copper salt and a reducing agent are added and the formed insoluble complex is precipitated and removed; (7) For cyanide. Biological treatment method in which cyanide is decomposed by acclimatized microorganisms (cyanide-degrading bacteria); (8) Cyanide-containing wastewater is held at high temperatures to hydrolyze cyanide compounds into ammonia and formic acid, and coexisting heavy metals are converted into simple substances or oxides. (9) A hydrothermal reaction method such as a wet oxidation method that oxidizes and decomposes organic pollutants in addition to the decomposition of cyanide.
具体的には、第四級アンモニウム化合物を用いるシアン含有廃水の処理方法が提案されている。
例えば、特開２００５－０８１１７０号公報（特許文献１）には、シアン化合物を含有する被処理液にシアン化合物と反応して析出物を生成する金属イオンを添加する反応工程と、反応工程で生成した析出物を被処理液から分離する金属シアン化合物分離除去工程と、析出物を分離除去した被処理液を活性炭と接触させてシアン化合物を吸着除去するシアン化合物吸着除去工程とを有するシアン化合物を含有する排水の処理方法が開示され、被処理液を活性炭に接触させる前に、セチルトリメチルアンモニウムブロミド（ＣＴＡＢ）のようなカチオン系界面活性剤を添加することが開示されている。
Specifically, a method for treating cyanide-containing wastewater using a quaternary ammonium compound has been proposed.
For example, Japanese Patent Application Laid-open No. 2005-081170 (Patent Document 1) describes a reaction process in which metal ions that react with cyanide to form precipitates are added to a liquid to be treated containing cyanide; A cyanide compound separation process includes a metal cyanide compound separation and removal process in which precipitates are separated from a liquid to be treated, and a cyanide adsorption and removal process in which the liquid to be treated from which precipitates have been separated and removed is brought into contact with activated carbon to adsorb and remove cyanide compounds. A method for treating the wastewater contained therein is disclosed, in which a cationic surfactant such as cetyltrimethylammonium bromide (CTAB) is added before contacting the liquid to be treated with activated carbon.
また、特開２０１４－００４５８１号公報（特許文献２）には、シアン含有廃水に、炭素数が５以上でありかつ廃水中でカチオンを生じる、特定のテトラアルキルアンモニウム化合物およびピリジニウム化合物から選択される有機含窒素化合物を添加し、シアン成分と有機含窒素化合物とを共存させることで廃水中のシアン成分を不溶化した後、不溶化されたシアン成分を固液分離する工程を有するシアン含有廃水の処理方法が開示され、特定の有機含窒素化合物を添加したシアン含有廃水を、Ｚｎ2+またはＣｕ+の少なくともいずれかのイオンを共存させた状態として、さらにはＦｅ2+、Ｆｅ3+、Ｃｕ2+、Ｍｎ2+およびＡｌ3+からなる群から選ばれる少なくともいずれかの金属イオンを共存させた状態で処理することが開示されている。 Furthermore, JP 2014-004581 A (Patent Document 2) discloses that cyanide-containing wastewater is treated with specific tetraalkylammonium compounds and pyridinium compounds that have 5 or more carbon atoms and produce cations in the wastewater. A method for treating cyanide-containing wastewater comprising the steps of adding an organic nitrogen-containing compound to insolubilize the cyanide component in wastewater by allowing the cyanide component and the organic nitrogen-containing compound to coexist, and then separating the insolubilized cyanide component from solid-liquid. is disclosed, in which cyanide-containing wastewater to which a specific organic nitrogen-containing compound has been added is treated in a state where at least one of Zn 2+ or Cu + ions coexists, and furthermore, Fe 2+ , Fe 3+ , Cu 2+ , Mn 2+ and Al 3+ are disclosed.
さらに、特開２０１５－１００７６７号公報（特許文献３）には、沈殿槽にシアン含有廃水を導入する前の段階で或いは導入すると同時に第一鉄塩を添加して、その後に特定のテトラアルキルアンモニウム化合物およびピリジニウム化合物から選択される有機含窒素化合物と第一銅塩とを添加して、処理対象とするシアン含有廃水中にさらにこれらの成分を共存させて廃水中のシアン成分を不溶化する工程を有するシアン含有廃水の処理方法が開示されている。 Furthermore, Japanese Patent Application Laid-open No. 2015-100767 (Patent Document 3) discloses that ferrous salt is added before or at the same time as cyanide-containing wastewater is introduced into a settling tank, and then a specific tetraalkylammonium salt is added. A step of adding an organic nitrogen-containing compound selected from compounds and pyridinium compounds and a cuprous salt to make these components coexist in the cyanide-containing wastewater to be treated to insolubilize the cyanide component in the wastewater. A method for treating cyanide-containing wastewater is disclosed.
また、特開２００８－０３６６０８号公報（特許文献４）には、シアン化合物を含有する被処理水に、硫酸第２銅のような２価の銅塩および重亜硫酸ナトリウムのような還元剤を添加して難溶性塩を生成させて分離する分離工程と、分離工程の処理水にアルカリ性条件下にて次亜塩素酸ナトリウムのような酸化剤を添加して該処理水中のシアン化合物を酸化する酸化工程とを有するシアン含有水の処理方法が開示されている。 Furthermore, in JP-A No. 2008-036608 (Patent Document 4), a divalent copper salt such as cupric sulfate and a reducing agent such as sodium bisulfite are added to water to be treated containing cyanide. a separation process in which hardly soluble salts are generated and separated; and an oxidation process in which an oxidizing agent such as sodium hypochlorite is added to the treated water in the separation process under alkaline conditions to oxidize cyanide compounds in the treated water. A method for treating cyanide-containing water is disclosed.
しかしながら、上記の先行技術では、煩雑な工程や操作が必要であり、それに伴い複数の反応槽が必要となる場合もある。また、シアン除去の効果が十分であっても、金属化合物を用いる方法では、処理において多量のスラッジが生成するため、その産業廃棄物処理にコストが掛かるという課題があった。 However, the above-mentioned prior art requires complicated steps and operations, and may require a plurality of reaction vessels accordingly. Further, even if the effect of removing cyanide is sufficient, the method using a metal compound has the problem that a large amount of sludge is generated during the treatment, which increases the cost of processing the industrial waste.
そこで、本発明は、従来よりも薬剤添加量を極力抑え、二酸化塩素ガスの発生およびそれによる設備への腐食などの作業環境の悪化を軽減し、従来よりも処理水におけるスラッジの発生量を低減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法を提供することを課題とする。 Therefore, the present invention minimizes the amount of added chemicals compared to conventional methods, reduces the deterioration of the working environment such as generation of chlorine dioxide gas and corrosion of equipment, and reduces the amount of sludge generated in treated water compared to conventional methods. An object of the present invention is to provide a method for treating cyanide-containing wastewater that can reliably remove cyanide from wastewater safely and inexpensively with simple operations.
本発明の発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、シアン含有廃水の処理において、有効量の二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、有効量の第四級アンモニウム化合物とを併用することにより、意外にも、従来よりも薬剤添加量を極力抑え、二酸化塩素ガスの発生およびそれによる設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し、さらに従来よりも処理水におけるスラッジの発生量を低減し得る事実を見出し、本発明を完成するに到った。 As a result of extensive research to solve the above problems, the inventors of the present invention have found that an effective amount of chlorine dioxide, hypochlorite, and N-chlorosulfamate can be selected from among chlorine dioxide, hypochlorite, and N-chlorosulfamate in the treatment of cyanide-containing wastewater. Surprisingly, by using one or more compounds and an effective amount of a quaternary ammonium compound, the amount of added chemicals can be minimized compared to conventional methods, and the generation of chlorine dioxide gas and the corrosion of equipment due to it can be prevented. We have discovered the fact that it is possible to reduce the deterioration of the working environment, reliably remove cyanide from wastewater safely and inexpensively with simple operations, and further reduce the amount of sludge generated in treated water compared to conventional methods, and have developed the present invention. It has been completed.
