JP2020104115A - Method for treating cyanogen-containing waste water - Google Patents
Method for treating cyanogen-containing waste water Download PDFInfo
- Publication number
- JP2020104115A JP2020104115A JP2020067566A JP2020067566A JP2020104115A JP 2020104115 A JP2020104115 A JP 2020104115A JP 2020067566 A JP2020067566 A JP 2020067566A JP 2020067566 A JP2020067566 A JP 2020067566A JP 2020104115 A JP2020104115 A JP 2020104115A
- Authority
- JP
- Japan
- Prior art keywords
- cyanide
- compound
- wastewater
- water
- cyan
- 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.)
- Granted
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 39
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 131
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 129
- -1 thiocyanate ions Chemical class 0.000 abstract description 41
- 239000000126 substance Substances 0.000 abstract description 16
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 69
- 230000000694 effects Effects 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 28
- 150000002736 metal compounds Chemical class 0.000 description 27
- 229910052742 iron Inorganic materials 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000005749 Copper compound Substances 0.000 description 22
- 150000001880 copper compounds Chemical class 0.000 description 22
- 239000005708 Sodium hypochlorite Substances 0.000 description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 20
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 20
- 229910001431 copper ion Inorganic materials 0.000 description 19
- 229910001437 manganese ion Inorganic materials 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 15
- 239000011565 manganese chloride Substances 0.000 description 15
- 235000002867 manganese chloride Nutrition 0.000 description 15
- 229940099607 manganese chloride Drugs 0.000 description 15
- 150000002506 iron compounds Chemical class 0.000 description 14
- 150000002697 manganese compounds Chemical class 0.000 description 12
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 150000002825 nitriles Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 230000002411 adverse Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 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
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-UHFFFAOYSA-L copper;octadec-9-enoate Chemical compound [Cu+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O SVOAENZIOKPANY-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000011641 cupric citrate Substances 0.000 description 1
- 235000019855 cupric citrate Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Abstract
Description
本発明は、従来よりも薬剤添加量を極力抑え、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得るシアン含有廃水の処理方法に関する。
本発明では、各種形態で廃水中に含有するすべてのシアン、すなわち難分解性シアン錯体、易分解性シアン錯体およびシアン化物イオンを簡便な操作で処理することができる。
TECHNICAL FIELD The present invention relates to a method for treating cyanide-containing wastewater capable of removing cyanide in wastewater safely and inexpensively by a simple operation, while suppressing the amount of chemicals added as much as possible.
In the present invention, all the cyanides contained in the wastewater in various forms, that is, the hardly decomposable cyan complex, the easily decomposable cyan complex and the cyanide ion can be treated by a simple operation.
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。
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、易分解性シアン錯体および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。
Since cyanide has a strong adverse effect on the ecosystem, cyanide-containing wastewater (also referred to as “cyan wastewater”) cannot be released to nature as it is. Cyan drainage standards are established based on the Water Pollution Control Law, and cyanide removal treatment is performed to satisfy this standard (1 mg/L or less), and only wastewater that has been rendered harmless can be discharged to sewage. In addition, in some regions, the ordinance defines additional drainage standards that are lower than the above drainage standards.
Cyan exists in the wastewater in the form of three kinds, that is, a hard-to-decompose cyan complex, a readily-decomposable cyan complex, and a cyanide ion, although the content thereof varies depending on the origin of the wastewater.
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。
Conventionally, various methods have been proposed and put to practical use as a treatment for removing cyanide from cyanide-containing wastewater, but each method has advantages and disadvantages and is used properly according to the situation of the wastewater.
For example, (1) after adjusting the cyanide-containing wastewater to be alkaline, an alkaline chlorine method in which chlorine is injected to oxidize and decompose cyan, (2) oxidative decomposition of cyan into nitrogen gas and hydrogen carbonate by strong ozone oxidizing power. (3) Oxidation decomposition method such as electrolytic oxidation method (electrolysis method) in which cyanide is electrolyzed using a non-dissolving electrode to perform an oxidation reaction (4) Iron ion in cyanide-containing wastewater As a supply compound of, for example, ferrous sulfate is added to form a sparingly soluble ferri/ferrocyanide, and a dark blue method of removing the precipitate is added. (5) Zinc chloride and a reducing agent are added to form an insoluble Insoluble complex method such as zinc white method for removing complex by precipitation and (6) reduced copper salt method for removing precipitated insoluble complex by adding divalent copper salt and reducing agent; (7) for cyan Biological treatment method for decomposing cyanide by acclimatized microorganisms (cyan-decomposing bacteria); (8) Cyan compound is hydrolyzed into ammonia and formic acid by maintaining cyanide-containing wastewater at high temperature, and coexisting heavy metals are used alone or as an oxide. In addition to the thermal hydrolysis method of precipitating as (1) and the decomposition of (9) cyanide, a hydrothermal reaction such as a wet oxidation method of oxidatively decomposing organic pollutants.
また、本発明の出願人は、次のようなシアン含有廃水の処理方法を提案してきた。
（Ａ）シアン含有廃水に、次亜塩素酸塩および水に可溶であり、水中でマンガンイオンを形成し得るマンガン化合物を添加し、生成した水不溶性のマンガン塩を廃水から除去して、廃水中のシアンを除去するシアン含有廃水の処理方法（特許第４１０６４１５号公報：特許文献１参照）
（Ｂ）シアン化合物含有廃水に含有シアン化合物量の１．４モル以上に相当する量のホルムアルデヒドを添加して第１段の反応を行った後、次いで実質的に有効反応量の過酸化水素を含有シアン化合物量の３．０モル以上添加し、ｐＨ７．０以上で第２段の反応を行うシアン化合物含有廃水の処理方法（特開平０２−３５９９１号公報：特許文献２参照）
Further, the applicant of the present invention has proposed the following method for treating cyanide-containing wastewater.
(A) To a cyanide-containing wastewater, a manganese compound that is soluble in hypochlorite and water and can form manganese ions in water is added, and the produced water-insoluble manganese salt is removed from the wastewater to obtain the wastewater. Cyan-containing wastewater treatment method for removing cyanide in the interior (Japanese Patent No. 4106415: see Patent Document 1)
(B) After adding formaldehyde in an amount corresponding to 1.4 mol or more of the amount of the cyan compound contained in the waste water containing the cyan compound to carry out the reaction in the first step, a substantially effective amount of hydrogen peroxide is then added. A method for treating cyanide compound-containing wastewater, in which 3.0 mol or more of the amount of cyanide compound contained is added and the second stage reaction is carried out at pH 7.0 or higher (Japanese Patent Laid-Open No. 02-35991: Patent Document 2).
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、チオシアン酸イオンやアンモニウムイオンが存在する廃水など、廃水の種類によってはシアン除去の効果が十分でなく、処理後の廃水のシアン濃度を排水基準（１ｍｇ／Ｌ以下）にすることができず、処理廃水をそのまま下水などに排出することができない場合もある。
また、水質汚濁防止法に基づき水素イオン濃度（ｐＨ）の排水基準は、海域では５．０〜９．０、海域外では５．８〜８．６と定められている。上記の先行技術において、廃水のｐＨを酸性やアルカリ性に調整した場合には、下水などに排出する前に、廃水のシアン濃度だけではなく、ｐＨも排水基準範囲内に調整する中和処理が必要になる場合もある。
However, in the above-mentioned prior art, complicated steps and operations are required, which may require a plurality of reaction vessels. In addition, depending on the type of wastewater, such as wastewater containing thiocyanate ions and ammonium ions, the effect of cyanide removal is not sufficient, and the cyanide concentration of the wastewater after treatment cannot be set to the wastewater standard (1 mg/L or less). In some cases, the treated wastewater cannot be discharged as it is to sewage.
Further, based on the Water Pollution Control Law, the drainage standard of hydrogen ion concentration (pH) is set to 5.0 to 9.0 in the sea area and 5.8 to 8.6 outside the water area. In the above prior art, when the pH of wastewater is adjusted to be acidic or alkaline, it is necessary to neutralize not only the cyan concentration of the wastewater but also the pH within the drainage standard range before discharging the wastewater. It may be.
例えば、上記の特許文献１の方法（Ａ）では、シアン含有廃水に対して過剰量の薬剤を添加すれば、シアン濃度を規定値以下にすることができるが、薬剤添加量を極力抑えて、より安全なシアン処理を行うことが求められている。
そこで、本発明は、従来よりも薬剤添加量を極力抑え、チオシアン酸イオンやアンモニウムイオンが存在するような廃水の種類に関係なく、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。
For example, in the method (A) of Patent Document 1 described above, the cyan concentration can be made equal to or lower than the specified value by adding an excessive amount of a chemical to the cyan-containing wastewater, but the chemical addition amount is suppressed as much as possible, It is required to perform safer cyan processing.
Therefore, the present invention suppresses the amount of chemicals added as much as possible than before, and removes cyanide in wastewater safely and inexpensively by a simple operation regardless of the type of wastewater in which thiocyanate ions and ammonium ions are present. An object of the present invention is to provide a method for treating obtained cyanine-containing wastewater.
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、有効量の次亜塩素酸塩および過酸化水素を同時または別々に添加することにより、意外にも、従来よりも薬剤添加量を極力抑え、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得る事実を見出し、本発明を完成するに到った。 The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by adding an effective amount of hypochlorite and hydrogen peroxide at the same time or separately, surprisingly, from the conventional As a result, they have found the fact that cyanide in wastewater can be removed safely and inexpensively by a simple operation while suppressing the amount of chemicals added as much as possible, and completed the present invention.
