JP2021016845A - Method for treating cyanide-containing wastewater - Google Patents
Method for treating cyanide-containing wastewater Download PDFInfo
- Publication number
- JP2021016845A JP2021016845A JP2019135562A JP2019135562A JP2021016845A JP 2021016845 A JP2021016845 A JP 2021016845A JP 2019135562 A JP2019135562 A JP 2019135562A JP 2019135562 A JP2019135562 A JP 2019135562A JP 2021016845 A JP2021016845 A JP 2021016845A
- Authority
- JP
- Japan
- Prior art keywords
- cyanide
- wastewater
- compound
- chlorite
- containing wastewater
- 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 181
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 62
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 62
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 58
- -1 chlorite ions Chemical class 0.000 claims abstract description 51
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000005749 Copper compound Substances 0.000 claims abstract description 21
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 21
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 14
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 10
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 23
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical group [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 22
- 229960002218 sodium chlorite Drugs 0.000 claims description 22
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 12
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 12
- 229940045803 cuprous chloride Drugs 0.000 claims description 12
- 229960003280 cupric chloride Drugs 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 17
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 229910001431 copper ion Inorganic materials 0.000 description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 11
- 229910001437 manganese ion Inorganic materials 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 7
- 230000002411 adverse Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 6
- 229940005993 chlorite ion Drugs 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 239000004155 Chlorine dioxide Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000019398 chlorine dioxide Nutrition 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid 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
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- 239000007788 liquid Substances 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical class [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000571 coke Substances 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
- 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
- 238000007599 discharging Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- NWAPVVCSZCCZCU-UHFFFAOYSA-L magnesium;dichlorite Chemical compound [Mg+2].[O-]Cl=O.[O-]Cl=O NWAPVVCSZCCZCU-UHFFFAOYSA-L 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
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 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
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000003034 coal gas Substances 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
- 229940076286 cupric acetate Drugs 0.000 description 1
- 239000011641 cupric citrate Substances 0.000 description 1
- 235000019855 cupric citrate Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002505 iron 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- KAGBQTDQNWOCND-UHFFFAOYSA-M lithium;chlorite Chemical compound [Li+].[O-]Cl=O KAGBQTDQNWOCND-UHFFFAOYSA-M 0.000 description 1
- 150000002696 manganese Chemical class 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ZUABIENWAVCHBJ-UHFFFAOYSA-M tetrabutylazanium;chlorite Chemical compound [O-]Cl=O.CCCC[N+](CCCC)(CCCC)CCCC ZUABIENWAVCHBJ-UHFFFAOYSA-M 0.000 description 1
- VDYFGPILOTVGIR-UHFFFAOYSA-M tetraethylazanium chlorite Chemical compound [O-]Cl=O.CC[N+](CC)(CC)CC VDYFGPILOTVGIR-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 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
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
本発明は、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法に関する。 The present invention reduces the amount of chemicals added as much as possible, reduces the deterioration of the working environment such as corrosion to equipment, and can reliably and inexpensively remove cyanide from wastewater with simple operations. Regarding the processing method of.
シアンは生態系に強い悪影響を及ぼすため、シアン含有廃水(「シアン廃水」ともいう)を自然界にそのまま放出することはできない。水質汚濁防止法に基づきシアンの排水基準が定められ、この基準(1mg/L以下)を満たすようにシアン除去処理を行い、無害化した廃水でなければ下水などに排出できない。また、地域によっては、条例により、上記の排水基準値よりもさらに低い上乗せ排水基準が定められている。また、廃水中に含まれるシアンの一部はシアン化水素ガスとして周辺に拡散し、作業環境が著しく損なわれるという問題もあり、労働安全衛生法では、シアン化水素の作業環境濃度は3ppm以下であることが規定されている。
シアンは、廃水の由来にも因り、含有量の多少はあるが、難分解性シアン錯体およびそのイオン、易分解性シアン錯体およびそのイオン、シアン化物イオンの3種の形態で廃水中に存在している。
Cyan has a strong adverse effect on the ecosystem, so cyan-containing wastewater (also called "cyan wastewater") cannot be released into the natural world as it is. Cyan wastewater standards have been established based on the Water Pollution Control Law, and cyanide removal treatment is performed so as to meet this standard (1 mg / L or less), and only detoxified wastewater can be discharged into sewage. In addition, depending on the region, the ordinance stipulates additional drainage standards that are even lower than the above drainage standard values. In addition, there is a problem that part of cyanide contained in wastewater diffuses to the surroundings as hydrogen cyanide gas, and the working environment is significantly impaired. The Industrial Safety and Health Act stipulates that the working environment concentration of hydrogen cyanide is 3 ppm or less. Has been done.
Cyan is present in wastewater in three forms: persistent cyan complex and its ions, easily degradable cyan complex and its ions, and cyanide ion, although the content varies depending on the origin of the wastewater. ing.
従来からシアン含有廃水中のシアンの除去処理として様々な方法が提案され、実用化されているが、いずれも一長一短があり、廃水の状況に応じて使い分けられている。
例えば、(1)シアン含有廃水をアルカリ性に調整した後、塩素を注入してシアンを酸化分解するアルカリ塩素法、(2)強力なオゾンの酸化力でシアンを窒素ガスと炭酸水素塩に酸化分解するオゾン酸化法および(3)非溶解性の電極を用いてシアンを電気分解し、酸化反応を行なう電解酸化法(電解法)などの酸化分解法;(4)シアン含有廃水中に、鉄イオンの供給化合物として、例えば硫酸第一鉄を添加し、難溶性のフェリ/フェロシアン化物を生成させ、これを沈殿除去する紺青法、(5)塩化亜鉛と還元剤とを添加し、生成した不溶錯体を沈殿除去する亜鉛白法および(6)2価の銅塩と還元剤とを添加し、生成した不溶錯体を沈殿除去する還元銅塩法などの不溶錯体法;(7)シアンに対して馴養させた微生物(シアン分解菌)にシアンを分解させる生物処理法;(8)シアン含有廃水を高温に保持してシアン化合物をアンモニアと蟻酸に加水分解させ、共存する重金属類を単体または酸化物として析出させる熱加水分解法および(9)シアンの分解以外に有機汚濁物をも酸化分解させる湿式酸化法などの熱水反応などがある。
Conventionally, various methods have been proposed and put into practical use as a treatment for removing cyanide from cyan-containing wastewater, but all of them have advantages and disadvantages, and are used properly according to the state of wastewater.