かくして、本発明によれば、シアン含有廃水に、二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物とを同時または別々に添加して、該廃水からシアンを除去することを特徴とするシアン含有廃水の処理方法が提供される。 Thus, according to the invention, one or more compounds selected from chlorine dioxide, hypochlorite and N-chlorosulfamate and a quaternary ammonium compound are simultaneously or separately added to cyanide-containing wastewater. A method for treating cyanide-containing wastewater is provided, the method comprising: adding cyanide to remove cyanide from the wastewater.
本発明によれば、従来よりも薬剤添加量を極力抑え、二酸化塩素ガスの発生およびそれによる設備への腐食などの作業環境の悪化を軽減し、従来よりも処理水におけるスラッジの発生量を低減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法を提供することができる。
すなわち、本発明によれば、各種形態で廃水中に含有するシアンを、従来よりも薬剤添加量を極力抑え、簡便な操作で処理することができ、さらに処理におけるスラッジの生成を抑えて、その産業廃棄物処理コストを低減できる。
また、廃水中のシアン濃度が排水規制（１ｍｇ／Ｌ以下）を満たすことで、周辺へのシアン化水素ガスの拡散も抑えられ、作業環境の改善も期待できる。
よって、本発明の方法で処理した廃水をそのまま自然界に放出しても、環境に対する影響が非常に少なく、また処理後に発生する懸濁物質（廃棄物）の量も少なくできることから、本発明の方法は産業上極めて有用である。
According to the present invention, the amount of added chemicals is minimized compared to conventional methods, the generation of chlorine dioxide gas and the resulting corrosion of equipment and other deterioration of the working environment are reduced, and the amount of sludge generated in treated water is reduced compared to conventional methods. In addition, it is possible to provide a method for treating cyanide-containing wastewater that can reliably remove cyanide from wastewater safely and inexpensively with simple operations.
In other words, according to the present invention, cyanide contained in various forms in wastewater can be treated with a simpler operation and with the added amount of chemicals being kept to a minimum compared to conventional methods, and the generation of sludge during the treatment can be suppressed. Industrial waste processing costs can be reduced.
Additionally, by ensuring that the cyanide concentration in the wastewater satisfies wastewater regulations (1 mg/L or less), diffusion of hydrogen cyanide gas into the surrounding area can be suppressed, and an improvement in the working environment can be expected.
Therefore, even if the wastewater treated by the method of the present invention is released into nature as it is, it has very little impact on the environment, and the amount of suspended solids (waste) generated after treatment can be reduced. is extremely useful industrially.
また、本発明のシアン含有廃水の処理方法は、次の条件のいずれか１つを満たす場合に、上記の効果をより発揮する。
（１）シアン含有廃水が、シアン濃度で２～２００ｍｇ／Ｌのシアン錯体を含有する廃水である。
（２）シアン含有廃水が、ｐＨ６～９である。
Furthermore, the method for treating cyanide-containing wastewater of the present invention exhibits the above effects more effectively when any one of the following conditions is satisfied.
(1) The cyanide-containing wastewater is wastewater containing a cyanide complex with a cyanide concentration of 2 to 200 mg/L.
(2) The cyanide-containing wastewater has a pH of 6 to 9.
本発明のシアン含有廃水の処理方法は、シアン含有廃水に、二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物とを同時または別々に添加して、該廃水からシアンを除去することを特徴とする。 The method for treating cyanide-containing wastewater of the present invention includes simultaneously adding one or more compounds selected from chlorine dioxide, hypochlorite, and N-chlorosulfamate and a quaternary ammonium compound to cyanide-containing wastewater. or separately added to remove cyanide from the wastewater.
（二酸化塩素）
本発明において用いられる二酸化塩素は、極めて不安定な化学物質であるため、その貯蔵や輸送は非常に困難である。したがって、二酸化塩素または廃水中で二酸化塩素を発生し得る化合物を廃水に直接添加してもよいが、その場で公知の方法により二酸化塩素を製造（生成）するか、または廃水中で二酸化塩素を発生し得る化合物を水に添加して二酸化塩素を発生させ、所望の添加濃度に調整して用いるのが好ましい。
例えば、次のような反応により二酸化塩素を製造することができ、市販の二酸化塩素発生器（装置）を用いることもできる。
（１）次亜塩素酸ナトリウムと塩酸と亜塩素酸ナトリウムとの反応
ＮａＯＣｌ＋２ＨＣｌ＋２ＮａＣｌＯ2 → ２ＣｌＯ2＋３ＮａＣｌ＋Ｈ2Ｏ
（２）亜塩素酸ナトリウムと塩酸との反応
５ＮａＣｌＯ2＋４ＨＣｌ → ４ＣｌＯ2＋５ＮａＣｌ＋２Ｈ2Ｏ
（３）塩素酸ナトリウム、過酸化水素および硫酸との反応
２ＮａＣｌＯ3＋Ｈ2Ｏ2＋Ｈ2ＳＯ4 → ２ＣｌＯ2＋Ｎａ2ＳＯ4＋Ｏ2＋２Ｈ2Ｏ
(chlorine dioxide)
Since chlorine dioxide used in the present invention is an extremely unstable chemical substance, it is extremely difficult to store and transport it. Therefore, although chlorine dioxide or a compound capable of generating chlorine dioxide in wastewater may be added directly to wastewater, chlorine dioxide may be produced (generated) on site by known methods, or chlorine dioxide may be produced in wastewater by It is preferable to generate chlorine dioxide by adding a compound that can be generated to water, and adjust the concentration to a desired concentration before use.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (device) can also be used.
(1) Reaction between sodium hypochlorite, hydrochloric acid, and sodium chlorite NaOCl+2HCl+2NaClO 2 → 2ClO 2 +3NaCl+H 2 O
(2) Reaction between sodium chlorite and hydrochloric acid 5NaClO 2 +4HCl → 4ClO 2 +5NaCl+2H 2 O
(3) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO 3 +H 2 O 2 +H 2 SO 4 → 2ClO 2 +Na 2 SO 4 +O 2 +2H 2 O
（次亜塩素酸塩）
本発明において用いられる次亜塩素酸塩は、水中で次亜塩素酸を生成して、本発明の効果を奏する化合物であれば特に限定されない。例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウム、次亜塩素酸マグネシウムなどの次亜塩素酸のアルカリ金属塩およびアルカリ土類金属塩が挙げられる。特に、次亜塩素酸ナトリウム、次亜塩素酸カリウムは工業的に入手し易く、本発明において好適に用いられる。また、食塩水や海水を電解槽で電解することによって得られる次亜塩素酸であってもよい。
次亜塩素酸塩を用いる場合には、薬剤添加量を極力抑える点で、過酸化水素を併用するのが好ましい。
(Hypochlorite)
The hypochlorite used in the present invention is not particularly limited as long as it is a compound that produces hypochlorous acid in water and exhibits the effects of the present invention. Examples include alkali metal salts and alkaline earth metal salts of hypochlorous acid, such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and magnesium hypochlorite. In particular, sodium hypochlorite and potassium hypochlorite are easily available industrially and are preferably used in the present invention. Alternatively, hypochlorous acid obtained by electrolyzing salt water or seawater in an electrolytic cell may be used.
When using hypochlorite, it is preferable to use hydrogen peroxide in combination in order to minimize the amount of added chemicals.
