CN115140864A - Method for producing sludge containing heavy metals - Google Patents
Method for producing sludge containing heavy metals Download PDFInfo
- Publication number
- CN115140864A CN115140864A CN202210320141.6A CN202210320141A CN115140864A CN 115140864 A CN115140864 A CN 115140864A CN 202210320141 A CN202210320141 A CN 202210320141A CN 115140864 A CN115140864 A CN 115140864A
- Authority
- CN
- China
- Prior art keywords
- sludge
- wastewater
- copper
- salt
- slurry
- 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.)
- Pending
Links
- 239000010802 sludge Substances 0.000 title claims abstract description 143
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 86
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 239000002002 slurry Substances 0.000 claims abstract description 50
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 29
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 25
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 25
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 108
- 229910052802 copper Inorganic materials 0.000 claims description 108
- 239000010949 copper Substances 0.000 claims description 108
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 26
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 74
- 239000000203 mixture Substances 0.000 description 42
- 238000003756 stirring Methods 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229920002873 Polyethylenimine Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- -1 and among them Chemical compound 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- JPGSFSFMINKKJZ-UHFFFAOYSA-N 2-[1,2-dicarboxyethyl(hydroxy)amino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)N(O)C(CC(O)=O)C(O)=O JPGSFSFMINKKJZ-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- DRAJWRKLRBNJRQ-UHFFFAOYSA-N Hydroxycarbamic acid Chemical compound ONC(O)=O DRAJWRKLRBNJRQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- MKBUQYWFFBCMFG-UHFFFAOYSA-N acetic acid propane-1,1-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CCC(N)N MKBUQYWFFBCMFG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- NLZXQOOZQAGNCY-UHFFFAOYSA-L dipotassium;piperazine-1,4-dicarbodithioate Chemical compound [K+].[K+].[S-]C(=S)N1CCN(C([S-])=S)CC1 NLZXQOOZQAGNCY-UHFFFAOYSA-L 0.000 description 2
- ZCVJLQSBJNPBQE-UHFFFAOYSA-L disodium;piperazine-1,4-dicarbodithioate Chemical compound [Na+].[Na+].[S-]C(=S)N1CCN(C([S-])=S)CC1 ZCVJLQSBJNPBQE-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- PNKGVPLMWAEASD-UHFFFAOYSA-N piperazine-1,4-dicarbodithioic acid Chemical compound SC(=S)N1CCN(C(S)=S)CC1 PNKGVPLMWAEASD-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- OJXAKZMMWGESHM-UHFFFAOYSA-L magnesium sulfanide Chemical compound [Mg++].[SH-].[SH-] OJXAKZMMWGESHM-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- OFZRVUCVOAUMDT-UHFFFAOYSA-M potassium;n,n-diethylcarbamodithioate Chemical compound [K+].CCN(CC)C([S-])=S OFZRVUCVOAUMDT-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a method for producing a sludge containing heavy metals. A conventionally known method for producing a heavy metal-containing sludge is characterized in that a sulfidizing agent such as sodium hydrosulfide is added to a heavy metal-containing wastewater while maintaining the pH at 1 to 5. However, the addition of sodium hydrosulfide under such acidic conditions has a problem that a highly toxic hydrogen sulfide gas is likely to be generated. A method for producing a sludge containing heavy metals, characterized by adding a salt of an alkali metal hydroxide and a dithiocarbamate to a wastewater containing heavy metals and then adding a polymeric flocculant to the wastewater to produce a slurry, or adding a salt of calcium hydroxide and a dithiocarbamate to a wastewater containing heavy metals to produce a slurry and then separating a solid component from the slurry.
Description
Technical Field
The present invention relates to a method for producing sludge containing heavy metals such as copper.
Background
As treatment methods for removing heavy metals from wastewater containing heavy metals, there are known: alkaline precipitation methods based on calcium hydroxide, sodium hydroxide, and the like; a coprecipitation method using iron salts such as ferric chloride and aluminum salts such as aluminum sulfate. These methods are easy to control the reaction and have high process safety, but may not reduce the heavy metals in the treated wastewater to a value equal to or less than the wastewater standard (wastewater standard by japanese water pollution prevention law).
Among the sludge containing heavy metals obtained by the above-described wastewater treatment, sludge containing valuable metals such as copper and nickel can be reused as a metal raw material. From the viewpoint of recycling of such valuable metals, it is preferable to increase the content of valuable metals in the sludge, and as a method therefor, a method using a sulfidizing agent such as sodium hydrosulfide has been reported (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2007-69068
Disclosure of Invention
Problems to be solved by the invention
The method described in patent document 1 is characterized by adding a sulfidizing agent such as sodium hydrosulfide to heavy metal-containing wastewater while maintaining the pH at 1 to 5. However, the addition of sodium hydrosulfide under such acidic conditions has a problem that a highly toxic hydrogen sulfide gas is likely to be generated.
Means for solving the problems
As a result of intensive studies to solve the above problems, the inventors of the present invention have found a method for producing a heavy metal-containing sludge, which comprises adding an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate to a heavy metal-containing wastewater, adding a polymeric flocculant to the wastewater to produce a slurry, and separating a solid component from the slurry, thereby completing the present invention.
That is, the present invention has the following gist.
[1]
A method for producing a heavy metal-containing sludge, characterized by adding an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate to a heavy metal-containing wastewater, then adding a polymeric flocculant to produce a slurry, and then separating a solid component from the slurry.