For example, (1) the alkaline chlorine method in which cyanide-containing wastewater is adjusted to alkaline and then chlorine is injected to oxidize and decompose cyanide, and (2) cyanide is oxidatively decomposed into nitrogen gas and hydrogen carbonate by the strong oxidizing power of ozone. Oxidation method such as the ozone oxidation method and (3) electrolytic oxidation method (electrolysis method) that electrolyzes cyanide using an insoluble electrode to perform an oxidation reaction; (4) iron ions in cyanide-containing wastewater. As a supply compound of, for example, ferrous sulfate is added to generate a sparingly soluble ferri / ferrocyanide, and the dark blue method for precipitating and removing this, (5) zinc chloride and a reducing agent are added to form an insoluble product. Insoluble complex methods such as the zinc white method for precipitating and removing the complex and the reduced copper salt method for precipitating and removing the produced insoluble complex by adding a divalent copper salt and a reducing agent; (7) for cyanide. Biological treatment method in which cyanide is decomposed by acclimatized microorganisms (cyanide-degrading bacteria); (8) Cyanide-containing wastewater is kept at a high temperature to hydrolyze cyanide compounds to ammonia and formic acid, and coexisting heavy metals are used alone or as oxides. In addition to the thermal hydrolysis method for precipitating cyanide and (9) decomposition of cyanide, there are hydrothermal reactions such as a wet oxidation method for oxidatively decomposing organic pollutants.
また、特開昭52−123976号公報(特許文献1)には、石炭乾留により石炭ガスおよびコークスを製造する工程から生ずる、シアン化合物などを含む排液を二酸化塩素で処理する排液処理方法、特開昭55−137087号公報(特許文献2)には、シアノ金属錯塩を含む水溶液に、pH8.0〜12.0未満において亜塩素酸ソーダを作用させ錯塩を形成しているシアンを酸化分解する、シアノ金属錯塩の分解方法が開示されている。
さらに、本発明の出願人は、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、シアン含有廃水の処理方法を提案してきた(国際公開第WO2016/190108号:特許文献3参照)。
Further, Japanese Patent Application Laid-Open No. 52-123796 (Patent Document 1) describes a effluent treatment method for treating effluent containing a cyanide or the like with chlorine dioxide, which is generated from the step of producing coal gas and coke by carbonization. Japanese Patent Application Laid-Open No. 55-137807 (Patent Document 2) oxidatively decomposes cyanide forming a complex salt by allowing sodium chlorite to act on an aqueous solution containing a cyanometal complex salt at a pH of less than 8.0 to 12.0. A method for decomposing a cyanide complex salt is disclosed.
Furthermore, the applicant of the present invention added hypochlorite and hydrogen peroxide to the cyan-containing wastewater simultaneously or separately to decompose cyan in the wastewater and / or to prepare a water-insoluble compound with cyanide. We have proposed a method for treating cyanide-containing wastewater, which causes generation and removes cyanide from the wastewater (see International Publication No. WO 2016/190108: Patent Document 3).
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, and a plurality of reaction tanks may be required accordingly. In addition, depending on the type of wastewater, such as wastewater containing thiocyanate ions and ammonium ions, the effect of removing cyan is not sufficient, and the cyan concentration of the treated wastewater cannot be set to the wastewater standard (1 mg / L or less). In some cases, the treated wastewater cannot be discharged to sewage as it is.
In addition, based on the Water Pollution Control Law, the effluent standard for hydrogen ion concentration (pH) is set to 5.0 to 9.0 in the sea area and 5.8 to 8.6 outside the sea area. In the above prior art, when the pH of wastewater is adjusted to acidic or alkaline, it is necessary to perform neutralization treatment to adjust not only the cyan concentration of wastewater but also the pH within the wastewater standard range before discharging it into sewage. It may become.
そこで、本発明は、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法を提供することを課題とする。 Therefore, the present invention reduces the amount of chemicals added as much as possible, reduces deterioration of the working environment such as corrosion to equipment, and can reliably and inexpensively remove cyanide in wastewater by simple operation. An object of the present invention is to provide a method for treating contained wastewater.
本発明の発明者は、上記の課題を解決すべく鋭意研究を重ねた結果、シアン含有廃水に、有効量の亜塩素酸塩または廃水中で亜塩素酸イオンを発生し得る化合物と、有効量の特定の金属化合物とを併用することにより、意外にも、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得る事実を見出し、本発明を完成するに到った。 As a result of intensive research to solve the above problems, the inventor of the present invention has added an effective amount of chlorite or a compound capable of generating chlorite ion in the wastewater to the cyan-containing wastewater, and an effective amount. Surprisingly, by using this in combination with a specific metal compound, the amount of chemicals added is suppressed as much as possible, the deterioration of the working environment such as corrosion to equipment is reduced, and wastewater is safely and inexpensively discharged with simple operations. We have found the fact that the cyanide in it can be reliably removed, and have completed the present invention.
かくして、本発明によれば、シアン含有廃水に、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、マンガン化合物、鉄化合物、亜鉛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とを併用して、該廃水からシアンを除去することを特徴とするシアン含有廃水の処理方法が提供される。 Thus, according to the present invention, the cyanide-containing wastewater is selected from a chlorite or a compound capable of generating chlorite ions in the wastewater, and a manganese compound, an iron compound, a zinc compound and a copper compound. Provided is a method for treating cyanide-containing wastewater, which comprises removing cyanide from the wastewater in combination with the above metal compounds.
本発明によれば、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを確実に除去し得るシアン含有廃水の処理方法を提供することができる。
すなわち、本発明によれば、各種形態で廃水中に含有するシアンを、従来よりも薬剤添加量を極力抑え、簡便な操作で処理することができる。
また、廃水中のシアン濃度が排水規制(1mg/L以下)を満たすことで、周辺へのシアン化水素ガスの拡散も抑えられ、作業環境の改善も期待できる。
よって、本発明の方法で処理した廃水をそのまま自然界に放出しても、環境に対する影響が非常に少なく、また処理後に発生する懸濁物質(廃棄物)の量も少なくできることから、本発明の方法は産業上極めて有用である。
According to the present invention, the amount of chemicals added is suppressed as much as possible, the deterioration of the working environment such as corrosion to equipment is reduced, and cyan in wastewater can be reliably and safely removed by simple operation. A method for treating contained wastewater can be provided.
That is, according to the present invention, cyanide contained in wastewater in various forms can be treated by a simple operation while suppressing the amount of chemicals added as much as possible.