本発明では、上記の次亜塩素酸塩の代わりに次亜臭素酸塩を用いることもできる。
本発明において用いられる次亜臭素酸塩は、水中で次亜臭素酸を生成して、本発明の効果を奏する化合物であれば特に限定されない。例えば、次亜臭素酸ナトリウム、次亜臭素酸カリウム、次亜臭素酸カルシウム、次亜臭素酸マグネシウムなどの次亜臭素酸のアルカリ金属塩およびアルカリ土類金属塩が挙げられる。特に、次亜臭素酸ナトリウム、次亜臭素酸カリウムは工業的に入手し易く、本発明において好適に用いられる。また、食塩水や海水を電解槽で電解することによって得られる次亜臭素酸であってもよい。
次亜臭素酸塩を用いる場合には薬剤添加量を極力抑える点で、過酸化水素を併用するのが好ましい。
In the present invention, hypobromite can also be used instead of the above-mentioned hypochlorite.
The hypobromite used in the present invention is not particularly limited as long as it is a compound that produces hypobromite in water and exhibits the effects of the present invention. Examples include alkali metal salts and alkaline earth metal salts of hypobromite such as sodium hypobromite, potassium hypobromite, calcium hypobromite, and magnesium hypobromite. In particular, sodium hypobromite and potassium hypobromite are easily available industrially and are preferably used in the present invention. Alternatively, hypobromous acid obtained by electrolyzing salt water or seawater in an electrolytic cell may be used.
When hypobromite is used, it is preferable to use hydrogen peroxide in combination with the aim of minimizing the amount of added chemicals.
（Ｎ－クロロスルファマート）
本発明において用いられるＮ－クロロスルファマートは、公知の方法、例えば、特表２００３－５０３３２３号公報、特開２００６－０２２０９７号公報、特表平１１－５０６１３９号、特表２００１－５０１８６９号公報、特表２００３－５０７３２６号公報及び特開２０１４－１０１２５１号公報などに記載の方法により調製することができる。例えば、スルファミン酸と、次亜塩素酸との反応生成物を好適に用いることができる。
Ｎ－クロロスルファマートを用いる場合には、薬剤添加量を極力抑える点で、過酸化水素を併用するのが好ましい。
(N-chlorosulfamate)
N-chlorosulfamate used in the present invention can be prepared by a known method, for example, Japanese Patent Application Publication No. 2003-503323, Japanese Patent Application Publication No. 2006-022097, Japanese Patent Application Publication No. 11-506139, Japanese Patent Application Publication No. 2001-501869. , Japanese Patent Application Publication No. 2003-507326 and Japanese Patent Application Laid-open No. 2014-101251. For example, a reaction product of sulfamic acid and hypochlorous acid can be suitably used.
When using N-chlorosulfamate, it is preferable to use hydrogen peroxide in combination in order to minimize the amount of added drug.
本発明では、上記のＮ－クロロスルファマートの代わりにＮ－ブロモスルファマートを用いることもできる。
本発明において用いられるＮ－ブロモスルファマートは、上記のＮ－クロロスルファマートと同様の公知の方法により調製することができる。例えば、スルファミン酸と、次亜臭素酸との反応生成物を好適に用いることができる。
Ｎ－ブロモスルファマートを用いる場合には、薬剤添加量を極力抑える点で、過酸化水素を併用するのが好ましい。
In the present invention, N-bromosulfamate can also be used in place of the above-mentioned N-chlorosulfamate.
N-bromosulfamate used in the present invention can be prepared by the same known method as the above-mentioned N-chlorosulfamate. For example, a reaction product of sulfamic acid and hypobromous acid can be suitably used.
When using N-bromosulfamate, it is preferable to use hydrogen peroxide in combination in order to minimize the amount of added drug.
（第四級アンモニウム化合物）
本発明において用いられる第四級アンモニウム化合物は、例えば、一般式（Ｉ）：
The quaternary ammonium compound used in the present invention has, for example, the general formula (I):
（式中、Ｒはβ位にヒドロキシ基を有してもよい炭素数８～２８の飽和もしくは不飽和の直鎖状脂肪族炭化水素基、Ｒ1は低級アルキル基、またはβ位にヒドロキシ基を有してもよい炭素数８～２８の飽和もしくは不飽和の直鎖状脂肪族炭化水素基、Ｒ2およびＲ3は同一または異なって低級アルキル基、Ｘは酸残基又は水酸基である）、または一般式（II）： (In the formula, R is a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 28 carbon atoms which may have a hydroxy group at the β position, R 1 is a lower alkyl group, or a hydroxy group at the β position. (a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 28 carbon atoms, which may have 8 to 28 carbon atoms, R 2 and R 3 are the same or different and are a lower alkyl group, and X is an acid residue or a hydroxyl group) , or general formula (II):
で表される。
It is expressed as
一般式（Ｉ）において、「炭素数８～２８の飽和もしくは不飽和の直鎖状脂肪族炭化水素基」としては、
オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシル、ヘニコシル、ドコシル、トリコシル、テトラコシル、ペンタコシル、ヘキサコシル、ヘプタコシル、オクタコシルなどの直鎖状飽和炭化水素基；
オクテニル、ノネニル、デケニル、ウンデケニル、ドデケニル、トリデケニル、テトラデケニル、ペンタデケニル、ヘキサデケニル、ヘプタデケニル、オクタデケニル（オレイル＝9-cis-オクタデケニル）、ノナデケニル、イコセニル、ヘニコセニル、ドコセニル、トリコセニル、テトラコセニル、ペンタコセニル、ヘキサコセニル、ヘプタコセニル、オクタコセニル、オクタデカジエニル（リノレイル＝ 9,12-オクタデカジエニル）など；
オクタジニル、ノナジニル、デカジニル、ウンデカジニル、ドデカジニル、トリデカジニル、テトラデカジニル、ペンタデカジニル、ヘキサデカジニル、ヘプタデカジニル、オクタデカジニル、ノナデカジニル、イコサジニル、ヘニコサジニル、ドコサジニル、トリコサジニル、テトラコサジニル、ペンタコサジニル、ヘキサコサジニル、ヘプタコサジニル、オクタコサジニルなどの直鎖状不飽和炭化水素基；
ヤシアルキル、牛脂アルキル、硬化牛脂アルキル、大豆アルキルなどが挙げられる。
In general formula (I), the "saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 28 carbon atoms" is
Straight chain saturated hydrocarbon groups such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl ;
Octenyl; Octacosenyl , octadecadienyl (linoleyl = 9,12-octadecadienyl), etc.;
Octazinyl, nonazinyl, decadinyl, undecazinyl, dodecazinyl, tridecazinyl, tetradecazinyl, pentadecadinyl, hexadecadinyl, heptadecadinyl, octadecazinyl, nonadecadinyl, icosazinyl, henicosazinyl, docosazinyl, tricosazinyl, tetracosazinyl, pentacosazinyl, hexacosazinyl, hep Linear unsaturated hydrocarbons such as tacosazinyl and octacosazinyl Base;
Examples include coconut alkyl, beef tallow alkyl, hardened beef tallow alkyl, and soybean alkyl.
ここで、ヤシアルキル、牛脂アルキル、硬化牛脂アルキル、大豆アルキルとは、ヤシ油もしくはヤシ脂肪、牛脂又は大豆油から公知の手段により製造された高級脂肪族モノもしくはポリアミンを構成するアルキル基である。なお、これらのアルキル基は、炭素数８～２８の間の任意の値を有する直鎖状の飽和もしくは不飽和の脂肪族炭化水素基を複数種含んでいてもよい。 Here, coconut alkyl, beef tallow alkyl, hardened beef tallow alkyl, and soybean alkyl are alkyl groups constituting higher aliphatic mono- or polyamines produced from coconut oil or coconut fat, beef tallow, or soybean oil by known means. Note that these alkyl groups may contain multiple types of linear saturated or unsaturated aliphatic hydrocarbon groups having any value between 8 and 28 carbon atoms.