かくして、本発明によれば、シアン含有廃水に、次亜塩素酸塩および過酸化水素を同時または別々に添加して、該廃水中のシアンの分解および／またはシアンとの水不溶性の化合物の生成を生じさせて該廃水からシアンを除去することからなるシアン含有廃水の処理方法が提供される。 Thus, according to the present invention, hypochlorite and hydrogen peroxide are added to cyanide-containing wastewater simultaneously or separately to decompose cyanide in the wastewater and/or to form a water-insoluble compound with cyanide. Is provided 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、チオシアン酸イオンやアンモニウムイオンが存在する廃水の種類に関係なく、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すべてのシアン、すなわち難分解性シアン錯体、易分解性シアン錯体およびシアン化物イオンを、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水不溶性塩（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, it is possible to suppress the amount of chemicals added as much as possible, and to remove cyanide in wastewater safely and inexpensively by a simple operation, regardless of the type of wastewater containing thiocyanate ions and ammonium ions. A method for treating contained wastewater can be provided.
That is, according to the present invention, all the cyanides contained in the wastewater in various forms, that is, the hardly-decomposable cyan complex, the easily-decomposable cyan complex and the cyanide ion, can be easily added by suppressing the drug addition amount as much as possible. Can be processed by operation.
Therefore, even if the wastewater treated by the method of the present invention is discharged to the natural environment as it is, the influence on the environment is very small, and the amount of water-insoluble salt (waste) generated after the treatment can be reduced, and thus the method of the present invention. Is extremely useful in industry.
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）シアン含有廃水中のシアン含有量を予め測定し、測定した含有量に対して、次亜塩素酸塩を有効塩素濃度として０．１モル当量以上かつ過酸化水素を０．１モル当量以上添加する、
（２）シアン含有廃水がマンガンイオン、鉄イオンおよび銅イオンから選択される１種以上の金属イオンを元々含有する、
（３）マンガン化合物、鉄化合物および銅化合物から選択される１種以上の金属化合物をさらに添加する、および
（４）シアン含有廃水がｐＨ９以下である
In addition, the method for treating cyanide-containing wastewater of the present invention exerts the above effect more when any one of the following conditions is satisfied.
(1) Cyan content in cyanide-containing wastewater is measured in advance, and hypochlorite is used as an effective chlorine concentration of 0.1 molar equivalent or more and hydrogen peroxide is 0.1 molar equivalent with respect to the measured content. Add more,
(2) Cyan-containing wastewater originally contains one or more metal ions selected from manganese ions, iron ions and copper ions,
(3) One or more metal compounds selected from manganese compounds, iron compounds and copper compounds are further added, and (4) cyanide-containing wastewater has a pH of 9 or less.
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、次亜塩素酸塩および過酸化水素を同時または別々に添加して、該廃水中のシアンの分解および／またはシアンとの水不溶性の化合物の生成を生じさせ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 is a method of adding hypochlorite and hydrogen peroxide to a cyanide-containing wastewater simultaneously or separately to decompose cyanide in the wastewater and/or to render it water-insoluble with cyanide. It is characterized by causing the formation of a compound to remove cyanogen from the wastewater.
本発明におけるシアン含有廃水からのシアンの除去は、「廃水中のシアンの分解」および「廃水中のシアンとの水不溶性の化合物の生成」が関与するが、その分解／生成機構は明らかでない。
本発明の発明者らは、「廃水中のシアンの分解」は、添加された次亜塩素酸および過酸化水素によりシアンが酸化され、さらに生成されたシアン酸が加水分解により炭酸水素アンモニウムを生成することによるものと考えている。
また、本発明の発明者らは、「廃水中のシアンとの水不溶性の化合物の生成」は、廃水中に金属イオンが存在する場合、シアン成分と金属イオンとによる水不溶性塩の生成によるものと考えている。
上記のように、また実施例の結果からも明らかなように、本発明のシアン含有廃水の処理方法は、次亜塩素酸塩と過酸化水素との併用効果により、また元々シアン含有廃水中に存在する金属イオンもしくはさらに添加する金属イオンとの併用効果により、これらの化合物および金属イオンがシアンの分解および／またはシアンとの水不溶性の化合物の生成に効果的に作用することから、従来よりも少ない薬剤添加量でも廃水中のシアンを除去できるものと考えられる。
Cyan removal from cyanide-containing wastewater according to the present invention involves "decomposition of cyanide in wastewater" and "formation of water-insoluble compound with cyanide in wastewater", but its decomposition/formation mechanism is not clear.
According to the inventors of the present invention, “decomposition of cyanide in wastewater” means that cyanide is oxidized by the added hypochlorous acid and hydrogen peroxide, and the produced cyanic acid is hydrolyzed to produce ammonium hydrogencarbonate. I think it is due to doing.
In addition, the inventors of the present invention "produce a water-insoluble compound with cyanide in wastewater" is due to the formation of a water-insoluble salt by the cyan component and the metal ion when a metal ion is present in the wastewater. I believe.
As described above, and as is clear from the results of the examples, the method for treating cyanide-containing wastewater of the present invention is based on the combined use effect of hypochlorite and hydrogen peroxide, and originally Due to the combined effect of the existing metal ion or the metal ion to be added, these compounds and the metal ion more effectively act on the decomposition of cyanide and/or the formation of a water-insoluble compound with cyan. It is considered that cyanide in wastewater can be removed even with a small amount of chemicals added.
（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得る化合物であれば特に限定されず、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、ヒダントイン誘導体が挙げられる。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塩であってもよい。
(Hypochlorite)
The hypochlorite used in the present invention is not particularly limited as long as it is a compound capable of generating hypochlorous acid in water, and for example, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite. , Alkali metal salts and alkaline earth metal salts of hypochlorous acid such as magnesium hypochlorite, and hydantoin derivatives. In particular, sodium hypochlorite and potassium hypochlorite are industrially easily available and are preferably used in the present invention. Further, it may be hypochlorite obtained by electrolyzing salt solution or seawater in an electrolytic cell.
（過酸化水素）
本発明において用いられる過酸化水素としては、主に工業用として市販されている濃度３〜６０％の過酸化水素水溶液が挙げられる。
また、過酸化水素供給化合物（「過酸化水素発生剤」ともいう）から発生させた過酸化水素や、用水またはアルカリ溶液の電気分解などで発生させた過酸化水素を用いることもできる。
過酸化水素供給化合物としては、過酸化水素を水中で放出し得る過炭酸、過ホウ酸、ペルオキシ硫酸などの無機過酸、過酢酸のような有機過酸およびこれらの塩類が挙げられる。これら塩類としては、過炭酸ナトリウム、過ホウ酸ナトリウムなどが挙げられる。
上記の過酸化水素および過酸化水素供給化合物は、添加に際して所望の過酸化水素濃度になるように水で希釈または溶解して用いてもよい。
(hydrogen peroxide)
Examples of the hydrogen peroxide used in the present invention include hydrogen peroxide aqueous solutions having a concentration of 3 to 60%, which are commercially available mainly for industrial use.
Alternatively, hydrogen peroxide generated from a hydrogen peroxide supply compound (also referred to as “hydrogen peroxide generator”) or hydrogen peroxide generated by electrolysis of water or an alkaline solution may be used.
Hydrogen peroxide-supplying compounds include percarbonate, perboric acid, inorganic peracids such as peroxysulfuric acid, organic peracids such as peracetic acid, and salts thereof that can release hydrogen peroxide in water. Examples of these salts include sodium percarbonate and sodium perborate.
The above-mentioned hydrogen peroxide and hydrogen peroxide-supplying compound may be used by diluting or dissolving with water so as to obtain a desired hydrogen peroxide concentration upon addition.
（化合物の添加）
本発明の方法によれば、シアン含有廃水に、該廃水中のシアンの分解および／または該廃水中のシアンと水不溶性の化合物の生成を生じさせて該廃水からシアンを除去するための次亜塩素酸塩および過酸化水素を同時または別々に添加する。
次亜塩素酸塩および過酸化水素はそれぞれ水溶液の形態で添加するのがよい。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く、具体的には、次亜塩素酸塩の濃度は１０〜７０００ｍｇ／Ｌ程度、過酸化水素の濃度は１０〜３５００ｍｇ／Ｌ程度である。
(Addition of compound)
According to the method of the present invention, a cyanide-containing wastewater is subjected to the decomposition of cyanide in the wastewater and/or the formation of a water-insoluble compound with cyanide in the wastewater to produce a cyanide for removing cyanide from the wastewater. Chlorate and hydrogen peroxide are added simultaneously or separately.
Hypochlorite and hydrogen peroxide are preferably added in the form of aqueous solutions. The concentration of each aqueous solution may be determined in consideration of workability when adding them to cyanide-containing wastewater, reactivity between cyanide and the added compound, and specifically, the concentration of hypochlorite. Is about 10 to 7,000 mg/L, and the concentration of hydrogen peroxide is about 10 to 3500 mg/L.
次亜塩素酸塩および過酸化水素の添加量は、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他の金属イオンの種類およびその濃度などの影響を受けるので、これらの添加量は条件に応じて適宜決定すればよい。具体的には、処理前のシアン含有廃水のシアン濃度などを予め測定しておき、この測定値に基づいて、各添加剤の添加量を決定すればよい。 The amount of hypochlorite and hydrogen peroxide added is affected by the type and concentration of cyanide contained in the cyanide-containing wastewater, as well as the type and concentration of other metal ions contained in the cyanide-containing wastewater. Therefore, the addition amount of these may be appropriately determined according to the conditions. Specifically, the cyan concentration of the cyanide-containing waste water before treatment may be measured in advance, and the addition amount of each additive may be determined based on the measured value.