In addition, if the cyanide concentration in the wastewater satisfies the wastewater regulation (1 mg / L or less), the diffusion of hydrogen cyanide gas to the surroundings can be suppressed, and an improvement in the working environment can be expected.
Therefore, even if the wastewater treated by the method of the present invention is discharged to the natural world as it is, the influence on the environment is very small, and the amount of suspended substances (waste) generated after the treatment can be reduced. Therefore, the method of the present invention. Is extremely useful industrially.
また、本発明のシアン含有廃水の処理方法は、次の条件のいずれか1つを満たす場合に、上記の効果をより発揮する。
(1)亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物がシアン含有廃水中のシアン含有量に対してモル比で少なくとも0.2倍の濃度であり、かつ金属化合物がシアン含有廃水中において0.1〜1000mg/Lの濃度である。
(2)シアン含有廃水中のシアン含有量および金属化合物濃度を予め測定し、測定したシアン含有量に応じた亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、測定した金属化合物濃度に応じた金属化合物とを、同時または別々に該廃水に添加する。
(3)シアン含有廃水が、pH6〜9である。
(4)亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物が亜塩素酸ナトリウムであり、かつ金属化合物が塩化第一銅、塩化第二銅または硫酸第二銅である。
Further, the method for treating cyanide-containing wastewater of the present invention more exerts the above-mentioned effect when any one of the following conditions is satisfied.
(1) The concentration of chlorite or a compound capable of generating chlorite ions in the wastewater is at least 0.2 times the molar ratio of the cyan content in the cyan-containing wastewater, and the metal compound is present. It has a concentration of 0.1 to 1000 mg / L in cyan-containing wastewater.
(2) The cyan content and the metal compound concentration in the cyan-containing waste water were measured in advance, and the chlorite or a compound capable of generating chlorite ions in the waste water was measured according to the measured cyan content. A metal compound according to the concentration of the metal compound is added to the waste water simultaneously or separately.
(3) Cyan-containing wastewater has a pH of 6 to 9.
(4) The chlorite or a compound capable of generating chlorite ions in the waste water is sodium chlorite, and the metal compound is cuprous chloride, cupric chloride or cupric sulfate.
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、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、マンガン化合物、鉄化合物、亜鉛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とを併用して、該廃水からシアンを除去することを特徴とする。 The method for treating cyanide-containing wastewater of the present invention is selected from chlorite or a compound capable of generating chlorite ions in the wastewater, and a manganese compound, an iron compound, a zinc compound and a copper compound. It is characterized in that cyanide is removed from the waste water in combination with one or more kinds of metal compounds.
本発明において「シアン含有廃水に亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と金属化合物とを併用する」とは、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と金属化合物とをシアン含有廃水中に存在させることを意味する。その併用は、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と金属化合物との添加によっても、後述するように、シアン含有廃水中での生成によってもよく、添加の場合その順序は特に限定されず、同時であっても別々であってもよい。また、充分な濃度の金属化合物を含有するシアン含有廃水に亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物を添加してもよい。さらに、シアン含有廃水を処理する設備内であれば、同一または別々の場所に二酸化塩素と金属化合物とを添加してもよい。 In the present invention, "a compound that can generate chlorite ion in cyanate or wastewater and a metal compound are used in combination" means that chlorite or chlorite ion in the wastewater is used in combination. It means that a compound capable of generating the above and a metal compound are present in the cyanide-containing wastewater. The combined use may be by addition of a metal compound and a chlorite or a compound capable of generating chlorite ions in the wastewater, or as described later, by formation in cyanide-containing wastewater, and in the case of addition. The order is not particularly limited and may be simultaneous or separate. Further, chlorite or a compound capable of generating chlorite ions in the wastewater may be added to the cyanide-containing wastewater containing a sufficient concentration of the metal compound. Further, chlorine dioxide and the metal compound may be added to the same or different places in the facility for treating the cyan-containing wastewater.
(1)亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物
本発明において用いられる亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物は、水中で亜塩素酸イオンを形成して、併用する金属化合物の金属イオンと共に、本発明のシアン化合物の除去効果を発揮するものと考えられる。
(1) Chlorite or a compound capable of generating chlorite ion in the waste water The chlorite used in the present invention or a compound capable of generating chlorite ion in the waste water is chlorite in water. It is considered that the acid ion is formed and the effect of removing the cyan compound of the present invention is exhibited together with the metal ion of the metal compound used in combination.
亜塩素酸塩としては、例えば、亜塩素酸リチウム、亜塩素酸ナトリウムおよび亜塩素酸カリウムのような亜塩素酸のアルカリ金属塩;亜塩素酸マグネシウムおよび亜塩素酸カルシウムのようなアルカリ土類金属塩;亜塩素酸アンモニウム(NH4ClO2)のようなアンモニウム亜塩素酸塩;ならびに亜塩素酸テトラメチルアンモニウム、亜塩素酸テトラエチルアンモニウムおよび亜塩素酸テトラブチルアンモニウムのような亜塩素酸テトラアルキルアンモニウムが挙げられる。
本発明においては、上記の亜塩素酸塩の1種を単独でまたは2種以上を組み合わせて用いることができ、上記の亜塩素酸塩の中でも、シアン化合物の除去効果の点や工業的に入手し易いなどのコストの点で、亜塩素酸ナトリウムおよび亜塩素酸マグネシウムが好ましく、亜塩素酸ナトリウムが特に好ましい。
Chlorites include, for example, alkali metal salts of chlorite such as lithium chlorite, sodium chlorite and potassium chlorite; alkaline earth metals such as magnesium chlorite and calcium chlorite. Salts; ammonium chlorites such as ammonium chlorite (NH 4 ClO 2 ); and tetraalkylammonium chlorites such as tetramethylammonium chlorite, tetraethylammonium chlorite and tetrabutylammonium chlorite. Can be mentioned.
In the present invention, one of the above chlorites can be used alone or in combination of two or more, and among the above chlorites, the effect of removing cyanide compounds and industrial acquisition Sodium chlorite and magnesium chlorite are preferable, and sodium chlorite is particularly preferable, in terms of cost such as easy operation.