また、「β位にヒドロキシ基を有する炭素数８～２８の飽和もしくは不飽和の直鎖状脂肪族炭化水素基」としては、前記「炭素数８～２８の飽和もしくは不飽和の直鎖状脂肪族炭化水素基」のβ位にヒドロキシ基を有する基が挙げられ、中でもβ－ヒドロキシドデシル、β－ヒドロキシヘキサデシルが好ましい。 In addition, "a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 28 carbon atoms and having a hydroxy group at the β-position" refers to the above-mentioned "saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 28 carbon atoms". Among them, β-hydroxydodecyl and β-hydroxyhexadecyl are preferred.
一般式（Ｉ）の「低級アルキル基」としては、炭素数１～４のアルキル基が好ましく、具体的には、メチル、エチル、n-プロピル、iso-プロピル、n-ブチル、iso-ブチル、sec-ブチル、tert-ブチルが挙げられる。
また、一般式（Ｉ）および（II）のＸとしては、塩酸、臭化水素酸、硝酸、硫酸、リン酸、蟻酸、酢酸、オレイン酸、ナフテン酸、アジピン酸、乳酸、クエン酸、安息香酸、サッカリンなどの酸残基、および水酸基挙げられ、これらの中でも塩酸および臭化水素酸の残基が特に好ましい。
The "lower alkyl group" in general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, specifically methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, Examples include sec-butyl and tert-butyl.
In addition, as X in general formulas (I) and (II), hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oleic acid, naphthenic acid, adipic acid, lactic acid, citric acid, benzoic acid , acid residues such as saccharin, and hydroxyl groups, and among these, hydrochloric acid and hydrobromic acid residues are particularly preferred.
本発明に用いることのできる一般式（Ｉ）で表される第四級アンモニウム化合物としては、
ドデシルトリメチルアンモニウム塩、ドデシルトリエチルアンモニウム塩、テトラデシルトリメチルアンモニウム塩、テトラデシルトリエチルアンモニウム塩、ヘキサデシルトリメチルアンモニウム塩、ヘキサデシルトリエチルアンモニウム塩、オクタデシルトリメチルアンモニウム塩、オクタデシルトリエチルアンモニウム塩、ヤシアルキルトリメチルアンモニウム塩、ヤシアルキルトリエチルアンモニウム塩、牛脂アルキルトリメチルアンモニウム塩、牛脂アルキルトリエチルアンモニウム塩；
ジオクチルジメチルアンモニウム塩、ジデシルジメチルアンモニウム塩、デシルテトラデシルジメチルアンモニウム塩、ジドデシルジメチルアンモニウム塩、ジヘキサデシルジメチルアンモニウム塩、ジオクタデシルジメチルアンモニウム塩、ジ牛脂アルキルジメチルアンモニウム塩；β－ヒドロキシドデシルトリメチルアンモニウム塩、β－ヒドロキシヘキサデシルトリメチルアンモニウム塩、β－ヒドロキシドデシルトリエチルアンモニウム塩、β－ヒドロキシヘキサデシルトリエチルアンモニウム塩が挙げられる。
Quaternary ammonium compounds represented by general formula (I) that can be used in the present invention include:
Dodecyltrimethylammonium salt, dodecyltriethylammonium salt, tetradecyltrimethylammonium salt, tetradecyltriethylammonium salt, hexadecyltrimethylammonium salt, hexadecyltriethylammonium salt, octadecyltrimethylammonium salt, octadecyltriethylammonium salt, coconut trimethylammonium salt, Coconut alkyltriethylammonium salt, tallow alkyltrimethylammonium salt, tallow alkyltriethylammonium salt;
Dioctyldimethylammonium salt, didecyldimethylammonium salt, decyltetradecyldimethylammonium salt, didodecyldimethylammonium salt, dihexadecyldimethylammonium salt, dioctadecyldimethylammonium salt, ditallowalkyldimethylammonium salt; β-hydroxydodecyltrimethylammonium salt, β-hydroxyhexadecyltrimethylammonium salt, β-hydroxydodecyltriethylammonium salt, and β-hydroxyhexadecyltriethylammonium salt.
また、本発明に用いることのできる一般式（II）で表される第四級アンモニウム化合物としては、ドデシルピリジニウム塩、ヘキサデシルピリジニウム塩、オクタデシルピリジニウム塩、ヤシアルキルピリジニウム塩、牛脂アルキルピリジニウム塩などが挙げられる。これらの第四級アンモニウム化合物は２種以上を混合してもよい。 Further, examples of the quaternary ammonium compound represented by the general formula (II) that can be used in the present invention include dodecylpyridinium salt, hexadecylpyridinium salt, octadecylpyridinium salt, coconut alkylpyridinium salt, tallow alkylpyridinium salt, etc. Can be mentioned. Two or more types of these quaternary ammonium compounds may be mixed.
本発明において用いられる一般式（Ｉ）および（II）以外の第四級アンモニウム化合物としては、塩化ベンザルコニウム（アルキルジメチルベンジルアンモニウムクロライド：ＢＤＤＡＣ）、ジアリルジメチルアンモニウムクロライド(ＤＡＤＭＡＣ)、ポリジアリルジメチルアンモニウムクロライドなどが挙げられる。
上記の第四級アンモニウム化合物の中でも、ジデシルジメチルアンモニウムクロライド（ＤＤＡＣ）のようなジデシルジメチルアンモニウム塩、塩化ベンザルコニウムが特に好ましい。
Examples of quaternary ammonium compounds other than general formulas (I) and (II) used in the present invention include benzalkonium chloride (alkyldimethylbenzylammonium chloride: BDDAC), diallyldimethylammonium chloride (DADMAC), polydiallyldimethylammonium Examples include chloride.
Among the above-mentioned quaternary ammonium compounds, didecyldimethylammonium salts such as didecyldimethylammonium chloride (DDAC) and benzalkonium chloride are particularly preferred.
（二酸化塩素の有効濃度）
二酸化塩素は、シアン含有廃水に含まれるシアンの種類およびその濃度のほかに、シアン含有廃水に含まれる金属化合物（イオン）の種類およびその濃度などの影響を受けるので、これらの条件に応じて適宜決定すればよいが、通常、シアン含有廃水中のシアン含有量に対してモル比で少なくとも０．２倍の濃度であるのが好ましい。より好ましくは、廃水中のシアン含有量に対してモル比で少なくとも１倍の濃度である。
(Effective concentration of chlorine dioxide)
Chlorine dioxide is affected by the type and concentration of cyanide contained in the cyanide-containing wastewater, as well as the type and concentration of metal compounds (ions) contained in the cyanide-containing wastewater. Although it may be determined, it is usually preferable that the concentration is at least 0.2 times the cyanide content in the cyanide-containing wastewater in terms of molar ratio. More preferably, the concentration is at least 1 times the cyanide content in the wastewater in molar ratio.
二酸化塩素がモル比で０．２倍未満では、廃水の種類によっては二酸化塩素が消費（分解）されるため、シアン除去の効果が不十分になることがある。
具体的な好ましい二酸化塩素のモル比の下限値は、例えば、０．２倍、０．４倍、０．５倍、１．０倍、２．０倍、５．０倍、１０倍である。
If the molar ratio of chlorine dioxide is less than 0.2 times, depending on the type of wastewater, chlorine dioxide is consumed (decomposed), so that the effect of removing cyanide may become insufficient.