上記のように化合物の添加量は対象となるシアン含有廃水中に含まれるシアンの含有量により異なるが、廃水中のシアン含有量に対して、次亜塩素酸塩が有効塩素濃度として０．１モル当量以上かつ過酸化水素が０．１モル当量以上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、次亜塩素酸塩が有効塩素濃度として０．５モル当量以上かつ過酸化水素が０．５モル当量以上である。
次亜塩素酸塩が有効塩素濃度として０．１モル当量未満では、廃水中のチオシアン酸イオンやアンモニウムイオンなど、廃水の種類によっては次亜塩素酸塩が消費（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。また、過酸化水素が０．１モル当量未満では、シアン除去の効果が不十分になることがある。
具体的な好ましい次亜塩素酸塩の有効塩素濃度の下限値（モル当量）は、例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、１．０、１．５である。
具体的な好ましい過酸化水素の下限値（モル当量）は、例えば、０．１、０．２、０．３、０．４、０．５、０．６、０．７、０．８、０．９、１．０、１．５である。
As described above, the amount of the compound added varies depending on the content of cyanide contained in the target cyanide-containing wastewater, but hypochlorite has an effective chlorine concentration of 0.1% or less relative to the cyanide content of the wastewater. It is preferred that the molar equivalent is not less than and the hydrogen peroxide is not less than 0.1 molar equivalent. More preferably, the hypochlorite is 0.5 molar equivalent or more and the hydrogen peroxide is 0.5 molar equivalent or more with respect to the cyanide content in the waste water as the effective chlorine concentration.
If hypochlorite has an effective chlorine concentration of less than 0.1 molar equivalent, hypochlorite is consumed (decomposed) depending on the type of wastewater such as thiocyanate ion and ammonium ion in the wastewater, so cyanide removal The effect of may become insufficient. If the amount of hydrogen peroxide is less than 0.1 molar equivalent, the effect of removing cyan may be insufficient.
Specific preferred lower limit values (molar equivalents) of effective chlorine concentration of hypochlorite are, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0. 7, 0.8, 0.9, 1.0 and 1.5.
Specific preferred lower limit values (molar equivalents) of hydrogen peroxide are, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.5.
（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、すなわちアンモニウムイオンを含有するシアン含有廃水の処理に好適である。
(Cyan-containing wastewater)
As the cyanide-containing wastewater to be treated in the present invention, a metal cyanide, a cyanide ion, a cyanide complex, a cyanide complex ion, etc., discharged from an iron factory, a chemical factory, a plating factory, a coke manufacturing factory, a metal surface treatment factory, or the like. And cyanide-containing wastewater discharged in the treatment step of radioactively contaminated water, and cyanide-containing wastewater discharged from a soil treatment device. In particular, the method for treating cyanide-containing wastewater of the present invention is suitable for treating cyanide-containing wastewater having a strong buffering action, that is, cyanide-containing wastewater containing ammonium ions, such as coke oven wastewater.
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、次亜塩素酸塩を、シアン含有廃水に対して有効塩素濃度として１０〜７０００ｍｇ／Ｌ、好ましくは１０〜２０００ｍｇ／Ｌとなるように、かつ過酸化水素を１０〜３５００ｍｇ／Ｌ、好ましくは１０〜１０００ｍｇ／Ｌとなるように、シアン含有廃水に添加すればよい。 The cyan content in the cyan-containing wastewater to be treated in the present invention is not particularly limited, but the above-mentioned cyan-containing wastewater generally has a total cyan concentration of about 2 to 500 mg/L. When treating such a cyanide-containing wastewater, the hypochlorite is added to the cyanide-containing wastewater so as to have an effective chlorine concentration of 10 to 7,000 mg/L, preferably 10 to 2000 mg/L. Hydrogen oxide may be added to the cyanide-containing wastewater so as to be 10 to 3500 mg/L, preferably 10 to 1000 mg/L.
シアン含有廃水は、マンガンイオン、鉄イオンおよび銅イオンから選択される１種以上の金属イオンを元々含有するのが好ましい。
シアン含有廃水が上記の金属イオンを元々含有することにより、廃水中のシアンとの反応で水不溶性のマンガン塩、鉄塩および銅塩をそれぞれ生成して本発明のシアンの除去効果を促進することになる。
金属イオンは、金属種によって種々の価数を取り得るが、本発明では、マンガンイオンは２価、鉄イオンは２価、銅イオンでは１価および２価であるのが好ましい。
The cyanide-containing wastewater preferably originally contains one or more metal ions selected from manganese ions, iron ions and copper ions.
When the cyanide-containing wastewater originally contains the above metal ions, water-insoluble manganese salt, iron salt and copper salt are respectively generated by the reaction with cyanide in the wastewater to promote the cyanide removal effect of the present invention. become.
The metal ion can have various valences depending on the metal species, but in the present invention, manganese ion is divalent, iron ion is divalent, and copper ion is preferably monovalent and divalent.
シアン含有廃水に含有するマンガンイオン濃度は、０．１〜５００ｍｇ／Ｌ程度である。
マンガンイオン濃度が０．１ｍｇ／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、マンガンイオン濃度が５００ｍｇ／Ｌを超えると、排水基準以上の溶解マンガンが残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的なマンガンイオン濃度（ｍｇ／Ｌ）は、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましいマンガンイオン濃度は、０．１〜１５０ｍｇ／Ｌであり、より好ましくは５〜１００ｍｇ／Ｌである。
The concentration of manganese ions contained in the cyanide-containing wastewater is about 0.1 to 500 mg/L.
If the manganese ion concentration is less than 0.1 mg/L, the effect of removing cyan may be insufficient. On the other hand, when the manganese ion concentration exceeds 500 mg/L, dissolved manganese above the drainage standard remains, which not only adversely affects the environment but is also economically unfavorable.
The specific manganese ion concentration (mg/L) is, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200. , 250, 300, 350, 400, 450, 500.
The manganese ion concentration is preferably 0.1 to 150 mg/L, more preferably 5 to 100 mg/L.
シアン含有廃水に含有する鉄イオン濃度は、０．１〜５００ｍｇ／Ｌ程度である。
鉄イオン濃度が０．１ｍｇ／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、鉄イオン濃度が５００ｍｇ／Ｌを超えると、排水基準以上の溶解鉄が残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的な鉄イオン濃度（ｍｇ／Ｌ）は、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましい鉄イオン濃度は、０．１〜１５０ｍｇ／Ｌであり、より好ましくは２〜１００ｍｇ／Ｌである。
The iron ion concentration contained in the cyanide-containing wastewater is about 0.1 to 500 mg/L.
If the iron ion concentration is less than 0.1 mg/L, the effect of removing cyan may be insufficient. On the other hand, when the iron ion concentration exceeds 500 mg/L, not only the dissolved iron above the drainage standard remains, adversely affecting the environment but also economically unfavorable.
Specific iron ion concentration (mg/L) is, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200. , 250, 300, 350, 400, 450, 500.
The preferred iron ion concentration is 0.1 to 150 mg/L, more preferably 2 to 100 mg/L.
シアン含有廃水に含有する銅イオン濃度は、０．１〜５００ｍｇ／Ｌ程度である。
銅イオン濃度が０．１ｍｇ／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、銅イオン濃度が５００ｍｇ／Ｌを超えると、排水基準以上の溶解銅が残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的な銅イオン濃度（ｍｇ／Ｌ）は、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましい銅イオン濃度は、０．１〜１５０ｍｇ／Ｌであり、より好ましくは２〜１００ｍｇ／Ｌである。
The concentration of copper ions contained in the cyanide-containing wastewater is about 0.1 to 500 mg/L.
If the copper ion concentration is less than 0.1 mg/L, the effect of removing cyan may be insufficient. On the other hand, when the copper ion concentration exceeds 500 mg/L, not only the dissolved copper above the drainage standard remains, which adversely affects the environment but also economically is not preferable.
The specific copper ion concentration (mg/L) is, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200. , 250, 300, 350, 400, 450, 500.
The preferred copper ion concentration is 0.1 to 150 mg/L, more preferably 2 to 100 mg/L.
（金属化合物）
本発明においては、シアン含有廃水にマンガン化合物、鉄化合物および銅化合物から選択される１種以上の金属化合物をさらに添加するのが好ましい。
シアン含有廃水がマンガンイオン、鉄イオン、銅イオンを元々含有しない場合、もしくは含有しても低濃度である場合には、シアン含有廃水に上記の金属化合物を添加することにより、上記と同様の効果を得ることができる。
(Metal compound)
In the present invention, it is preferable to further add one or more metal compounds selected from manganese compounds, iron compounds and copper compounds to the cyan-containing wastewater.
If the cyanide-containing wastewater does not originally contain manganese ions, iron ions, or copper ions, or if it contains a low concentration, by adding the above metal compound to the cyanide-containing wastewater, the same effect as above can be obtained. Can be obtained.
（マンガン化合物）
本発明において用いられるマンガン化合物は、水に可溶であり、水中でマンガンイオンを形成し得る化合物であれば特に限定されず、例えば、塩化マンガン、硫酸マンガン、硝酸マンガン、酢酸マンガンなどが挙げられる。これらの中でもシアン化合物の除去効果の点では、塩化マンガンおよび硫酸マンガンが特に好ましく、さらにシアン含有廃水の処理コストの点では、塩化マンガンが特に好ましい。
本発明において「水に可溶」とは、化合物が水１００ｇに対して約１ｇ以上の溶解度を有することを意味する。
(Manganese compound)
The manganese compound used in the present invention is not particularly limited as long as it is a compound that is soluble in water and can form manganese ions in water, and examples thereof include manganese chloride, manganese sulfate, manganese nitrate, and manganese acetate. .. Among these, manganese chloride and manganese sulfate are particularly preferable in terms of the effect of removing the cyan compound, and manganese chloride is particularly preferable in terms of the treatment cost of the cyanide-containing wastewater.
In the present invention, “soluble in water” means that the compound has a solubility of about 1 g or more in 100 g of water.
（鉄化合物）
本発明において用いられる鉄化合物は、水に可溶であれば特に限定されず、例えば、塩化第一鉄、硫酸第一鉄、硝酸第一鉄、酢酸第一鉄などの水中で２価の鉄イオンを形成し得る化合物が挙げられる。これらの中でもシアン化合物の除去効果の点では、塩化第一鉄および硫酸第一鉄が特に好ましく、さらにシアン含有廃水の処理コストの点では、塩化第一鉄が特に好ましい。
(Iron compound)
The iron compound used in the present invention is not particularly limited as long as it is soluble in water, and examples thereof include divalent iron in water such as ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate. The compound which can form an ion is mentioned. Of these, ferrous chloride and ferrous sulfate are particularly preferable in terms of the effect of removing cyanide compounds, and ferrous chloride is particularly preferable in terms of the treatment cost of cyanide-containing wastewater.