廃水中で亜塩素酸イオンを発生し得る化合物を廃水に直接添加してもよい。
亜塩素酸塩は、公知の方法により製造することができ、例えば、工業的には次のような反応により亜塩素酸ナトリウムを製造することができる。
まず、塩素酸ナトリウムNaClO3に塩酸または硫酸と還元剤とを共に反応塔に入れ、二酸化塩素ClO2を発生させる。次いで、発生した二酸化塩素ガスを洗浄塔で洗ったのち吸収塔に入れ、水酸化ナトリウムと反応させる。この際、還元剤の添加は、ClO2が再びNaClO3に戻ることを防止し、収率を高めるためである。この還元剤には、過酸化水素、過酸化物、Znなどの金属粉末、炭素、PbOなどの金属酸化物、硫黄アマルガムなどがある。次いで、吸収塔から回収した水溶液を濾過、乾燥して亜塩素酸ナトリウムの製品とする。また亜塩素酸ナトリウムは液状でも市販されている。
Compounds that can generate chlorite ions in the wastewater may be added directly to the wastewater.
The chlorite can be produced by a known method, and for example, industrially, sodium chlorite can be produced by the following reaction.
First, hydrochloric acid or sulfuric acid and a reducing agent are put together in sodium chlorate NaClO 3 in a reaction column to generate chlorine dioxide ClO 2 . Next, the generated chlorine dioxide gas is washed in a scrubber and then placed in an absorption tower to react with sodium hydroxide. At this time, the addition of the reducing agent is for preventing ClO 2 from returning to NaCl O 3 again and increasing the yield. Examples of this reducing agent include hydrogen peroxide, peroxides, metal powders such as Zn, metal oxides such as carbon and PbO, and sulfur amalgam. Next, the aqueous solution recovered from the absorption tower is filtered and dried to obtain a sodium chlorite product. Sodium chlorite is also commercially available in liquid form.
(2)金属化合物
本発明において用いられる金属化合物は、マンガン化合物、鉄化合物、亜鉛化合物および銅化合物から選択される1種以上であり、併用する、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物の亜塩素酸イオンと共に、本発明のシアン化合物の除去効果を発揮するものと考えられる。
以下に各金属化合物について説明するが、これらの金属化合物の中でも、シアン除去効果の点で銅化合物が特に好ましい。
(2) Metal Compound The metal compound used in the present invention is one or more selected from manganese compounds, iron compounds, zinc compounds and copper compounds, and is used in combination with chlorite or chlorite in the waste water. It is considered that the cyan compound of the present invention can be removed together with the chlorite ion of the compound capable of generating ions.
Each metal compound will be described below, but among these metal compounds, a copper compound is particularly preferable in terms of cyanide removing effect.
(2−1)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。
(2-1) 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, for example, manganese chloride, manganese sulfate, manganese nitrate. , Manganese acetate and the like. Among these, manganese chloride and manganese sulfate are particularly preferable in terms of the effect of removing cyanide compounds, and manganese chloride is particularly preferable in terms of the treatment cost of 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.
(2−2)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。
(2-2) Iron compound The iron compound used in the present invention is not particularly limited as long as it is soluble in water, and for example, ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous acetate and the like. Examples include compounds capable of forming divalent iron ions in water. Among 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、チオ硫酸塩などが挙げられる。
In the method of the present invention, as an iron compound, an iron compound capable of forming trivalent iron ions in water is added to cyan-containing wastewater together with a reducing agent, or trivalent iron ions in water are added to reducing cyan-containing wastewater. It contains a divalent iron ion supply compound produced by adding an iron compound capable of forming the above and reducing the iron compound capable of forming a trivalent iron ion in the waste water.
Examples of the reducing agent include sulfites and thiosulfates.
(2−3)亜鉛化合物
本発明において用いられる亜鉛化合物は、水に可溶であり、水中で亜鉛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、塩化亜鉛、酸化亜鉛、水酸化亜鉛、炭酸亜鉛、過酸化亜鉛、硫酸亜鉛、硝酸亜鉛などが挙げられる。これらの中でもシアン化合物の除去効果の点では、塩化亜鉛および硫酸亜鉛が特に好ましく、さらにシアン含有廃水の処理コストの点では、塩化亜鉛が特に好ましい。
(2-3) Zinc Compound The zinc 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 zinc ions in water, and is, for example, zinc chloride, zinc oxide, or hydroxide. Examples include zinc, zinc carbonate, zinc peroxide, zinc sulfate, zinc nitrate and the like. Among these, zinc chloride and zinc sulfate are particularly preferable in terms of the effect of removing cyanide compounds, and zinc chloride is particularly preferable in terms of the treatment cost of cyanide-containing wastewater.
(2−4)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。
(2-4) Copper Compound The copper compound used in the present invention is not particularly limited as long as it is a copper compound that is soluble or easily dispersed in water and can form copper ions in water, and is not particularly limited to the first copper compound and the first copper compound. Examples thereof include dicopper compounds, which may be either 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、無機第一銅化合物および無機第二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. Formable cuprous compounds and divalent copper ions in water such as cupric chloride, cupric fluoride, cupric bromide, cupric iodide, cupric nitrate, cupric sulfate Examples include cupric compounds that can be formed.
Since the organic copper compound may increase the COD in the treated cyan-containing waste water, the inorganic cuprous compound and the inorganic cupric compound are preferable among the above-mentioned copper compounds, and the effect of removing cyan and the cyan-containing waste water are preferable. Inorganic cuprous compounds are more preferred, cuprous chloride and cuprous sulfate are even more preferred, and cuprous chloride is particularly preferred in terms of processing costs.
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の一部として用い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、チオ硫酸塩などが挙げられる。
When the cuprous compound is a cuprous salt, the cuprous salt solution uses hydrogen chloride water, an aqueous alkali metal halide solution or ethanol as a part of the solvent. It is preferable from the viewpoint of stability.
In the method of the present invention, as a copper compound, a cupric compound is added to cyan-containing wastewater together with a reducing agent, or a cupric compound is added to reducing cyan-containing wastewater, and cupric is added to the wastewater. It contains a cuprous ion supply compound produced by reducing a compound.
Examples of the above-mentioned reducing agent include sulfites, divalent iron salts, thiosulfates and the like.
本発明のシアン含有廃水の処理方法は、上記の化合物のいずれの組み合わせによっても本発明の優れたシアン化合物の除去効果が得られるが、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物が亜塩素酸ナトリウムであり、かつ金属化合物が塩化第一銅、塩化第二銅または硫酸第二銅であるのが特に好ましい。 The method for treating cyanide-containing wastewater of the present invention can obtain the excellent effect of removing the cyanide compound of the present invention by any combination of the above compounds, but generates chlorite ions in chlorite or the wastewater. It is particularly preferred that the possible compound is sodium chlorite and the metal compound is cuprous chloride, cupric chloride or cupric sulfate.