Specific preferred lower limits of the molar ratio of chlorine dioxide are, for example, 0.2 times, 0.4 times, 0.5 times, 1.0 times, 2.0 times, 5.0 times, and 10 times. .
（次亜塩素酸塩の有効濃度）
次亜塩素酸塩は、シアン含有廃水に含まれるシアンの種類およびその濃度のほかに、シアン含有廃水に含まれる金属化合物（イオン）の種類およびその濃度などの影響を受けるので、これらの条件に応じて適宜決定すればよいが、通常、シアン含有廃水中において次亜塩素酸として１０～７０００ｍｇ／Ｌの濃度であるのが好ましく、１０～３５００ｍｇ／Ｌの濃度であるのがより好ましい。
次亜塩素酸濃度が１０ｍｇ／Ｌ未満では、シアン除去の効果が不十分になることがある。一方、次亜塩素酸濃度が７０００ｍｇ／Ｌを超えると、廃水中の塩化物イオン濃度が高くなり、設備への腐食などの作業環境の悪化をまねくことがある。
(Effective concentration of hypochlorite)
Hypochlorite is affected by the type and concentration of cyanide contained in cyanide-containing wastewater, as well as the type and concentration of metal compounds (ions) contained in cyanide-containing wastewater, so Although it may be determined as appropriate, the concentration of hypochlorous acid in cyanide-containing wastewater is preferably 10 to 7000 mg/L, more preferably 10 to 3500 mg/L.
If the hypochlorous acid concentration is less than 10 mg/L, the cyanide removal effect may be insufficient. On the other hand, when the hypochlorous acid concentration exceeds 7000 mg/L, the chloride ion concentration in the wastewater increases, which may lead to deterioration of the working environment such as corrosion to equipment.
（Ｎ－クロロスルファマートの有効濃度）
Ｎ－クロロスルファマートは、シアン含有廃水に含まれるシアンの種類およびその濃度のほかに、シアン含有廃水に含まれる金属化合物（イオン）の種類およびその濃度などの影響を受けるので、これらの条件に応じて適宜決定すればよいが、通常、シアン含有廃水中において有効塩素濃度として１０～３０００ｍｇ／Ｌの濃度であるのが好ましく、１０～１５００ｍｇ／Ｌの濃度であるのがより好ましい。
Ｎ－クロロスルファマート濃度が１０ｍｇ／Ｌ未満では、シアン除去の効果が不十分になることがある。一方、Ｎ－クロロスルファマート濃度が３０００ｍｇ／Ｌを超えると、廃水中の窒素濃度が高くなり、窒素処理が必要になることがある。
(Effective concentration of N-chlorosulfamate)
N-chlorosulfamate is affected by the type and concentration of cyanide contained in cyanide-containing wastewater, as well as the type and concentration of metal compounds (ions) contained in cyanide-containing wastewater, so these conditions Although the effective chlorine concentration in cyanide-containing wastewater may be determined as appropriate, it is generally preferable that the effective chlorine concentration is 10 to 3000 mg/L, more preferably 10 to 1500 mg/L.
If the N-chlorosulfamate concentration is less than 10 mg/L, the cyanide removal effect may be insufficient. On the other hand, when the N-chlorosulfamate concentration exceeds 3000 mg/L, the nitrogen concentration in the wastewater becomes high and nitrogen treatment may be necessary.
（第四級アンモニウム化合物の有効濃度）
第四級アンモニウム化合物は、シアン含有廃水に含まれるシアンの種類およびその濃度のほかに、シアン含有廃水に含まれる金属化合物（イオン）の種類およびその濃度などの影響を受けるので、これらの条件に応じて適宜決定すればよいが、通常、シアン含有廃水中において第四級アンモニウム化合物として５～４０００ｍｇ／Ｌの濃度であるのが好ましく、５～２０００ｍｇ／Ｌの濃度であるのがより好ましい。
第四級アンモニウム化合物が５ｍｇ／Ｌ未満では、シアン除去の効果が不十分になることがある。一方、第四級アンモニウム化合物濃度が４０００ｍｇ／Ｌを超えると、廃水中の窒素濃度が高くなり、窒素処理が必要になることがある。
(Effective concentration of quaternary ammonium compound)
Quaternary ammonium compounds are affected by the type and concentration of cyanide contained in cyanide-containing wastewater, as well as the type and concentration of metal compounds (ions) contained in cyanide-containing wastewater, so Although it may be determined as appropriate, the concentration of quaternary ammonium compounds in cyanide-containing wastewater is usually preferably 5 to 4000 mg/L, more preferably 5 to 2000 mg/L.
If the content of the quaternary ammonium compound is less than 5 mg/L, the effect of removing cyanide may be insufficient. On the other hand, when the quaternary ammonium compound concentration exceeds 4000 mg/L, the nitrogen concentration in the wastewater becomes high and nitrogen treatment may be necessary.
（化合物の添加方法）
本発明においては、シアン含有廃水中のシアン含有量を予め測定し、測定したシアン含有量に応じた有効成分の化合物を、同時または別々に該廃水に添加するのが好ましい。
具体的には、処理前（処理直前から約３時間前まで）のシアン含有廃水中のシアン濃度、必要に応じて金属化合物の濃度などを予め測定しておき、得られた測定値に基づいて、各添加剤の添加量を決定すればよい。
二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される２種以上を第四級アンモニウム化合物と組み合わせて用いることもできるが、経済的な観点からこれらの化合物群から選択される１種を第四級アンモニウム化合物と組み合わせて用いるのが好ましい。
何れの組み合せであっても本発明の優れた効果を得ることができるが、これらの中でも、薬剤どうしの反応が起こり難く、かつ窒素濃度の過度な上昇を避ける観点から二酸化塩素と第四級アンモニウム化合物との組み合わせが特に好ましい。
(Method of adding compound)
In the present invention, it is preferable to measure the cyanide content in cyanide-containing wastewater in advance, and add active ingredient compounds corresponding to the measured cyanide content to the wastewater simultaneously or separately.
Specifically, the cyanide concentration in cyanide-containing wastewater before treatment (from just before treatment to about 3 hours before treatment) and the concentration of metal compounds as necessary are measured in advance, and based on the measured values, , the amount of each additive to be added may be determined.
Two or more selected from chlorine dioxide, hypochlorite and N-chlorosulfamate can also be used in combination with a quaternary ammonium compound, but from an economical point of view, the compound selected from these groups is selected. It is preferable to use one type in combination with a quaternary ammonium compound.
Although the excellent effects of the present invention can be obtained with any combination, chlorine dioxide and quaternary ammonium are preferred from the viewpoint of making it difficult for reactions between the drugs to occur and avoiding an excessive increase in nitrogen concentration. Combinations with compounds are particularly preferred.
本発明において用いられる有効成分の化合物はそれぞれ水溶液の形態で添加するのが好ましく、各水溶液の濃度は、それらをシアン含有廃水に添加する際の作業性、シアンと添加した化合物との反応性などを考慮して決定すればよい。
具体的には、二酸化塩素は二酸化塩素濃度として１～２５００ｍｇ／Ｌ程度、次亜塩素酸塩は次亜塩素酸濃度として１０～７０００ｍｇ／Ｌ程度、Ｎ－クロロスルファマートは有効塩素濃度として１０～３０００ｍｇ／Ｌ程度、第四級アンモニウム化合物は５～４０００ｍｇ／Ｌ程度である。
また、シアン含有廃水への二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物との添加順序は特に限定されず、両化合物を同時に添加してもよく、また上記の記載順もしくは逆順で別々に添加してもよい。
The active ingredient compounds used in the present invention are preferably added in the form of aqueous solutions, and the concentration of each aqueous solution is determined by factors such as workability when adding them to cyanide-containing wastewater and reactivity between cyanide and the added compounds. The decision should be made taking into consideration.