本発明の方法では、鉄化合物として、水中で３価の鉄イオンを形成し得る鉄化合物を還元剤と共にシアン含有廃水に添加するか、または還元性のシアン含有廃水に水中で３価の鉄イオンを形成し得る鉄化合物を添加して、該廃水中で３価の鉄イオンを形成し得る鉄化合物を還元させて生成した２価の鉄イオン供給化合物を含む。
上記の還元剤としては、例えば、亜硫酸塩、ヒドラジンなどが挙げられる。
In the method of the present invention, as an iron compound, an iron compound capable of forming a trivalent iron ion in water is added to a cyanide-containing wastewater together with a reducing agent, or a reducing cyanide-containing wastewater is trivalent iron ion in water. And a divalent iron ion-supplying compound produced by reducing the iron compound capable of forming trivalent iron ions in the waste water.
Examples of the reducing agent include sulfite and hydrazine.
（銅化合物）
本発明において用いられる銅化合物は、水に可溶または易分散であり、水中で銅イオンを形成し得る銅化合物であれば特に限定されず、第一銅化合物および第二銅化合物が挙げられ、それらは有機銅化合物、無機銅化合物のいずれであってもよい。
有機銅化合物としては、例えば、酢酸第二銅、安息香酸第二銅、クエン酸第二銅、ナフテン酸銅、オレイン酸第二銅などの第二銅化合物が挙げられる。
(Copper compound)
The copper compound used in the present invention is soluble or easily dispersed in water and is not particularly limited as long as it is a copper compound capable of forming copper ions in water, and examples thereof include a cuprous compound and a cupric compound. They may be organic copper compounds or inorganic copper compounds.
Examples of the organic copper compound include cupric compounds such as cupric acetate, cupric benzoate, cupric citrate, copper naphthenate and cupric oleate.
無機銅化合物としては、例えば、塩化第一銅、フッ化第一銅、臭化第一銅、ヨウ化第一銅、硝酸第一銅、硫酸第一銅などの水中で１価の銅イオンを形成し得る第一銅化合物および塩化第二銅、フッ化第二銅、臭化第二銅、ヨウ化第二銅、硝酸第二銅、硫酸第二銅などの水中で２価の銅イオンを形成し得る第二銅化合物が挙げられる。
有機銅化合物は処理後のシアン含有廃水中のＣＯＤを上昇させることがあるため、上記の銅化合物の中でも、無機銅化合物が好ましく、シアンの除去効果およびシアン含有廃水の処理コストの点で、無機第一銅化合物がより好ましく、塩化第一銅および硫酸第一銅がさらに好ましく、塩化第一銅が特に好ましい。
Examples of the inorganic copper compound include monovalent copper ions in water such as cuprous chloride, cuprous fluoride, cuprous bromide, cuprous iodide, cuprous nitrate, and cuprous sulfate. A cuprous compound capable of forming and a divalent copper ion in water such as cupric chloride, cupric fluoride, cupric bromide, cupric iodide, cupric nitrate and cupric sulfate. Examples include cupric compounds that can form.
Since the organic copper compound may increase the COD in the cyanide-containing wastewater after the treatment, among the above-mentioned copper compounds, the inorganic copper compound is preferable, and the inorganic copper compound is preferable in terms of the effect of removing cyanide and the treatment cost of the cyanide-containing wastewater. A cuprous compound is more preferable, cuprous chloride and cuprous sulfate are further preferable, and cuprous chloride is particularly preferable.
また、第一銅化合物が第一銅塩である場合には、塩化水素水、ハロゲン化アルカリ金属水溶液またはエタノールを溶媒とする第一銅塩溶液とするのが、第一銅塩の安定性の点から好ましい。
本発明の方法では、銅化合物として、第二銅化合物を還元剤と共にシアン含有廃水に添加するか、または還元性のシアン含有廃水に第二銅化合物を添加して、該廃水中で第二銅化合物を還元させて生成した第一銅イオン供給化合物を含む。
上記の還元剤としては、例えば、亜硫酸塩、二価の鉄塩、ヒドラジンなどが挙げられる。
In addition, when the cuprous compound is a cuprous salt, hydrogen chloride water, an aqueous solution of an alkali metal halide or a cuprous salt solution using ethanol as a solvent is the stability of the cuprous salt. It is preferable from the point.
In the method of the present invention, as a copper compound, a cupric compound is added to a cyanide-containing wastewater together with a reducing agent, or a cupric compound is added to a reducing cyanide-containing wastewater to form a cupric acid in the wastewater. It includes a cuprous ion-providing compound produced by reducing the compound.
Examples of the reducing agent include sulfite, divalent iron salt, hydrazine and the like.
（化合物の添加形態と濃度）
上記の金属化合物は、シアン含有廃水への添加に際して所望の金属換算濃度となるように、金属捕集剤による処理を用いてもよい。また、工業用水などの水で希釈または溶解して用いてもよい。
上記の金属捕集剤としては、例えば、液体キレート剤などが挙げられる。
(Form of addition of compound and concentration)
The above metal compound may be treated with a metal scavenger so as to have a desired metal conversion concentration when added to the cyanide-containing wastewater. Further, it may be diluted or dissolved with water such as industrial water before use.
Examples of the above-mentioned metal scavengers include liquid chelating agents.
また、金属化合物は、水溶液の形態で添加するのがよい。水溶液の濃度は、それ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く、具体的には、マンガン化合物はマンガンイオン濃度として０．１〜５００ｍｇ／Ｌ程度、鉄化合物は鉄イオン濃度として０．１〜５００ｍｇ／Ｌ程度、銅化合物は銅イオン濃度として０．１〜５００ｍｇ／Ｌ程度である。
シアン含有廃水がマンガンイオン、鉄イオン、銅イオンを含有する場合には、その含有量を考慮して、マンガン化合物、鉄化合物および銅化合物の添加量を設定すればよい。
Also, the metal compound is preferably added in the form of an aqueous solution. The concentration of the aqueous solution may be determined in consideration of workability when adding it to the cyanide-containing wastewater, reactivity of the cyanide with the added compound, and the like. Specifically, the manganese compound has a manganese ion concentration of 0. 1 to 500 mg/L, an iron compound has an iron ion concentration of about 0.1 to 500 mg/L, and a copper compound has a copper ion concentration of about 0.1 to 500 mg/L.
When the cyanide-containing wastewater contains manganese ions, iron ions, and copper ions, the addition amounts of the manganese compound, iron compound, and copper compound may be set in consideration of their contents.
上記のように化合物の添加量は対象となるシアン含有廃水により異なるが、添加するマンガン化合物の濃度は、マンガンイオン濃度として０．１〜５００ｍｇ／Ｌ程度である。
マンガン化合物の濃度がマンガンイオン濃度として０．１ｍｇ／Ｌ未満では、シアン除去の効果が不十分であることがある。一方、マンガン化合物の濃度がマンガンイオン濃度として５００ｍｇ／Ｌを超えると、排水基準以上の溶解マンガンが残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的なマンガ化合物の濃度は、マンガンイオン濃度（ｍｇ／Ｌ）として、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましいマンガン化合物の濃度は、マンガンイオン濃度として０．１〜１５０ｍｇ／Ｌであり、より好ましくは５〜１００ｍｇ／Ｌである。
Although the amount of the compound added varies depending on the target cyanide-containing wastewater as described above, the concentration of the added manganese compound is about 0.1 to 500 mg/L as the manganese ion concentration.
If the concentration of the manganese compound is less than 0.1 mg/L as the manganese ion concentration, the effect of removing cyan may be insufficient. On the other hand, when the concentration of the manganese compound exceeds 500 mg/L as the manganese ion concentration, dissolved manganese above the drainage standard remains, not only adversely affecting the environment but also economically unfavorable.
Specific manganese compound concentrations are, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100 as manganese ion concentrations (mg/L). , 125, 150, 200, 250, 300, 350, 400, 450, 500.
The concentration of the manganese compound is preferably 0.1 to 150 mg/L as the manganese ion concentration, and more preferably 5 to 100 mg/L.
上記のように化合物の添加量は対象となるシアン含有廃水により異なるが、添加する鉄化合物の濃度は、鉄イオン濃度として０．１〜５００ｍｇ／Ｌ程度である。
鉄化合物の濃度が鉄イオン濃度として０．１ｍｇ／Ｌ未満では、シアン除去の効果が不十分であることがある。一方、鉄化合物の濃度が鉄イオン濃度として５００ｍｇ／Ｌを超えると、排水基準以上の溶解鉄が残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的な鉄化合物の濃度は、鉄イオン濃度（ｍｇ／Ｌ）として、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましい鉄化合物の濃度は、鉄イオン濃度として０．１〜１５０ｍｇ／Ｌであり、より好ましくは２〜１００ｍｇ／Ｌである。
As described above, the addition amount of the compound varies depending on the target cyanide-containing wastewater, but the concentration of the iron compound to be added is about 0.1 to 500 mg/L as the iron ion concentration.
If the concentration of the iron compound is less than 0.1 mg/L as the iron ion concentration, the effect of removing cyan may be insufficient. On the other hand, when the concentration of the iron compound exceeds 500 mg/L as the iron ion concentration, not only the dissolved iron above the drainage standard remains, which adversely affects the environment, but also economically unfavorable.
The specific iron compound concentration is, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100 as the iron ion concentration (mg/L). , 125, 150, 200, 250, 300, 350, 400, 450, 500.
The concentration of the iron compound is preferably 0.1 to 150 mg/L as the iron ion concentration, and more preferably 2 to 100 mg/L.