(3)化合物の併用
本発明のシアン含有廃水の処理方法では、シアン含有廃水に、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、マンガン化合物、鉄化合物、亜鉛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とを併用する。
シアン含有廃水に上記の化合物を併用するためには、例えば、シアン含有廃水に、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、金属化合物とを添加すればよく、それらの添加順序は特に限定されず、両化合物を同時に、上記の記載順またはその逆順で別々に添加してもよい。
また、添加には、上記の各化合物を水溶液の形態で用いるのが好ましい。
なお、過剰の金属化合物が残存するような場合には、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。
各水溶液の濃度は、それらをシアン含有廃水に添加する際の作業性、シアンと添加した化合物との反応性などを考慮して決定すればよい。
(3) Combined use of compounds In the method for treating cyanide-containing wastewater of the present invention, chlorite or a compound capable of generating chlorite ions in the wastewater, a manganese compound, an iron compound, and a zinc compound are added to the cyanide-containing wastewater. And one or more metal compounds selected from copper compounds are used in combination.
In order to use the above compound in combination with the cyan-containing wastewater, for example, chlorite or a compound capable of generating chlorite ions in the wastewater and a metal compound may be added to the cyan-containing wastewater. The order of addition thereof is not particularly limited, and both compounds may be added separately at the same time in the above-mentioned order or vice versa.
Further, for addition, it is preferable to use each of the above compounds in the form of an aqueous solution.
If an excess metal compound remains, treatment with a metal collecting agent may be used. Further, it may be diluted or dissolved in water such as industrial water before use.
Examples of the above-mentioned metal collecting agent include a liquid chelating agent and the like.
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 the like.
(4)化合物の濃度
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物は、シアン含有廃水中のシアン含有量に対してモル比で少なくとも0.2倍の濃度であるのが好ましい。
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物の濃度は、シアン含有廃水に含まれるシアンの種類およびその濃度のほかに、シアン含有廃水に含まれる金属イオンの種類およびその濃度などの影響を受けるので、これらの条件に応じて適宜決定すればよい。具体的には、処理前(処理直前から約3時間前まで)のシアン含有廃水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、濃度を決定すればよい。
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物の濃度がシアン含有廃水中のシアン含有量に対してモル比で0.2倍未満では、シアン除去の効果が不十分になることがある。
具体的な好ましい亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物の濃度の下限値は、0.2倍、0.4倍、0.5倍、1.0倍、2.0倍、5.0倍、10倍である。
上記の下限値を超える濃度で亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物を用いても、濃度に見合う効果が得られないことがあり、薬剤使用量が多くなることで経済的に好ましくない。
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物を過剰量添加することで、後段の処理に悪影響を及ぼすおそれがある場合には、亜硫酸塩、二価の鉄塩、チオ硫酸塩などの還元剤を用いて処理してもよい。
(4) Concentration of compound The concentration of chlorite or a compound capable of generating chlorite ions in the wastewater is at least 0.2 times the molar ratio of the cyan content in the cyan-containing wastewater. Is preferable.
The concentration of chlorite or a compound capable of generating chlorite ions in the wastewater includes the types of cyanide contained in cyanide-containing wastewater and its concentration, as well as the types of metal ions contained in cyanide-containing wastewater and their concentrations. Since it is affected by the concentration and the like, it may be appropriately determined according to these conditions. Specifically, the cyan concentration of the cyan-containing wastewater before the treatment (from immediately before the treatment to about 3 hours before) may be measured in advance, and the concentration may be determined based on the measured value.
If the concentration of chlorite or a compound that can generate chlorite ions in the wastewater is less than 0.2 times the molar ratio of the cyan content in the cyan-containing wastewater, the effect of removing cyan is insufficient. May become.
The lower limit of the concentration of a specific preferable chlorite or a compound capable of generating chlorite ions in the wastewater is 0.2 times, 0.4 times, 0.5 times, 1.0 times, 2 times. It is 0.0 times, 5.0 times, and 10 times.
Even if a chlorite or a compound capable of generating chlorite ions in the wastewater is used at a concentration exceeding the above lower limit, an effect commensurate with the concentration may not be obtained, and the amount of the drug used increases. It is not economically preferable.
If an excessive amount of chlorite or a compound capable of generating chlorite ions in the waste water may adversely affect the subsequent treatment, sulfites, divalent iron salts, or thio It may be treated with a reducing agent such as sulfate.
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物は、溶液の形態で添加するのがよい。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、2.5〜10000mg/L程度であり、好ましくは10〜2600mg/L程度である。 Chlorite or a compound capable of generating chlorite ions in the wastewater should be added in the form of a solution. The concentration of the solution may be determined in consideration of workability when adding it to cyanide-containing wastewater, reactivity between cyanide and the added compound, and more specifically, about 2.5 to 10,000 mg / L. It is preferably about 10 to 2600 mg / L.
金属化合物は、シアン含有廃水中において0.1〜1000mg/Lの濃度であるのが好ましい。
金属化合物の濃度は、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、シアン含有廃水に元々含まれる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、これらの条件に応じて適宜決定すればよい。具体的には、処理前(処理直前から約3時間前まで)の金属化合物濃度などを予め測定しておき、この測定値に基づいて、濃度を決定すればよい。
金属化合物の濃度が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、金属化合物の濃度が1000mg/Lを超えると、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。
The metal compound preferably has a concentration of 0.1 to 1000 mg / L in cyan-containing wastewater.
The concentration of the metal compound is affected by the type and concentration of cyanide contained in the cyanide-containing wastewater, as well as the type and concentration of metal ions originally contained in the cyanide-containing wastewater. Therefore, it is appropriate according to these conditions. You just have to decide. Specifically, the concentration of the metal compound before the treatment (from immediately before the treatment to about 3 hours before) may be measured in advance, and the concentration may be determined based on the measured value.
If the concentration of the metal compound is less than 0.1 mg / L, the effect of removing cyanide may be insufficient. On the other hand, if the concentration of the metal compound exceeds 1000 mg / L, it not only adversely affects the environment but is also economically unfavorable.