Specifically, chlorine dioxide has a chlorine dioxide concentration of about 1 to 2,500 mg/L, hypochlorite has a hypochlorous acid concentration of about 10 to 7,000 mg/L, and N-chlorosulfamate has an effective chlorine concentration of 10 to 2,500 mg/L. ~3000mg/L, and for quaternary ammonium compounds it is around 5~4000mg/L.
Furthermore, the order in which the quaternary ammonium compound and one or more compounds selected from chlorine dioxide, hypochlorite, and N-chlorosulfamate are added to the cyanide-containing wastewater is not particularly limited; may be added at the same time, or may be added separately in the above-mentioned order or in the reverse order.
（シアン含有廃水）
本発明において処理対象となるシアン含有廃水としては、製鉄工場、化学工場、メッキ工場、コークス製造工場、金属表面処理工場などから排出される金属のシアン化合物、シアンイオン、シアン錯体、シアノ錯イオンなどを含むシアン含有廃水、放射能汚染水の処理工程において排出されるシアン含有廃水、土壌の処理装置から排出されるシアン含有廃水が挙げられる。特に、本発明のシアン含有廃水の処理方法は、コークス炉廃水のような、緩衝作用の強いシアン含有廃水、すなわちチオシアン酸イオンおよびその塩ならびにアンモニウムイオンなどの共存物質を含有するシアン含有廃水の処理に好適である。
また。本発明のシアン含有廃水の処理方法は、シアン含有廃水がシアン化物イオン、易分解性シアン錯体および難分解性シアン錯体のうちの少なくとも１種を含有する廃水である場合の処理に好適であり、特にシアン含有廃水が、シアン濃度で２～２００ｍｇ／Ｌのシアン錯体を含有する廃水である場合の処理に好適である。
さらに、本発明のシアン含有廃水の処理方法は、シアン含有廃水がチオシアン酸イオンおよびその塩ならびにアンモニウムイオンから選択される１種以上の共存物質を含有する廃水である場合の処理にも好適である。
(Cyanide-containing wastewater)
Cyanide-containing wastewater to be treated in the present invention includes metal cyanide compounds, cyanide ions, cyanide complexes, cyano complex ions, etc. discharged from steel plants, chemical plants, plating plants, coke manufacturing plants, metal surface treatment plants, etc. Examples include cyanide-containing wastewater containing cyanide, cyanide-containing wastewater discharged in the treatment process of radioactively contaminated water, and cyanide-containing wastewater discharged from soil treatment equipment. In particular, the method for treating cyanide-containing wastewater of the present invention is for treating cyanide-containing wastewater that has a strong buffering effect, such as coke oven wastewater, that is, cyanide-containing wastewater that contains coexisting substances such as thiocyanate ions and their salts and ammonium ions. suitable for
Also. The method for treating cyanide-containing wastewater of the present invention is suitable for treatment when the cyanide-containing wastewater is wastewater containing at least one of cyanide ions, easily decomposable cyanide complexes, and refractory cyanide complexes, It is particularly suitable for treatment when cyanide-containing wastewater contains a cyanide complex with a cyanide concentration of 2 to 200 mg/L.
Furthermore, the method for treating cyanide-containing wastewater of the present invention is also suitable for treatment when the cyanide-containing wastewater is wastewater containing one or more coexisting substances selected from thiocyanate ions and their salts, and ammonium ions. .
本発明において処理対象となるシアン含有廃水におけるシアンの含有量は、特に限定されないが、上記のシアン含有廃水は、一般に全シアン濃度で２～５００ｍｇ／Ｌ程度である。このようなシアン含有廃水を処理する場合には、シアン含有廃水に対して、二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物とを上記の添加量になるように添加すればよい。
例えば、二酸化塩素と第四級アンモニウム化合物とを併用する場合、それぞれ１～２５００ｍｇ／Ｌおよび５～４０００ｍｇ／Ｌになるようにシアン含有廃水に添加すればよい。
The content of cyanide in the cyanide-containing wastewater to be treated in the present invention is not particularly limited, but the cyanide-containing wastewater described above generally has a total cyanide concentration of about 2 to 500 mg/L. When treating such cyanide-containing wastewater, one or more compounds selected from chlorine dioxide, hypochlorite, and N-chlorosulfamate and quaternary ammonium are added to the cyanide-containing wastewater. The compound may be added in the above-mentioned amount.
For example, when chlorine dioxide and a quaternary ammonium compound are used together, they may be added to cyanide-containing wastewater in amounts of 1 to 2,500 mg/L and 5 to 4,000 mg/L, respectively.
（シアン含有廃水のｐＨ）
シアン含有廃水は、ｐＨ６～９であるのが好ましい。
シアン含有廃水がｐＨ６未満またはｐＨ９を超えると、シアンと添加する化合物との反応が不完全になり、効率的にシアンを除去できないことがある。
処理対象のシアン含有廃水は、通常、ｐＨ６～９程度であることからｐＨ調整の必要はないが、必要に応じて、本発明の処理における反応を妨げない酸またはアルカリ、例えば硫酸または水酸化ナトリウムを処理廃水に添加して、ｐＨ調整をすればよい。
(pH of cyanide-containing wastewater)
Preferably, the cyanide-containing wastewater has a pH of 6 to 9.
If the pH of the cyanide-containing wastewater is less than 6 or more than 9, the reaction between cyanide and the compound to be added may be incomplete, and cyanide may not be removed efficiently.
The cyanide-containing wastewater to be treated usually has a pH of about 6 to 9, so there is no need to adjust the pH, but if necessary, an acid or alkali that does not interfere with the reaction in the treatment of the present invention, such as sulfuric acid or sodium hydroxide, may be added. may be added to the treated wastewater to adjust the pH.
（撹拌）
二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物との添加時、およびこれらの化合物とシアンとの反応時には、シアンの除去効果の点で、混合溶液を撹拌するのが好ましい。この撹拌は、各化合物の添加毎に実施するのが好ましい。
また、撹拌時の反応を促進する意味で、混合溶液は、添加した化合物が分解されない、ある程度加温された状態であるのが好ましく、その液温は２０～５０℃程度である。
さらに、撹拌時の反応に要する時間は、シアン含有廃水の量、シアンの種類およびその濃度、処理装置の形態およびその規模などにより異なるが、シアンと添加した化合物とが十分に接触するように適宜決定すればよい。通常、撹拌時間は１０分以上であればよい。
(stirring)
Removal of cyanide upon addition of quaternary ammonium compounds with one or more compounds selected from chlorine dioxide, hypochlorite and N-chlorosulfamate, and upon reaction of these compounds with cyanide. In terms of effectiveness, it is preferable to stir the mixed solution. This stirring is preferably carried out after each addition of each compound.
Further, in order to promote the reaction during stirring, the mixed solution is preferably heated to a certain degree so that the added compound is not decomposed, and the liquid temperature is about 20 to 50°C.
Furthermore, the time required for the reaction during stirring varies depending on the amount of cyanide-containing wastewater, the type and concentration of cyanide, the form and scale of the treatment equipment, etc. All you have to do is decide. Usually, the stirring time should be 10 minutes or more.