上記のように化合物の添加量は対象となるシアン含有廃水により異なるが、添加する銅化合物の濃度は、銅イオン濃度として０．１〜５００ｍｇ／Ｌ程度である。
銅化合物の濃度が銅イオン濃度として０．１ｍｇ／Ｌ未満では、シアン除去の効果が不十分であることがある。一方、銅化合物の濃度が銅イオン濃度として５００ｍｇ／Ｌを超えると、排水基準以上の溶解銅が残存し、環境に悪影響を与えるだけでなく、経済的にも好ましくない。
具体的な銅化合物の濃度は、銅イオン濃度（ｍｇ／Ｌ）として、例えば、０．１、０．５、１．０、２．０、５．０、１０、２５、５０、７５、１００、１２５、１５０、２００、２５０、３００、３５０、４００、４５０、５００である。
好ましい銅化合物の濃度は、銅イオン濃度として０．１〜１５０ｍｇ／Ｌであり、より好ましくは２〜１００ｍｇ／Ｌである。
Although the amount of the compound added varies depending on the target cyanide-containing wastewater as described above, the concentration of the copper compound added is about 0.1 to 500 mg/L as the copper ion concentration.
If the concentration of the copper compound is less than 0.1 mg/L as the copper ion concentration, the effect of removing cyan may be insufficient. On the other hand, when the concentration of the copper compound exceeds 500 mg/L as the copper ion concentration, not only the dissolved copper having a drainage standard or higher remains, which adversely affects the environment but is also economically unfavorable.
The specific copper compound concentration is, for example, 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100 as the copper ion concentration (mg/L). , 125, 150, 200, 250, 300, 350, 400, 450, 500.
The concentration of the copper compound is preferably 0.1 to 150 mg/L as the copper ion concentration, and more preferably 2 to 100 mg/L.
（化合物の添加方法）
シアン含有廃水への次亜塩素酸塩および過酸化水素の添加順序は特に限定されず、両化合物を同時に、次亜塩素酸塩および過酸化水素の順または逆順で別々に添加してもよい。
また、金属化合物をさらに添加する場合にもその添加順序は特に限定されず、シアン含有廃水に次亜塩素酸塩、過酸化水素および金属化合物を同時に、３種の化合物をそれぞれ別々に、３種の内の２種を同時に残りの１種をその後に添加してもよい。
(Method of adding compound)
The order of adding hypochlorite and hydrogen peroxide to the cyanide-containing wastewater is not particularly limited, and both compounds may be added simultaneously in the order of hypochlorite and hydrogen peroxide or in the reverse order.
Also, when the metal compound is further added, the order of addition is not particularly limited, and the cyanide-containing wastewater is simultaneously added with hypochlorite, hydrogen peroxide, and a metal compound, and the three compounds are separately separated into three kinds. Two of the above may be added at the same time and the remaining one may be added thereafter.
すなわち、添加方法としては、１段処理、２段処理および３段処理があり、次のような組み合わせが挙げられる。下記の「／」は処理の区切りを、「（Ａ＋Ｂ）」はＡとＢとの同時添加（同一段での処理）を意味する。
１段処理
（１−１）（次亜塩素酸塩＋過酸化水素）
（１−２）（次亜塩素酸塩＋過酸化水素＋金属化合物）
That is, as the addition method, there are one-step treatment, two-step treatment, and three-step treatment, and the following combinations can be mentioned. In the following, “/” means a treatment delimiter, and “(A+B)” means simultaneous addition of A and B (treatment at the same stage).
One-step treatment (1-1) (hypochlorite + hydrogen peroxide)
(1-2) (hypochlorite + hydrogen peroxide + metal compound)
２段処理
（２−１）（次亜塩素酸塩）／（過酸化水素）
（２−２）（過酸化水素）／（次亜塩素酸塩）
（２−３）（次亜塩素酸塩＋金属化合物）／（過酸化水素）
（２−４）（過酸化水素＋金属化合物）／（次亜塩素酸塩）
（２−５）（次亜塩素酸塩＋過酸化水素）／（金属化合物）
（２−６）（次亜塩素酸塩）／（過酸化水素＋金属化合物）
（２−７）（過酸化水素）／（次亜塩素酸塩＋金属化合物）
（２−８）（金属化合物）／（次亜塩素酸塩＋過酸化水素）
Two-step treatment (2-1) (hypochlorite)/(hydrogen peroxide)
(2-2) (hydrogen peroxide)/(hypochlorite)
(2-3) (hypochlorite + metal compound)/(hydrogen peroxide)
(2-4) (hydrogen peroxide + metal compound)/(hypochlorite)
(2-5) (hypochlorite + hydrogen peroxide)/(metal compound)
(2-6) (hypochlorite)/(hydrogen peroxide + metal compound)
(2-7) (hydrogen peroxide)/(hypochlorite + metal compound)
(2-8) (metal compound)/(hypochlorite + hydrogen peroxide)
３段処理
（３−１）（次亜塩素酸塩）／（過酸化水素）／（金属化合物）
（３−２）（次亜塩素酸塩）／（金属化合物）／（過酸化水素）
（３−３）（過酸化水素）／（次亜塩素酸塩）／（金属化合物）
（３−４）（過酸化水素）／（金属化合物）／（次亜塩素酸塩）
（３−５）（金属化合物）／（過酸化水素）／（次亜塩素酸塩）
（３−６）（金属化合物）／（次亜塩素酸塩）／（過酸化水素）
Three-step treatment (3-1) (hypochlorite)/(hydrogen peroxide)/(metal compound)
(3-2) (hypochlorite)/(metal compound)/(hydrogen peroxide)
(3-3) (hydrogen peroxide)/(hypochlorite)/(metal compound)
(3-4) (hydrogen peroxide)/(metal compound)/(hypochlorite)
(3-5) (metal compound)/(hydrogen peroxide)/(hypochlorite)
(3-6) (metal compound)/(hypochlorite)/(hydrogen peroxide)
これらの中でも、作業効率の点で１段処理または２段処理が好ましい。
また、複数段処理の場合、各段の間またはすべての処理後、特に金属化合物での処理後に、処理廃水を沈降分離するのが好ましい。各段の間に沈降分離した場合には、得られた上澄み液に次段の化合物を添加する。具体例としては、試験例３が挙げられる。
なお、ＣＯＤ（ＣＯＤMn：酸性高温過マンガン酸法による化学的酸素要求量）値が５０ｍｇ／Ｌ以上の比較的高いシアン廃水を現場で２段処理する場合には、次亜塩素酸塩を前段で添加することが望ましい。また、安全面の点において過酸化水素を後段で添加することが望ましい。
Among these, the one-step treatment or the two-step treatment is preferable from the viewpoint of work efficiency.
Further, in the case of a multi-stage treatment, it is preferable to separate the treated wastewater by sedimentation during or after each stage, especially after the treatment with a metal compound. When sedimentation occurs between each stage, the compound of the next stage is added to the obtained supernatant. Test Example 3 is a specific example.
In addition, when treating CO2 (COD Mn : chemical oxygen demand by acidic high temperature permanganate method) value of 50 mg/L or higher, which is a relatively high level, for cyanogen wastewater in two stages, hypochlorite is used as the former stage. It is desirable to add in. Further, from the viewpoint of safety, it is desirable to add hydrogen peroxide at a later stage.
（シアン含有廃水および上澄み液のｐＨ）
シアン含有廃水は、ｐＨ９以下であるのが好ましい。
シアン含有廃水がｐＨ９を超えると、水不溶性の化合物の生成が不完全になり、効率的にシアンを除去できないことがある。
また、金属化合物をさらに添加する場合の上澄み液も、ｐＨ９以下であるのが好ましい。
上澄み液がｐＨ９を超えると、同様に水不溶性の化合物の生成が不完全になり、効率的にシアンを除去できないことがある。
シアン含有廃水および上澄み液の好ましいｐＨの下限は６程度であるが、処理対象のシアン含有廃水のｐＨは、通常、６〜９程度であることからｐＨ調整の必要はない。
しかしながら、シアン含有廃水および上澄み液がｐＨ９を超える場合およびｐＨ６未満の場合には、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すればよい。
(PH of cyanide-containing wastewater and supernatant)
Cyan-containing wastewater preferably has a pH of 9 or less.
When the pH of the cyanide-containing wastewater exceeds 9, the formation of water-insoluble compounds may be incomplete, and cyan may not be efficiently removed.
Also, the pH of the supernatant liquid when a metal compound is further added is preferably 9 or less.
When the pH of the supernatant liquid exceeds 9, similarly, the formation of water-insoluble compounds becomes incomplete, and cyan may not be efficiently removed.
The lower limit of the preferable pH of the cyan-containing wastewater and the supernatant liquid is about 6, but the pH of the cyan-containing wastewater to be treated is usually about 6 to 9, and therefore it is not necessary to adjust the pH.
However, when the cyanide-containing wastewater and the supernatant liquid have a pH of more than 9 and a pH of less than 6, 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 to the treated wastewater.
次亜塩素酸塩、過酸化水素および金属化合物の添加時、およびこれらの添加された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分以上であればよく、２０〜６０分とするのがより好ましい。
It is preferable to stir the mixed solution at the time of adding hypochlorite, hydrogen peroxide and a metal compound, and at the time of reacting these added compounds with cyan, from the viewpoint of the effect of removing cyan. This stirring is preferably performed after each addition of each compound.
In addition, in order to promote the reaction during stirring, the mixed solution is preferably in a heated state to some extent so that the added compound is not decomposed, and the liquid temperature thereof is about 20 to 50°C.
Furthermore, the time required for the reaction at the time of stirring varies depending on the amount of waste water containing cyanide, the type and concentration of cyanide, the form and scale of the processing equipment, etc., but is appropriately adjusted so that the cyanide and the added compound sufficiently come into contact with each other. Just decide. Usually, the stirring time may be 10 minutes or more, and more preferably 20 to 60 minutes.
（処理および沈殿分離）
化合物の添加、撹拌混合、沈降分離、水不溶性塩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「水不溶性」とは、化合物（塩）が２０℃における水１００ｇに対して１ｇ以下の溶解度を有し、その化合物は、沈降分離や濾別により液相と分離可能であることを意味する。
(Treatment and sedimentation)
For a series of operations such as addition of compounds, stirring and mixing, sedimentation separation, and removal of water-insoluble salts, known devices such as an additive tank, a reaction treatment tank, a thickener, and a turbidity settling tank can be used. The device may be diverted.