また、上記の金属化合物は、溶液の形態で添加するのがよい。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0.1〜1000mg/L程度、鉄化合物は鉄イオン濃度として0.1〜1000mg/L程度、亜鉛化合物は亜鉛イオン濃度として0.1〜1000mg/L程度、銅化合物は銅イオン濃度として0.1〜1000mg/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、亜鉛イオン、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、亜鉛化合物、銅化合物の添加量を設定すればよい。
In addition, the above metal compounds are preferably added in the form of a solution. The concentration of the solution may be determined in consideration of workability when adding it to cyan-containing wastewater, reactivity between cyanide and the added compound, and specifically, the manganese compound has a manganese ion concentration of 0. .1-1 to 1000 mg / L, iron compounds have an iron ion concentration of about 0.1 to 1000 mg / L, zinc compounds have a zinc ion concentration of about 0.1 to 1000 mg / L, and copper compounds have a copper ion concentration of 0.1. It is about 1000 mg / L.
When the cyanide-containing wastewater contains manganese ions, iron ions, zinc ions, and copper ions, the amount of manganese compound, iron compound, zinc compound, and copper compound added may be set in consideration of the contents.
したがって、本発明のシアン含有廃水の処理方法は、亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物がシアン含有廃水中のシアン含有量に対してモル比で少なくとも0.2倍の濃度であり、かつ金属化合物がシアン含有廃水中において0.1〜1000mg/Lの濃度であるのが好ましい。
また、本発明のシアン含有廃水の処理方法は、シアン含有廃水中のシアン含有量および金属化合物濃度を予め測定し、測定したシアン含有量に応じた亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、測定した金属化合物濃度に応じた金属化合物とを、同時または別々に該廃水に添加するのが好ましい。
Therefore, in the method for treating cyanide-containing wastewater of the present invention, the molar ratio of chlorite or a compound capable of generating chlorite ions in the wastewater is at least 0.2 with respect to the cyan content in the cyanide-containing wastewater. It is preferable that the concentration is double and the concentration of the metal compound is 0.1 to 1000 mg / L in the cyan-containing wastewater.
Further, in the method for treating cyanide-containing wastewater of the present invention, the cyanide content and metal compound concentration in the cyanide-containing wastewater are measured in advance, and chlorite or chlorite in the wastewater according to the measured cyanide content. It is preferable to add the compound capable of generating ions and the metal compound according to the measured concentration of the metal compound to the waste water simultaneously or separately.
(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、チオシアン酸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。
また。本発明のシアン含有廃水の処理方法は、シアン含有廃水がシアン化物イオン、易分解性シアン錯体および難分解性シアン錯体のうちの少なくとも1種を含有する廃水である場合の処理に好適である。
(5) Cyanide-containing wastewater The cyanide-containing wastewater to be treated in the present invention includes metallic cyanide, cyanide, and cyanide discharged from iron making factories, chemical factories, plating factories, coke manufacturing factories, metal surface treatment factories, and the like. Examples thereof include cyanide-containing wastewater containing complexes, cyanide complex ions, thiocyanide ions, etc., cyanide-containing wastewater discharged in the treatment process of radioactively contaminated water, and cyanide-containing wastewater discharged from a soil treatment apparatus. In particular, the method for treating cyan-containing wastewater of the present invention is suitable for treating cyan-containing wastewater having a strong buffering action, that is, cyan-containing wastewater containing ammonium ions, such as coke oven wastewater.
Also. The method for treating cyanide-containing wastewater of the present invention is suitable for treatment when the cyanide-containing wastewater is wastewater containing at least one of cyanide ion, easily decomposable cyanide complex and persistent cyanide complex.
(5−1)金属イオン
シアン含有廃水は、併用する金属化合物に相当する金属イオンを含有していてもよく、マンガンイオン、鉄イオン、亜鉛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。
シアン含有廃水が添加する金属化合物に相当する金属イオンを元々含有する場合には、廃水中のシアンとの反応によってマンガン塩、鉄塩、亜鉛塩および銅塩のような金属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り、その含有量を考慮して、金属化合物の添加量を設定すればよい。
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価および3価、亜鉛イオンは2価、銅イオンでは1価および2価であるのが好ましい。
シアン含有廃水がマンガンイオン、鉄イオン、亜鉛イオン、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、上記のようにシアン含有廃水に金属化合物を添加すればよい。その際、金属イオン濃度と金属化合物濃度とは、化合物により換算すればよい。
(5-1) Metal Ion The cyan-containing wastewater may contain a metal ion corresponding to the metal compound used in combination, and one or more metal ions selected from manganese ion, iron ion, zinc ion and copper ion. Is originally contained.
When the cyan-containing wastewater originally contains a metal ion corresponding to a metal compound added, the reaction with cyanide in the wastewater produces metal salts such as manganese salt, iron salt, zinc salt and copper salt, respectively. The effect of removing cyanide of the present invention will be promoted, and the amount of the metal compound added may be set in consideration of the content thereof.
The metal ion can have various valences depending on the metal species, but in the present invention, the manganese ion is divalent, the iron ion is divalent and trivalent, the zinc ion is divalent, and the copper ion is monovalent and divalent. It is preferable to have it.
When the cyanine-containing wastewater does not originally contain manganese ions, iron ions, zinc ions, and copper ions, or when the concentration is low even if it is contained, a metal compound may be added to the cyanese-containing wastewater as described above. At that time, the metal ion concentration and the metal compound concentration may be converted by the compound.
シアン含有廃水に含有するマンガンイオン濃度は、0.1〜1000mg/L程度である。
マンガンイオン濃度が0.1mg/L未満では、シアン除去の促進効果が十分に得られないことがある。一方、マンガンイオン濃度が1000mg/Lを超えると、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、600、700、800、900、1000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 cyan-containing wastewater is about 0.1 to 1000 mg / L.
If the manganese ion concentration is less than 0.1 mg / L, the effect of promoting the removal of cyanide may not be sufficiently obtained. On the other hand, if the manganese ion concentration exceeds 1000 mg / L, it 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, 600, 700, 800, 900, 1000.
The preferred manganese ion concentration is 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、0.1〜1000mg/L程度である。
鉄イオン濃度が0.1mg/L未満では、シアン除去の促進効果が十分に得られないことがある。一方、鉄イオン濃度が1000mg/Lを超えると、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、600、700、800、900、1000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 cyan-containing wastewater is about 0.1 to 1000 mg / L.
If the iron ion concentration is less than 0.1 mg / L, the effect of promoting the removal of cyanide may not be sufficiently obtained. On the other hand, if the iron ion concentration exceeds 1000 mg / L, it not only adversely affects the environment but is also economically unfavorable.
The 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, 600, 700, 800, 900, 1000.