（処理および沈殿分離）
化合物の添加、撹拌混合、沈降分離、水不溶化物の除去などの一連の操作には、添加剤槽、反応処理槽、シックナーおよび除濁沈殿池などの公知の装置を用いることができ、既設の装置を転用してもよい。
本発明のシアン含有廃水の処理方法では、本発明の効果を阻害しない範囲で、防錆剤、腐食防止剤、スケール分散剤、スライムコントロール剤、消泡剤などの公知の薬剤を併用してもよい。
また、沈降分離においては、本発明の効果を阻害しない範囲で、界面活性剤や凝集剤を添加してもよい。
ここで、本発明において「水不溶化物」とは、温度２０℃における水１００ｇに対して１ｇ以下の溶解度を有し、沈降分離や濾別により液相と分離可能である化合物を意味する。
(treatment and precipitation separation)
For a series of operations such as addition of compounds, stirring and mixing, sedimentation separation, and removal of water-insolubilized substances, known equipment such as additive tanks, reaction treatment tanks, thickeners, and turbidity/sedimentation tanks can be used, and existing equipment can be used. The equipment may be repurposed.
In the cyanide-containing wastewater treatment method of the present invention, known agents such as rust preventives, corrosion inhibitors, scale dispersants, slime control agents, and antifoaming agents may be used in combination as long as the effects of the present invention are not impaired. good.
In addition, in sedimentation separation, a surfactant or a flocculant may be added within a range that does not impede the effects of the present invention.
Here, in the present invention, the term "water-insolubilized material" means a compound that has a solubility of 1 g or less per 100 g of water at a temperature of 20° C. and can be separated from the liquid phase by sedimentation or filtration.
以上の処理により、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを除去し、処理前のシアン濃度（全シアン含有量（ｍｇ／Ｌ））を排水基準値以下に顕著に低減させることができ、処理後の廃水を中和処理なしに、沈降分離や濾別処理なしもしくは簡易な処理に付して、下水などに排出または再利用することができる。
本発明の方法において、処理排水をそのまま放流する場合には、全シアン濃度を排水基準値以下に低下させるのに必要な量の化合物を添加すればよいが、処理排水を他の排水で希釈して放流する場合には、希釈後の排水が上記の排水基準値以下になるように化合物を添加すればよい。
Through the above treatment, the amount of chemicals added is minimized compared to conventional methods, reducing deterioration of the working environment such as corrosion of equipment, and removing cyanide from wastewater safely and inexpensively with simple operations. The concentration (total cyanide content (mg/L)) can be significantly reduced to below the wastewater standard value, and the treated wastewater can be treated without neutralization, sedimentation or filtration, or simple treatment. It can then be discharged into sewage or reused.
In the method of the present invention, when the treated wastewater is discharged as it is, it is sufficient to add the amount of compound necessary to reduce the total cyanide concentration below the wastewater standard value, but the treated wastewater may be diluted with other wastewater. When discharging the waste water, the compound may be added so that the diluted waste water is below the above-mentioned waste water standard value.
本発明を試験例により具体的に説明するが、本発明はこれらの試験例により限定されるものではない。 The present invention will be specifically explained using test examples, but the present invention is not limited to these test examples.
（試験例１）
試験例１では、表１に示す水質を有する実機模擬水（全シアン３０ｍｇ／Ｌ、シアン化物イオン２５ｍｇ／Ｌ、錯シアン５ｍｇ／Ｌ含有、ｐＨ８．２）を用いた。
具体的には、ヘキサシアノ鉄（II）酸カリウム、シアン化カリウム水溶液、塩化カルシウム２水和物、塩化ナトリウム、硫酸ナトリウム、塩化アンモニウムおよび炭酸水素ナトリウムを用いて実機模擬水を調製した。
(Test example 1)
In Test Example 1, actual simulated water (containing 30 mg/L of total cyanide, 25 mg/L of cyanide ions, and 5 mg/L of complex cyanide, pH 8.2) having the water quality shown in Table 1 was used.
Specifically, an actual simulated water was prepared using potassium hexacyanoferrate (II), potassium cyanide aqueous solution, calcium chloride dihydrate, sodium chloride, sodium sulfate, ammonium chloride, and sodium hydrogen carbonate.
第１反応槽としての容量２００ｍＬのビーカーに、それぞれ実機模擬水を１００ｍＬ分注し、表２に示す濃度になるように、二酸化塩素、次亜塩素酸ナトリウムまたはＮ－クロロスルファマートを、第四級アンモニウム化合物としてジデシルジメチルアンモニウムクロライド（ＤＤＡＣ）または塩化ベンザルコニウム（ＢＤＤＡＣ）を添加し、ｐＨ調整剤として硫酸水溶液または水酸化ナトリウム水溶液を添加して、試験水のｐＨが表２に示す値になるように調整して試験水を得た（実施例１～５）。
また、比較として、表２に示す濃度になるように、二酸化塩素のみを添加するか、第四級アンモニウム化合物としてＤＤＡＣのみを添加し、硫酸水溶液または水酸化ナトリウム水溶液を添加して、試験水のｐＨが表２に示す値になるように調整して試験水を得た（比較例１～２）。
試験水の調製では、室温下（温度２５±５℃）、撹拌装置（アズワン株式会社製、マグネチックスターラーＲＥＸＩＭ、品番：ＲＳ－４ＡＲ）を用いて回転数２００ｒｐｍで１時間撹拌した。
第１反応槽での処理後に、ガラス濾紙（ＡＤＶＡＮＴＥＣグループ、東洋濾紙株式会社製、品名：ＧＳ－２５）を用いて、不溶化物を吸引濾過し、残渣をガラス濾紙と共に温度１０５℃で２時間加熱乾燥し、デシケータ内で放冷後に秤量し、予め測定しておいたガラス濾紙の質量を差し引き、残渣の乾燥質量を算出し、これをスラッジ量（ｇ）とした。
Pour 100 mL of actual water into each beaker with a capacity of 200 mL as the first reaction tank, and add chlorine dioxide, sodium hypochlorite, or N-chlorosulfamate to the concentration shown in Table 2. Didecyldimethylammonium chloride (DDAC) or benzalkonium chloride (BDDAC) was added as a quaternary ammonium compound, and a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added as a pH adjuster, so that the pH of the test water was as shown in Table 2. Test waters were obtained by adjusting the values to meet the following values (Examples 1 to 5).
For comparison, we added only chlorine dioxide, or added only DDAC as a quaternary ammonium compound, and added an aqueous sulfuric acid solution or an aqueous sodium hydroxide solution to the test water so that the concentrations shown in Table 2 were obtained. Test water was obtained by adjusting the pH to the values shown in Table 2 (Comparative Examples 1 and 2).
To prepare the test water, the water was stirred at room temperature (temperature 25±5°C) for 1 hour at a rotational speed of 200 rpm using a stirring device (manufactured by As One Corporation, magnetic stirrer REXIM, product number: RS-4AR).
After the treatment in the first reaction tank, the insolubilized matter is suction filtered using a glass filter paper (manufactured by ADVANTEC Group, Toyo Roshi Co., Ltd., product name: GS-25), and the residue is heated together with the glass filter paper at a temperature of 105°C for 2 hours. It was dried, left to cool in a desiccator, and weighed. The mass of the glass filter paper measured in advance was subtracted to calculate the dry mass of the residue, which was defined as the amount of sludge (g).