In the method for treating cyanide-containing wastewater of the present invention, known agents such as a rust inhibitor, a corrosion inhibitor, a scale dispersant, and a slime control agent may be used in combination within a range that does not impair the effects of the present invention.
Further, in the sedimentation separation, a surfactant or a coagulant may be added as long as the effect of the present invention is not impaired.
Here, in the present invention, “water-insoluble” means that the compound (salt) has a solubility of 1 g or less in 100 g of water at 20° C., and the compound can be separated from the liquid phase by sedimentation separation or filtration. Means there is.
以上の処理により、従来よりも薬剤添加量を極力抑え、チオシアン酸イオンやアンモニウムイオンが存在する廃水の種類に関係なく、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、そのまま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。
通常、工場などにおいては、処理排水を他の排水で希釈して放流する場合が多く、費用に対する効果を考慮して、各有効成分の添加量をコントロールするのが好ましい。
よって、処理後の全シアン濃度が１ｍｇ／Ｌ以下にならない場合、概ね５ｍｇ／Ｌ以下になる場合も本発明に含まれる処理であることが理解される。
By the above treatment, the amount of chemicals added is suppressed as much as possible than before, regardless of the type of wastewater containing thiocyanate ions and ammonium ions, cyanide in the wastewater can be removed safely and inexpensively by a simple operation. Cyan concentration (total cyan content (mg/L)) can be remarkably reduced to below the standard value of wastewater, and wastewater after treatment can be directly discharged or reused as sewage without neutralization treatment. it can.
In the method of the present invention, when the treated effluent is discharged as it is, it is sufficient to add the compound in an amount necessary for reducing the total cyanide concentration below the effluent standard value, but the treated effluent is diluted with another effluent. In the case of discharging by discharging the compound, the compound may be added so that the wastewater after dilution becomes equal to or less than the above-mentioned wastewater standard value.
Usually, in a factory or the like, the treated wastewater is often diluted with other wastewater before being discharged, and it is preferable to control the added amount of each active ingredient in consideration of cost effectiveness.
Therefore, it is understood that the case where the total cyan density after the treatment does not fall below 1 mg/L, or the case where the total cyan concentration falls below 5 mg/L, is a treatment included in the present invention.
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 described with reference to test examples, but the present invention is not limited to these test examples.
下記の試験例１−１では、某製鉄所のコークス炉廃水ラインより採取した、表１に示す水質を有するシアン含有廃水Ａ（ｐＨ８．３）を用いた。 In the following Test Example 1-1, the cyanide-containing wastewater A (pH 8.3) having the water quality shown in Table 1, which was collected from the coke oven wastewater line of a certain steel mill, was used.
下記の試験例１−２では、某製鉄所の高炉集塵水の原水より採取した、表２に示す水質を有するシアン含有廃水Ｂ（ｐＨ７．８）を用いた。 In Test Example 1-2 below, a cyanide-containing waste water B (pH 7.8) having the water quality shown in Table 2 was used, which was collected from raw water of blast furnace dust collection water of a certain steel mill.
下記の試験例２−１、２−３および２−４では、次のように調製した、表３に示す水質を有するシアン含有廃水Ｃ（ｐＨ８．０）を用いた。
シアン含有廃水Ｃは、フェロシアン化カリウム水溶液、シアン化カリウム水溶液、チオシアン酸カリウム水溶液、塩化カルシウム２水和物水溶液、塩化ナトリウム水溶液、硫酸ナトリウム水溶液、塩化アンモニウム水溶液および炭酸水素ナトリウム水溶液を用いて調製した。
In the following Test Examples 2-1, 2-3 and 2-4, the cyanide-containing wastewater C (pH 8.0) having the water quality shown in Table 3 prepared as follows was used.
Cyan-containing wastewater C was prepared using a potassium ferrocyanide aqueous solution, a potassium cyanide aqueous solution, a potassium thiocyanate aqueous solution, a calcium chloride dihydrate aqueous solution, a sodium chloride aqueous solution, a sodium sulfate aqueous solution, an ammonium chloride aqueous solution and a sodium hydrogen carbonate aqueous solution.
下記の試験例２−２では、次のように調製した、表４に示す水質を有するシアン含有廃水Ｄ（ｐＨ８．０）を用いた。
シアン含有廃水Ｄは、シアン化カリウム水溶液、塩化カルシウム２水和物水溶液、塩化ナトリウム水溶液、硫酸ナトリウム水溶液および炭酸水素ナトリウム水溶液を用いて調製した。
In Test Example 2-2 below, cyanide-containing wastewater D (pH 8.0) having the water quality shown in Table 4 prepared as follows was used.
Cyan-containing wastewater D was prepared using an aqueous potassium cyanide solution, an aqueous calcium chloride dihydrate solution, an aqueous sodium chloride solution, an aqueous sodium sulfate solution, and an aqueous sodium hydrogen carbonate solution.
（試験例１−１）
容量３００ｍＬのビーカーに、それぞれシアン含有廃水Ａを３００ｍＬ分注し、表５に示す濃度になるように次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素をそれぞれ添加して試験水を得た。
一部の試験水には、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５に示す値になるように調整した。
次いで、得られた試験水を、撹拌装置（株式会社宮本製作所製、ジャーテスター（試水凝集反応装置）、型式：ＭＪＳ−６、撹拌翼形状：２枚羽根、撹拌翼最大径６０ｍｍ）を用いて回転数１２０ｒｐｍで３０分間撹拌した。
次いで、試験水中の全シアン濃度（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、次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素を添加しないブランク試験（比較例４）を同時に行った。
得られた結果を、添加化合物とその添加量および試験水のｐＨと共に表５に示す。
(Test Example 1-1)
To a beaker having a volume of 300 mL, 300 mL of the cyanogen-containing wastewater A was dispensed, and sodium hypochlorite, manganese chloride and hydrogen peroxide were added so as to have the concentrations shown in Table 5 to obtain test water.
An aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide was added to a part of the test water to adjust the pH of the test water to the value shown in Table 5.
Then, the obtained test water was used with a stirrer (manufactured by Miyamoto Seisakusho Co., Ltd., jar tester (test water agglomeration reactor), model: MJS-6, stirrer blade shape: two blades, maximum stirrer diameter 60 mm). And the mixture was stirred at a rotation speed of 120 rpm for 30 minutes.
Next, the total cyan concentration (T-CN) in the test water was measured according to JIS K0102, and the effect of removing the cyan compound in each test water was evaluated.
In this test, a blank test (Comparative Example 4) in which sodium hypochlorite, manganese chloride and hydrogen peroxide were not added was simultaneously performed.
The obtained results are shown in Table 5 together with the added compound, its addition amount, and the pH of the test water.
表５の試験結果から次のことがわかる。
・ｐＨ７〜９における次亜塩素酸ナトリウムと過酸化水素との併用処理（実施例１〜３）、ｐＨ８および９における次亜塩素酸ナトリウム、塩化マンガン、および過酸化水素の併用処理（実施例４〜７）では、十分なシアン除去効果を有すること
・これに対して、次亜塩素酸ナトリウムのみを用いた処理（比較例１）では、ブランク（比較例４）よりも処理液のシアン含有量が増加すること（これは廃水に含まれるチオシアン酸イオンが酸化されてシアンになったものと考えられる）
・アルカリ塩素法による処理（比較例２）においては、過剰量の次亜塩素酸ナトリウムを添加したにも拘わらず、十分なシアン除去の効果が得られないこと
・次亜塩素酸ナトリウムと塩化マンガンとの併用処理（比較例３）では、シアン除去の効果が得られるものと想定していたが、薬剤添加量が不十分であることも考えられ、十分なシアン除去の効果が得られないこと
The test results in Table 5 show the following.
Combined treatment of sodium hypochlorite and hydrogen peroxide at pH 7 to 9 (Examples 1 to 3), combined treatment of sodium hypochlorite, manganese chloride, and hydrogen peroxide at pH 8 and 9 (Example 4) 7 to 7) has a sufficient cyanide removing effect. On the other hand, in the treatment using only sodium hypochlorite (Comparative Example 1), the cyan content of the treatment liquid was higher than that in the blank (Comparative Example 4). Increase (this is considered to be due to the oxidation of thiocyanate ions contained in wastewater to cyanide)
-In the treatment by the alkali chlorine method (Comparative Example 2), despite the addition of an excessive amount of sodium hypochlorite, a sufficient cyanide-removing effect cannot be obtained.-Sodium hypochlorite and manganese chloride It was assumed that the combined use treatment with and (comparative example 3) would bring about the effect of removing cyan, but the amount of chemicals added may be insufficient, and sufficient effect of removing cyan cannot be obtained.
（試験例１−２）
容量１Ｌのビーカーに、シアン含有廃水Ｂを１Ｌ分注し、５５℃に設定したウォーターバスで加温した。表６に示す濃度になるように塩化マンガンを添加して２分間撹拌し、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８．０になるように調整した。
次いで、得られた試験水に、表６に示す濃度になるように次亜塩素酸ナトリウムを添加し、撹拌装置（株式会社宮本製作所製、ジャーテスター（試水凝集反応装置）、型式：ＭＪＳ−６、撹拌翼形状：２枚羽根、撹拌翼最大径６０ｍｍ）を用いて回転数１２０ｒｐｍで１時間撹拌した。
試験水は、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８．０になるように調整した。得られた試験水（１）のシアン含有量（Ｔ−ＣＮ）と化学的酸素要求量（ＣＯＤMn）を測定した。
(Test Example 1-2)
1 L of cyanide-containing wastewater B was dispensed into a 1 L beaker and heated in a water bath set at 55°C. Manganese chloride was added to the concentration shown in Table 6 and stirred for 2 minutes, and a sulfuric acid aqueous solution or sodium hydroxide aqueous solution was added to adjust the pH of the test water to 8.0.