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亜鉛イオン濃度は、0.1〜1000mg/L程度である。
亜鉛イオン濃度が0.1mg/L未満では、シアン除去の促進効果が十分に得られないことがある。一方、亜鉛イオン濃度が1000mg/Lを超えると、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。
具体的な亜鉛イオン濃度(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、600、700、800、900、1000である。
好ましい亜鉛イオン濃度は、0.1〜150mg/Lであり、より好ましくは5〜100mg/Lである。
The zinc ion concentration contained in the cyan-containing wastewater is about 0.1 to 1000 mg / L.
If the zinc ion concentration is less than 0.1 mg / L, the effect of promoting the removal of cyanide may not be sufficiently obtained. On the other hand, if the zinc ion concentration exceeds 1000 mg / L, it not only adversely affects the environment but is also economically unfavorable.
Specific zinc ion concentrations (mg / L) are, 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, 600, 700, 800, 900, 1000.
The preferred zinc ion concentration is 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銅イオン濃度は、0.1〜1000mg/L程度である。
銅イオン濃度が0.1mg/L未満では、シアン除去の促進効果が十分に得られないことがある。一方、銅イオン濃度が1000mg/Lを超えると、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、600、700、800、900、1000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 cyan-containing wastewater is about 0.1 to 1000 mg / L.
If the copper ion concentration is less than 0.1 mg / L, the effect of promoting the removal of cyanide may not be sufficiently obtained. On the other hand, if the copper ion concentration exceeds 1000 mg / L, it not only adversely affects the environment but is also economically unfavorable.
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, 600, 700, 800, 900, 1000.
The preferred copper ion concentration is 0.1 to 150 mg / L, more preferably 2 to 100 mg / L.
本発明において処理対象となるシアン含有廃水におけるシアンの含有量は、特に限定されないが、上記のシアン含有廃水は、一般に全シアン濃度で2〜500mg/L程度である。このようなシアン含有廃水を処理する場合には、シアン含有廃水に対して、亜塩素酸濃度として2.5〜10000mg/Lの亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物と、0.1〜1000mg/Lの濃度の金属化合物をシアン含有廃水に併用すればよい。 The content of cyanide in the cyanide-containing wastewater to be treated in the present invention is not particularly limited, but the above-mentioned cyanide-containing wastewater generally has a total cyanide concentration of about 2 to 500 mg / L. When treating such cyan-containing wastewater, chlorite ions having a chlorite concentration of 2.5 to 10,000 mg / L or the wastewater can be generated with respect to the cyan-containing wastewater. The compound and a metal compound having a concentration of 0.1 to 1000 mg / L may be used in combination with the cyanide-containing wastewater.
(5−2)シアン含有廃水のpH
シアン含有廃水は、pH6〜9であるのが好ましい。
シアン含有廃水がpH6未満またはpH9を超えると、シアンと併用する化合物との反応が不完全になり、効率的にシアンを除去できないことがある。
処理対象のシアン含有廃水は、通常、pH6〜9程度であることからpH調整の必要はないが、必要に応じて、本発明の処理における反応を妨げない酸またはアルカリ、例えば硫酸または水酸化ナトリウムを処理廃水に添加して、pH調整をすればよい。
(5-2) pH of cyan-containing wastewater
The cyan-containing wastewater preferably has a pH of 6 to 9.
If the cyan-containing wastewater is less than pH 6 or more than pH 9, the reaction with the compound used in combination with cyan becomes incomplete, and cyan may not be removed efficiently.
Since the pH of the cyan-containing wastewater to be treated is usually about 6 to 9, it is not necessary to adjust the pH, but if necessary, an acid or alkali that does not interfere with the reaction in the treatment of the present invention, for example, sulfuric acid or sodium hydroxide. May be added to the treated wastewater to adjust the pH.
(5−3)処理および沈殿分離
亜塩素酸塩または該廃水中で亜塩素酸イオンを発生し得る化合物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分以上であればよい。
(5-3) Treatment and Separation Separation When adding compounds and metal compounds that can generate chlorite ions in chlorite or the waste water, and when reacting these added compounds with cyanide, cyanide In terms of removal effect, it is preferable to stir the mixed solution. This stirring is preferably carried out with each addition of each compound.
Further, in order to promote the reaction during stirring, the mixed solution is preferably in a state of being heated to some extent so that the added compound is not decomposed, and the liquid temperature thereof is about 20 to 50 ° C.
Further, the time required for the reaction during stirring varies depending on the amount of cyanide-containing wastewater, the type and concentration of cyanide, the form of the treatment apparatus and its scale, etc., but it is appropriate so that the cyanide and the added compound come into sufficient contact with each other. You just have to decide. Usually, the stirring time may be 10 minutes or more.
併用する化合物の添加、撹拌混合、沈降分離、懸濁物質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、凝集剤を添加してもよい。
Known devices such as additive tanks, reaction treatment tanks, thickeners and turbidity sedimentation basins can be used for a series of operations such as addition of compounds to be used, stirring and mixing, sedimentation separation, and removal of suspended substances. The existing device may be diverted.
In the method for treating cyanide-containing wastewater of the present invention, known agents such as rust preventives, corrosion inhibitors, scale dispersants, and slime control agents may be used in combination as long as the effects of the present invention are not impaired.
Further, in the sedimentation separation, a flocculant may be added as long as the effect of the present invention is not impaired.
以上の処理により、従来よりも薬剤添加量を極力抑え、設備への腐食などの作業環境の悪化を軽減し、簡便な操作で安全にかつ安価に廃水中のシアンを除去し、処理前のシアン濃度(全シアン含有量(mg/L))を排水基準値以下に顕著に低減させることができ、処理後の廃水を中和処理なしに、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。
Through the above treatment, the amount of chemicals added is suppressed as much as possible, the deterioration of the working environment such as corrosion to equipment is reduced, and cyan in wastewater is safely and inexpensively removed by simple operation, and cyan before treatment. The concentration (total cyan content (mg / L)) can be significantly reduced below the wastewater standard value, and the treated wastewater can be discharged or reused as it is into sewage or the like without neutralization treatment.
In the method of the present invention, when the treated wastewater is discharged as it is, an amount of a compound necessary for reducing the total cyan concentration to the wastewater standard value or less may be added, but the treated wastewater is diluted with another wastewater. In the case of discharging the wastewater, the compound may be added so that the wastewater after dilution is equal to or less than the above-mentioned wastewater standard value.
本発明を試験例により具体的に説明するが、本発明はこれらの試験例により限定されるものではない。 The present invention will be specifically described with reference to Test Examples, but the present invention is not limited to these Test Examples.