特許文献４の追試として、表２に示す濃度になるように、硫酸第２銅および重亜硫酸ナトリウムを添加し、ｐＨ調整剤を添加して、試験水のｐＨが表２に示す値になるように調整して試験水を得た（比較例３）。試験水の調製では、室温下、撹拌装置を用いて回転数２００ｒｐｍで３０分間撹拌した。
次いで、第１反応槽での処理後に、ガラス濾紙を用いて、不溶化物を吸引濾過し、残渣をガラス濾紙と共に加熱乾燥し、デシケータ内で放冷後に秤量し、予め測定しておいたガラス濾紙の質量を差し引き、残渣の乾燥質量を算出した。
濾過により得られた濾液を第２反応槽としての容量２００ｍＬのビーカーに移し、１２％次亜塩素酸ナトリウムを添加し、ｐＨ調整剤を添加して、試験水のｐＨが表２に示す値になるように調整し、室温下、撹拌装置を用いて回転数２００ｒｐｍで撹拌した（アルカリ塩素法処理）。
次いで、第２反応槽での処理後に、ガラス濾紙を用いて、不溶化物を吸引濾過し、残渣をガラス濾紙と共に加熱乾燥し、デシケータ内で放冷後に秤量し、予め測定しておいたガラス濾紙の質量を差し引き、残渣の乾燥質量を算出し、これに第１反応槽での残渣の乾燥重量を加算して、これをスラッジ量（ｇ）とした。
濾過により得られた濾液を第３反応槽としての容量２００ｍＬのビーカーに移し、１２％次亜塩素酸ナトリウムを添加し、ｐＨ調整剤を添加して、試験水のｐＨが表２に示す値になるように調整し、室温下、撹拌装置を用いて回転数２００ｒｐｍで撹拌した（アルカリ塩素法処理）。
第２および第３反応槽での１２％次亜塩素酸ナトリウムの添加合計量を表２に示す量（約１／２量を使用）とし、また第２および第３反応槽での合計処理（撹拌）時間を４０分間（各２０分間）とした。
As a supplementary test to Patent Document 4, cupric sulfate and sodium bisulfite were added to the concentrations shown in Table 2, and a pH adjuster was added to adjust the pH of the test water to the values shown in Table 2. Test water was obtained (Comparative Example 3). In preparing the test water, the test water was stirred for 30 minutes at room temperature using a stirring device at a rotation speed of 200 rpm.
Next, after the treatment in the first reaction tank, the insolubilized material is suction filtered using a glass filter paper, the residue is heated and dried together with the glass filter paper, and after being left to cool in a desiccator, it is weighed, and the glass filter paper that has been measured in advance is The dry mass of the residue was calculated by subtracting the mass of .
The filtrate obtained by filtration was transferred to a 200 mL beaker serving as a second reaction tank, 12% sodium hypochlorite was added, and a pH adjuster was added to adjust the pH of the test water to the value shown in Table 2. The mixture was stirred at room temperature using a stirring device at a rotational speed of 200 rpm (alkali chlorine method treatment).
Next, after the treatment in the second reaction tank, the insolubilized material is suction filtered using a glass filter paper, the residue is heated and dried together with the glass filter paper, and after being left to cool in a desiccator, it is weighed and the glass filter paper that has been measured in advance is The dry weight of the residue was calculated by subtracting the mass of the residue, and the dry weight of the residue in the first reaction tank was added to this to obtain the sludge amount (g).
The filtrate obtained by filtration was transferred to a 200 mL beaker serving as a third reaction tank, 12% sodium hypochlorite was added, and a pH adjuster was added to adjust the pH of the test water to the value shown in Table 2. The mixture was stirred at room temperature using a stirring device at a rotational speed of 200 rpm (alkali chlorine method treatment).
The total amount of 12% sodium hypochlorite added in the second and third reaction tanks was the amount shown in Table 2 (approximately 1/2 amount was used), and the total amount of 12% sodium hypochlorite added in the second and third reaction tanks ( The stirring time was 40 minutes (20 minutes each).
特許文献２の追試として、表２に示す濃度になるように、塩化第１銅、塩化第２銅およびＤＤＡＤを添加し、ｐＨ調整剤を添加して、試験水のｐＨが表２に示す値になるように調整して試験水を得た（比較例４）。試験水の調製では、室温下、撹拌装置を用いて回転数２００ｒｐｍで１時間撹拌した。
第１反応槽での処理後に、ガラス濾紙を用いて、不溶化物を吸引濾過し、残渣をガラス濾紙と共に加熱乾燥し、デシケータ内で放冷後に秤量し、予め測定しておいたガラス濾紙の質量を差し引き、残渣の乾燥質量を算出し、これをスラッジ量（ｇ）とした。
As a supplementary test to Patent Document 2, cuprous chloride, cupric chloride, and DDAD were added to the concentrations shown in Table 2, and a pH adjuster was added, so that the pH of the test water was the value shown in Table 2. Test water was obtained by adjusting it so that it was (Comparative Example 4). In preparing the test water, the water was stirred at room temperature using a stirring device at a rotation speed of 200 rpm for 1 hour.
After the treatment in the first reaction tank, the insolubilized material is suction-filtered using a glass filter paper, the residue is heated and dried together with the glass filter paper, and after being left to cool in a desiccator, it is weighed to obtain the pre-measured mass of the glass filter paper. was subtracted to calculate the dry mass of the residue, which was defined as the amount of sludge (g).
最終的に得られた濾液の全シアン濃度（Ｔ-ＣＮ）をＪＩＳ Ｋ０１０２に準拠して測定し、各試験水におけるシアン化合物の除去効果を評価した。
この試験においては、薬剤を添加しないブランク試験（比較例５）を同時に行った。
得られた結果を、添加化合物、その添加量および添加方法と共に表２に示す。
The total cyanide concentration (T-CN) of the finally obtained filtrate was measured in accordance with JIS K0102, and the cyanide compound removal effect in each test water was evaluated.
In this test, a blank test (Comparative Example 5) in which no drug was added was conducted at the same time.
The obtained results are shown in Table 2 together with the added compounds, their amounts added, and the methods of addition.
表２の試験結果から次のことがわかる。
（１）二酸化塩素、次亜塩素酸塩およびＮ－クロロスルファマートから選択される１種以上の化合物と、第四級アンモニウム化合物との併用処理（実施例１～５）では、十分なシアン除去効果が得られ、かつ生成スラッジ量が少なく、しかも１つの反応槽で処理が完了すること
（２）ｐＨがそれぞれ７．５および９．０の試験水に同種同量の化合物を添加しても、同等の十分なシアン除去効果と生成スラッジの減量効果が得られること（実施例１および２）
（３）これに対して、金属化合物および還元剤を用いる不溶錯体法と、アルカリ塩素法とを併用する処理（比較例３：特許文献４の追試）では、十分なシアン除去効果が得られるものの、３つの反応槽が必要になり、工程が多く煩雑になり、生成スラッジ量が多いこと
（４）また、２種の金属化合物およびＤＤＡＣを併用する不溶錯体法（比較例４：特許文献２の追試）では、１つの反応槽で処理が完了し、十分なシアン除去効果が得られるものの、生成スラッジ量が多いこと
（５）二酸化塩素およびＤＤＡＣの何れか一方を用いる処理（比較例２および３）では、金属化合物を用いていないので生成スラッジ量が少ないが、十分なシアン除去効果が得られないこと
The following can be seen from the test results in Table 2.
(1) In the combined treatment with a quaternary ammonium compound and one or more compounds selected from chlorine dioxide, hypochlorite, and N-chlorosulfamate (Examples 1 to 5), sufficient cyanogen A removal effect can be obtained, the amount of sludge produced is small, and the treatment can be completed in one reaction tank. Also, the same sufficient cyanide removal effect and sludge reduction effect can be obtained (Examples 1 and 2).
(3) On the other hand, a treatment that uses a combination of an insoluble complex method using a metal compound and a reducing agent and an alkali chlorine method (Comparative Example 3: follow-up to Patent Document 4) does not provide sufficient cyanide removal effect. (4) In addition, the insoluble complex method using two types of metal compounds and DDAC (Comparative Example 4: Patent Document 2) Supplementary test), the treatment was completed in one reaction tank and a sufficient cyanide removal effect was obtained, but the amount of generated sludge was large (5) Treatment using either chlorine dioxide or DDAC (comparative examples 2 and 3) ) does not use metal compounds, so the amount of sludge produced is small, but it does not provide sufficient cyanide removal effect.
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