Next, sodium hypochlorite was added to the obtained test water so as to have a concentration shown in Table 6, and a stirring device (manufactured by Miyamoto Seisakusho Co., Ltd., Jar tester (test water agglutination reaction device), model: MJS- 6. Stirring blade shape: Two blades, stirring blade maximum diameter 60 mm) was used and stirring was performed for 1 hour at a rotation speed of 120 rpm.
The test water was adjusted so that the pH of the test water was 8.0 by adding an aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide. The cyan content (T-CN) and the chemical oxygen demand (COD Mn ) of the obtained test water (1) were measured.
次いで、得られた試験水（１）に、無機凝集剤（ポリ塩化アルミニウム）を３ｍｇ／Ｌとなるように添加し、撹拌装置を用いて回転数２００ｒｐｍで２分間撹拌した。さらに、高分子凝集剤（製品名：フロクランＡ−１２４０、株式会社片山化学工業研究所製）を１ｍｇ／Ｌとなるように添加し、撹拌装置を用いて回転数１２０ｒｐｍで３０分間、その後回転数６０ｒｐｍで１分３０秒撹拌した。得られた試験水を５分間静置後、外観観察を行なった。
次いで、得られた試験水の上澄み液を２５０ｍＬ採取し、３００ｍＬのビーカーに移し、５５℃に設定したウォーターバスで加温した。残りはＮｏ．５Ａの濾紙でろ過した。
得られた上澄み試験水に、表６に示す濃度になるように過酸化水素を添加し、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８．０になるように調整後、撹拌装置を用いて回転数１２０ｒｐｍで２時間撹拌した。
撹拌後にＮｏ．５Ａの濾紙でろ過し、試験水（２）のシアン含有量（Ｔ−ＣＮ）と化学的酸素要求量（ＣＯＤMn）を測定した。
得られた結果を、表６に示す。
Next, an inorganic coagulant (polyaluminum chloride) was added to the obtained test water (1) so that the concentration was 3 mg/L, and the mixture was stirred for 2 minutes at a rotation speed of 200 rpm using a stirring device. Further, a polymer flocculant (product name: Floclan A-1240, manufactured by Katayama Chemical Industry Laboratory Co., Ltd.) was added so as to be 1 mg/L, and a stirring device was used for 30 minutes at a rotation speed of 120 rpm, and then the rotation speed. The mixture was stirred at 60 rpm for 1 minute and 30 seconds. The test water obtained was allowed to stand for 5 minutes, and then the appearance was observed.
Next, 250 mL of the obtained supernatant of the test water was collected, transferred to a 300 mL beaker, and heated in a water bath set at 55°C. The rest is No. It was filtered with a filter paper of 5A.
After adding hydrogen peroxide to the obtained supernatant test water to a concentration shown in Table 6 and adding an aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide, the pH of the test water was adjusted to 8.0. The mixture was stirred for 2 hours at a rotation speed of 120 rpm using a stirring device.
No. after stirring. After filtering through a 5 A filter paper, the cyanide content (T-CN) and the chemical oxygen demand (COD Mn ) of the test water (2) were measured.
The obtained results are shown in Table 6.
表６の試験結果から次のことがわかる。
・１段処理後では、シアン含有量（Ｔ−ＣＮ）は３ｍｇ／Ｌ程度に減少し、化学的酸素要求量（ＣＯＤMn）も減少したこと
・実施例８および９では、過酸化水素を添加した後、シアン含有量（Ｔ−ＣＮ）は１ｍｇ／Ｌ未満となったこと
The test results in Table 6 show the following.
After the first step treatment, the cyan content (T-CN) was reduced to about 3 mg/L and the chemical oxygen demand (COD Mn ) was also reduced. In Examples 8 and 9, hydrogen peroxide was added. After that, the cyan content (T-CN) became less than 1 mg/L.
（試験例２−１／シアノ錯体を含有するシアン含有廃水の１段処理試験）
シアン含有廃水としてシアン含有廃水Ｃを用い、表７に示す濃度になるように次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素をそれぞれ添加すること以外は、試験例１と同様にしてシアン含有廃水Ｃを処理した。
一部の試験水には、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７に示す値になるように調整した。
次いで、試験水中の水不溶性の生成物を濾別し、濾液中の全シアン濃度（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、次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素を添加しないブランク試験（比較例１１）を同時に行った。
得られた結果を、添加化合物とその添加量および試験水のｐＨと共に表７に示す。
(Test Example 2-1 1-stage treatment test of cyanide-containing wastewater containing cyano complex)
Cyan-containing wastewater was used in the same manner as in Test Example 1 except that cyanide-containing wastewater C was used as the cyanogen-containing wastewater and sodium hypochlorite, manganese chloride, and hydrogen peroxide were added so that the concentrations were as shown in Table 7. C was treated.
An aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide was added to some of the test waters to adjust the pH of the test waters to the values shown in Table 7.
Next, the water-insoluble product in the test water was filtered off, the total cyanide concentration (T-CN) in the filtrate was measured according to JIS K0102, and the effect of removing the cyanide compound in each test water was evaluated.
In this test, a blank test (Comparative Example 11) in which sodium hypochlorite, manganese chloride and hydrogen peroxide were not added was simultaneously performed.
The obtained results are shown in Table 7 together with the added compound, its addition amount, and the pH of the test water.
表７の試験結果から次のことがわかる。
・次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素とを併用したｐＨ６．５〜９の添加化合物（実施例１０〜１６）で処理した場合において、十分なシアン除去効果を有すること
・これに対して、ｐＨ８における次亜塩素酸ナトリウムのみを用いた処理（比較例５）およびｐＨ８における塩化マンガンのみを用いた処理（比較例６）では、十分なシアン除去の効果が得られないこと
・ｐＨ８および９における次亜塩素酸ナトリウムと塩化マンガンとの併用処理（比較例７〜９）では、シアン除去の効果が得られるものと想定していたが、この廃水においてはその効果が十分ではないこと
・過酸化水素のみを用いた処理（比較例１０）では、過剰量の過酸化水素を添加したにも拘わらず、ほとんど効果が得られないこと
The following can be seen from the test results in Table 7.
· Having a sufficient cyanide removing effect when treated with an additive compound (Examples 10 to 16) having a pH of 6.5 to 9 in combination with sodium hypochlorite, manganese chloride and hydrogen peroxide. In the treatment using only sodium hypochlorite at pH 8 (Comparative Example 5) and the treatment using only manganese chloride at pH 8 (Comparative Example 6), sufficient cyan removal effect cannot be obtained. It was assumed that the combined treatment of sodium hypochlorite and manganese chloride in Example 9 (Comparative Examples 7 to 9) would provide the effect of removing cyan, but this effect is not sufficient in this wastewater. Almost no effect was obtained by the treatment using only hydrogen peroxide (Comparative Example 10), even though an excessive amount of hydrogen peroxide was added.
（試験例２−２／シアン化物イオンを含有するシアン含有廃水の１段処理試験）
シアン含有廃水としてシアン含有廃水Ｄを用い、表８に示す濃度になるように次亜塩素酸ナトリウムおよび過酸化水素をそれぞれ添加すること以外は、試験例２−１と同様にしてシアン含有廃水Ｄを処理した。
一部の試験水には、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８に示す値になるように調整した。
次いで、試験水中の水不溶性の生成物を濾別し、濾液中の全シアン濃度（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。
得られた結果を、添加化合物とその添加量および試験水のｐＨと共に表８に示す。
(Test Example 2-2/One-stage treatment test of cyanide-containing wastewater containing cyanide ion)
Cyan-containing wastewater D was used in the same manner as in Test Example 2-1, except that cyanide-containing wastewater D was used as the cyanide-containing wastewater and sodium hypochlorite and hydrogen peroxide were added so that the concentrations were as shown in Table 8. Was processed.
An aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide was added to a part of the test water to adjust the pH of the test water to the value shown in Table 8.
Next, the water-insoluble product in the test water was filtered off, the total cyanide concentration (T-CN) in the filtrate was measured according to JIS K0102, and the effect of removing the cyanide compound in each test water was evaluated.
The obtained results are shown in Table 8 together with the added compound, its addition amount, and the pH of the test water.
表８の試験結果から次のことがわかる。
・次亜塩素酸ナトリウムと過酸化水素とを併用したｐＨ８の添加化合物（実施例１７〜１９）で処理した場合において、十分なシアン除去効果を有すること
The test results in Table 8 show the following.
-Having a sufficient cyanide-removing effect when treated with an additive compound (Examples 17 to 19) having a pH of 8 in which sodium hypochlorite and hydrogen peroxide are used in combination.
（試験例２−３／シアノ錯体を含有するシアン含有廃水の２段処理試験）
容量３００ｍＬのビーカーに、それぞれシアン含有廃水Ｃを３００ｍＬ分注し、表９に示す濃度になるように次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素から選択される１種または２種をそれぞれ添加して試験水を得た。
一部の試験水には、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９に示す値になるように調整した。
次いで、得られた試験水を、前記の撹拌装置を用いて回転数１２０ｒｐｍで３０分間撹拌した。
次いで、試験水中の水不溶性の生成物を濾別し、容量２００ｍＬのビーカーに、それぞれ濾液（上澄み液）を分取し、表９に示す濃度になるように次亜塩素酸ナトリウム、塩化マンガンおよび過酸化水素から選択される１種または２種をそれぞれ添加して、前記の撹拌装置を用いて回転数１２０ｒｐｍで３０分間撹拌した。
次いで、試験水中の全シアン濃度（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。
得られた結果を、添加化合物とその添加量および試験水のｐＨと共に表９に示す。
(Test Example 2-3/Two-stage treatment test of cyanide-containing wastewater containing cyano complex)
To a beaker having a capacity of 300 mL, 300 mL of waste water C containing cyan was dispensed, and one or two kinds selected from sodium hypochlorite, manganese chloride and hydrogen peroxide were added so that the concentrations shown in Table 9 were obtained. Then, test water was obtained.