(試験例1)
試験例1では、表1に示す水質を有するシアン含有廃水A(全シアン30mg/L、錯シアン5mg/L含有、pH8.2)を用いた。
具体的には、ヘキサシアノ鉄(II)酸カリウム、シアン化カリウム水溶液、塩化カルシウム2水和物、塩化ナトリウム、硫酸ナトリウム、塩化アンモニウムおよび炭酸水素ナトリウムを用いてシアン含有廃水Aを調製した。
(Test Example 1)
In Test Example 1, cyanide-containing wastewater A having the water quality shown in Table 1 (total cyanide 30 mg / L, complex cyanide 5 mg / L content, pH 8.2) was used.
Specifically, cyanide-containing wastewater A was prepared using potassium hexacyanoferrate (II) acid, an aqueous potassium cyanide solution, calcium chloride dihydrate, sodium chloride, sodium sulfate, ammonium chloride and sodium hydrogen carbonate.
容量100mLのビーカーに、それぞれシアン含有廃水Aを100mL分注し、表2に示す濃度になるように、亜塩素酸ナトリウムまたは金属化合物としての塩化第一銅(CuCl)もしくは塩化第二銅(CuCl2)もしくは硫酸第二銅(CuSO4)を添加し、残りの1種の化合物を添加するか(実施例1〜7)、亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅を同時に添加するか(実施例8)、亜塩素酸ナトリウムのみを添加するか(比較例1)、金属化合物としての塩化第一銅のみを添加するか(比較例2)、亜塩素酸ナトリウムの代わりに次亜塩素酸ナトリウムを添加し、次いで金属化合物としての塩化第一銅を添加して(比較例3)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2に示す値になるように調整した。
Dispense 100 mL of cyan-containing wastewater A into a beaker with a capacity of 100 mL, and make sodium chlorite or cupric chloride (CuCl) or cupric chloride (CuCl) as a metal compound so as to have the concentrations shown in Table 2. 2 ) or cupric sulfate (CuSO 4 ) is added and the remaining one compound is added (Examples 1 to 7), or sodium chlorite and cupric chloride as a metal compound are added at the same time. (Example 8), whether to add only sodium chlorite (Comparative Example 1), or to add only cupric chloride as a metal compound (Comparative Example 2), or hypochlorite instead of sodium chlorite. Sodium chlorite was added, and then copper chloride as a metal compound was added (Comparative Example 3) to obtain test water.
A sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to some of the test waters to adjust the pH of the test waters to the values shown in Table 2.
試験水の調製では、撹拌装置(アズワン株式会社製、マグネチックスターラーREXIM、品番:RS−4AR)を用いて回転数200rpmで30分間撹拌した。
試験水の調製時に2種の化合物を2段階で添加する場合には残りの1種の化合物を、30分間撹拌後、直ちに添加し、同様に回転数200rpmで30分間撹拌した(実施例1〜7、比較例3)。
試験水の調製時に2種の化合物を1段階で(同時に)添加する場合、または1種の化合物のみ添加する場合には、30分間撹拌後、引き続いて同様に回転数200rpmで30分間撹拌した(実施例8、比較例1〜2)。
合計60分間の撹拌終了後、試験水中の懸濁物質を濾別し、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、亜塩素酸ナトリウムおよび金属化合物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、その添加量および添加方法と共に表2に示す。
In the preparation of the test water, a stirrer (manufactured by AS ONE Corporation, magnetic stirrer REXIM, product number: RS-4AR) was used to stir at a rotation speed of 200 rpm for 30 minutes.
When two kinds of compounds are added in two steps at the time of preparing test water, the remaining one kind of compound is added immediately after stirring for 30 minutes, and similarly stirred at a rotation speed of 200 rpm for 30 minutes (Examples 1 to 1). 7. Comparative example 3).
When two compounds were added in one step (simultaneously) at the time of preparing the test water, or when only one compound was added, the mixture was stirred for 30 minutes and then similarly stirred at a rotation speed of 200 rpm for 30 minutes (). Example 8, Comparative Examples 1 and 2).
After stirring for a total of 60 minutes, the suspended substance 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 measured. evaluated.
In this test, a blank test (Comparative Example 4) in which sodium chlorite and a metal compound were not added was carried out at the same time.
The obtained results are shown in Table 2 together with the added compound, the amount of the added compound, and the method of addition.
表2の試験結果から次のことがわかる。
・pH6〜9における亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅もしくは、塩化第二銅もしくは硫酸第二銅の併用処理(実施例1〜8)では、亜塩素酸ナトリウムおよび金属化合物の添加順序に関係なく、十分なシアン除去効果が得られること
・これに対して、pH6.5における亜塩素酸ナトリウムまたは金属化合物としての塩化第一銅を用いた単剤処理(比較例1〜2)では、十分なシアン除去効果が得られないこと
・亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅の併用処理(実施例1および4〜8)では、pH6〜9の範囲で十分なシアン除去効果が得られること
・pH6.5における亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅の併用処理(実施例1、5および6)では、金属化合物の濃度が7.8〜156mg/Lの範囲で十分なシアン除去効果が得られること
・次亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅の併用処理(比較例3)では、亜塩素酸ナトリウムおよび金属化合物としての塩化第一銅の併用処理(実施例8)と比べて低添加量では十分なシアン除去効果が得られないこと
The following can be seen from the test results in Table 2.
-In the combined treatment of sodium chlorite and cuprous chloride as a metal compound, cupric chloride or cupric sulfate (Examples 1 to 8) at pH 6 to 9, addition of sodium chlorite and a metal compound. Sufficient cyanide removal effect can be obtained regardless of the order. In contrast, single agent treatment using sodium chlorite or cuprous chloride as a metal compound at pH 6.5 (Comparative Examples 1 and 2). -Sufficient cyanide removal effect cannot be obtained.-In the combined treatment of sodium chlorite and cuprous chloride as a metal compound (Examples 1 and 4 to 8), sufficient cyanide removal is performed in the pH range of 6 to 9. Effect-In the combined treatment of sodium chlorite and cuprous chloride as a metal compound at pH 6.5 (Examples 1, 5 and 6), the concentration of the metal compound was 7.8 to 156 mg / L. Sufficient cyanide removal effect can be obtained in the range.-In the combined treatment of sodium hypochlorite and cuprous chloride as a metal compound (Comparative Example 3), sodium chlorite and cuprous chloride as a metal compound A sufficient cyanide removal effect cannot be obtained with a low addition amount as compared with the combined treatment (Example 8).
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