An aqueous solution of sulfuric acid or an aqueous solution of sodium hydroxide was added to a part of the test water to adjust the pH of the test water to the value shown in Table 9.
Next, the obtained test water was stirred for 30 minutes at a rotation speed of 120 rpm using the above stirring device.
Then, the water-insoluble product in the test water was filtered off, and the filtrate (supernatant solution) was collected into a beaker having a volume of 200 mL, and sodium hypochlorite, manganese chloride and One kind or two kinds selected from hydrogen peroxide were added, respectively, and stirred for 30 minutes at a rotation speed of 120 rpm using the above stirring device.
Next, the total cyan concentration (T-CN) in the test water was measured according to JIS K0102, and the effect of removing the cyan compound in each test water was evaluated.
The obtained results are shown in Table 9 together with the added compound, its addition amount, and the pH of the test water.
表９の試験結果から、本発明の方法で使用する薬剤を２段階で使用した場合においても、十分なシアン除去効果を発揮することがわかる。 From the test results in Table 9, it can be seen that even when the agent used in the method of the present invention is used in two steps, a sufficient cyanide removing effect is exhibited.
（試験例２−４／シアノ錯体を含有するシアン含有廃水の１段処理試験）
表１０に示す濃度になるように、次亜塩素酸ナトリウム、金属化合物および過酸化水素をそれぞれ添加すること以外は、試験例２−１と同様にしてシアン含有廃水Ｃを処理した。なお、金属化合物については、塩化第一鉄４水和物（Ｆｅ2+）、塩化亜鉛（Ｚｎ2+）、塩化第一銅（Ｃｕ+）および硫酸第二銅５水和物（Ｃｕ2+）をそれぞれ用いた。
得られた結果を添加化合物とその添加量および試験水のｐＨと共に表１０に示す。
(Test Example 2-4/One-stage treatment test of cyanide-containing wastewater containing cyano complex)
Cyan-containing wastewater C was treated in the same manner as in Test Example 2-1 except that sodium hypochlorite, a metal compound and hydrogen peroxide were added so that the concentrations were as shown in Table 10. As for the metal compound, ferrous chloride tetrahydrate (Fe 2+ ), zinc chloride (Zn 2+ ), cuprous chloride (Cu + ), and cupric sulfate pentahydrate (Cu 2+ ). ) Were used respectively.
The obtained results are shown in Table 10 together with the added compound, its addition amount and the pH of the test water.
表１０の試験結果から次のことがわかる。
・次亜塩素酸ナトリウムと特定の金属化合物（水中で２価の鉄イオンを形成し得る化合物および銅化合物）と過酸化水素とを併用した添加化合物（実施例２７〜３２）で処理した場合において、十分なシアン除去効果を有すること。
The following can be seen from the test results in Table 10.
When treated with an additive compound (Examples 27 to 32) in which sodium hypochlorite and a specific metal compound (a compound capable of forming a divalent iron ion in water and a copper compound) and hydrogen peroxide are used in combination , Must have sufficient cyan removal effect.
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| JP (2) | JPWO2016190108A1 (en) |
| KR (1) | KR102119234B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7448129B2 (en) | 2022-07-29 | 2024-03-12 | 株式会社片山化学工業研究所 | How to treat wastewater |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017104802A (en) * | 2015-12-09 | 2017-06-15 | 日鉄住金環境株式会社 | Method for treating cyanide-containing wastewater |
| JP6547055B2 (en) * | 2017-12-20 | 2019-07-17 | 日鉄環境株式会社 | Method for suppressing formation of cyano complex, method for treating exhaust gas, and exhaust gas treatment system |
| JP7353619B2 (en) * | 2019-07-23 | 2023-10-02 | 株式会社片山化学工業研究所 | Treatment method for cyanide-containing wastewater |
| CN110980916B (en) * | 2019-11-14 | 2021-03-26 | 东北大学 | Method for degrading thiocyanate in cyanogen-containing barren solution under acidic condition |
| JP7440031B2 (en) | 2019-11-14 | 2024-02-28 | 株式会社片山化学工業研究所 | Treatment method for cyanide-containing wastewater |
| CN113800703B (en) * | 2021-11-15 | 2023-06-06 | 大唐环境产业集团股份有限公司 | Catalyst flue gas washing wastewater treatment method and system |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167672A (en) * | 1974-12-10 | 1976-06-11 | Mitsubishi Petrochemical Co | SHIANSAKUIONGANJUHAISUINO SHORIHOHO |
| JPS51121957A (en) * | 1975-04-18 | 1976-10-25 | Asahi Chem Ind Co Ltd | Method of treating waste liquid |
| JPS5226762A (en) * | 1975-08-22 | 1977-02-28 | Ugine Kuhlmann | Oxidizing purification method of water |
| JPH0235991A (en) * | 1988-07-22 | 1990-02-06 | Katayama Chem Works Co Ltd | Treatment of waste water containing cyanic compound |
| JPH0568979A (en) * | 1991-03-27 | 1993-03-23 | Degussa Ag | Method of making aqueous solution containing cyanide and/or cyano complex harmful |
| US5792336A (en) * | 1995-09-18 | 1998-08-11 | Elif Technologies Ltd. | Method for purification of wastewater from soluble substances |
| JPH1133571A (en) * | 1997-07-17 | 1999-02-09 | Kurita Water Ind Ltd | Wastewater treatment method |
| JP2001300553A (en) * | 2000-04-21 | 2001-10-30 | Katayama Chem Works Co Ltd | Method for treating cyanide-containing wastewater |
| JP2004074087A (en) * | 2002-08-21 | 2004-03-11 | Mitsubishi Gas Chem Co Inc | Treatment method for cyanogen compound-containing waste liquid |
| JP2005279571A (en) * | 2004-03-30 | 2005-10-13 | Jfe Steel Kk | Cyanogen-containing wastewater treatment method |
| JP2009254959A (en) * | 2008-04-15 | 2009-11-05 | Sumitomo Heavy Industries Environment Co Ltd | Method and apparatus for treating wastewater |
| CN102329026A (en) * | 2011-09-07 | 2012-01-25 | 南昌市国昌环保科技有限公司 | Treatment method of coking wastewater subjected to biochemical treatment |
| JP2012157798A (en) * | 2011-01-31 | 2012-08-23 | Jfe Steel Corp | Method for treating cyanide-containing wastewater |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274806B (en) * | 2007-03-30 | 2010-09-29 | 北京清华紫光英力化工技术有限责任公司 | Novel process for reclaiming waste water containing CN- and NH3 or NH4- |
| CN104163518B (en) * | 2014-05-15 | 2016-07-06 | 浙江海洋学院 | A kind of processing method of cyanide wastewater of printing and dyeing |
| CN104261548A (en) * | 2014-10-17 | 2015-01-07 | 苏州新协力环保科技有限公司 | Novel oxidation treatment method for chemical waste water |
-
2016
- 2016-05-11 KR KR1020177036783A patent/KR102119234B1/en active IP Right Grant
- 2016-05-11 JP JP2017520614A patent/JPWO2016190108A1/en active Pending
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- 2016-05-11 AU AU2016268593A patent/AU2016268593A1/en not_active Abandoned
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-
2020
- 2020-04-03 JP JP2020067566A patent/JP7204140B2/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167672A (en) * | 1974-12-10 | 1976-06-11 | Mitsubishi Petrochemical Co | SHIANSAKUIONGANJUHAISUINO SHORIHOHO |
| JPS51121957A (en) * | 1975-04-18 | 1976-10-25 | Asahi Chem Ind Co Ltd | Method of treating waste liquid |
| JPS5226762A (en) * | 1975-08-22 | 1977-02-28 | Ugine Kuhlmann | Oxidizing purification method of water |
| JPH0235991A (en) * | 1988-07-22 | 1990-02-06 | Katayama Chem Works Co Ltd | Treatment of waste water containing cyanic compound |
| JPH0568979A (en) * | 1991-03-27 | 1993-03-23 | Degussa Ag | Method of making aqueous solution containing cyanide and/or cyano complex harmful |
| US5792336A (en) * | 1995-09-18 | 1998-08-11 | Elif Technologies Ltd. | Method for purification of wastewater from soluble substances |
| JPH1133571A (en) * | 1997-07-17 | 1999-02-09 | Kurita Water Ind Ltd | Wastewater treatment method |
| JP2001300553A (en) * | 2000-04-21 | 2001-10-30 | Katayama Chem Works Co Ltd | Method for treating cyanide-containing wastewater |
| JP4106415B2 (en) * | 2000-04-21 | 2008-06-25 | 株式会社片山化学工業研究所 | Treatment method of wastewater containing cyanide |
| JP2004074087A (en) * | 2002-08-21 | 2004-03-11 | Mitsubishi Gas Chem Co Inc | Treatment method for cyanogen compound-containing waste liquid |
| JP2005279571A (en) * | 2004-03-30 | 2005-10-13 | Jfe Steel Kk | Cyanogen-containing wastewater treatment method |
| JP2009254959A (en) * | 2008-04-15 | 2009-11-05 | Sumitomo Heavy Industries Environment Co Ltd | Method and apparatus for treating wastewater |
| JP2012157798A (en) * | 2011-01-31 | 2012-08-23 | Jfe Steel Corp | Method for treating cyanide-containing wastewater |
| CN102329026A (en) * | 2011-09-07 | 2012-01-25 | 南昌市国昌环保科技有限公司 | Treatment method of coking wastewater subjected to biochemical treatment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7448129B2 (en) | 2022-07-29 | 2024-03-12 | 株式会社片山化学工業研究所 | How to treat wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016190108A1 (en) | 2018-03-08 |
| CN107614444A (en) | 2018-01-19 |
| AU2016268593A1 (en) | 2017-12-21 |
| KR102119234B1 (en) | 2020-06-04 |
| WO2016190108A1 (en) | 2016-12-01 |
| KR20180010244A (en) | 2018-01-30 |
| JP7204140B2 (en) | 2023-01-16 |
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