[2]
The method for producing a heavy metal-containing sludge according to [1], wherein an alkali metal hydroxide or calcium hydroxide is added to the heavy metal-containing wastewater to adjust the pH to a range of 6 to 11, and then a salt of a dithiocarbamate is added to produce a slurry, and then a solid component is separated from the slurry.
[3]
The method for producing a heavy metal-containing sludge according to [1] or [2], wherein the heavy metal is copper, and the heavy metal-containing wastewater is wastewater containing copper at a concentration of 20mg/L to 1500 mg/L.
[4]
The method for producing a heavy metal-containing sludge according to any one of [1] to [3], wherein the salt of the dithiocarbamate is piperazine-1,4-potassium bisdithiocarboxylate, piperazine-1,4-sodium bisdithiocarboxylate, or a reaction product of tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide.
[5]
The method for producing a heavy metal-containing sludge according to any one of [1] to [4], wherein the alkali metal hydroxide added to the heavy metal-containing wastewater is sodium hydroxide or potassium hydroxide.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide: compared with the prior art, the method for preparing the sludge containing the heavy metals basically does not generate hydrogen sulfide gas.
Further, according to the present invention, the following effects are exhibited: compared with the prior art, the content of valuable metals in the sludge containing heavy metals can be improved, and the recycling treatment efficiency of the valuable metals can be improved.
Further, the method for producing a heavy metal-containing sludge of the present invention can be carried out at a pH in the neutral region, and therefore, is industrially extremely useful in that the pH adjustment step required in the prior art for discharging final wastewater can be omitted.
Detailed Description
The present invention will be described in detail below.
One embodiment of the present invention relates to a method for producing a heavy metal-containing sludge, characterized by adding an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate to a heavy metal-containing wastewater, then adding a polymeric flocculant to produce a slurry, and then separating a solid component from the slurry.
The heavy metal-containing wastewater used in the present invention is not particularly limited, and examples thereof include: containing 1 or more than 2 kinds of heavy metal-containing wastewater selected from the group consisting of cadmium, chromium, copper, iron, mercury, nickel, lead, zinc, palladium, gold, silver, platinum, cobalt, indium, molybdenum, antimony, tin, titanium, zirconium, manganese and tungsten. Among these, copper-containing wastewater is preferable in terms of excellent production efficiency of sludge containing heavy metals.
The concentration of the heavy metal in the heavy metal-containing wastewater is not particularly limited, but is preferably 20mg/L to 1500mg/L, more preferably 20mg/L to 1000mg/L, and further preferably 20mg/L to 500mg/L, in terms of excellent efficiency of producing the sludge containing the heavy metal.
That is, the wastewater containing heavy metals used in the present invention preferably contains copper and has a copper content of 20mg/L to 1500mg/L, preferably contains copper and has a copper content of 20mg/L to 1000mg/L, and preferably contains copper and has a copper content of 20mg/L to 500 mg/L.
The wastewater containing heavy metals is not particularly limited, and examples thereof include industrial wastewater and domestic wastewater, and more specifically, wastewater from plating plants, metal processing plants, and automobile plants.
Examples of the alkali metal hydroxide used in the present invention include sodium hydroxide, potassium hydroxide, and lithium hydroxide, and among them, sodium hydroxide and potassium hydroxide are preferable in terms of easy availability.
The salt of a dithiocarbamate used in the present invention is not particularly limited as long as it is a compound having a dithiocarbamate group in the molecule. Examples thereof include: a compound obtained by reacting an amine compound having at least 1 amino group selected from the group consisting of a primary amino group and a secondary amino group, carbon disulfide, and an alkali metal hydroxide. More preferably, the compound is obtained by reacting an amine compound having 2 or more amino groups selected from the group consisting of a primary amino group and a secondary amino group, carbon disulfide, and an alkali metal hydroxide.
As the amine compound having at least 1 amino group selected from the group consisting of a primary amino group and a secondary amino group, specifically, diethylamine, piperazine, pyrrolidine, piperidine, diethylenetriamine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, polyethyleneimine, a condensate of polyethyleneimine and benzyl chloride, and the like can be exemplified.
The salt of the dithiocarbamate used in the present invention is preferably a reaction product of piperazine, tetraethylenepentamine or diethylamine with carbon disulfide and an alkali metal hydroxide in terms of excellent efficiency of producing a sludge containing heavy metals and stability of the compound.
The reaction product of piperazine with carbon disulfide and an alkali metal hydroxide includes, for example, piperazine-1,4-bisdithiocarboxylic acid potassium salt, or piperazine-1,4-bisdithiocarboxylic acid sodium salt.
Examples of the reaction product of diethylamine, carbon disulfide and an alkali metal hydroxide include potassium N, N-diethyldithiocarbamate and sodium N, N-diethyldithiocarbamate.
Tetraethylenepentamine is industrially produced in the form of a composition containing a linear body [ see the following formula (1) ] of the main component and the like [ see the following formulas (2) to (4) ], and therefore, a salt of dithiocarbamic acid obtained by a reaction of tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide becomes a composition corresponding to the composition of tetraethylenepentamine as a raw material.
The alkali metal hydroxide used for obtaining the salt of the dithiocarbamic acid used in the present invention includes sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like, and sodium hydroxide and potassium hydroxide are particularly preferable in terms of easy availability.
As the salt of dithiocarbamic acid used in the present invention, a potassium salt of piperazine-1,4-bisdithiocarboxylic acid, a sodium salt of piperazine-1,4-bisdithiocarboxylic acid, or a reaction product of tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide is preferable in terms of excellent efficiency in producing a sludge containing a heavy metal, more preferably piperazine-1,4-bisdithiocarboxylic acid potassium salt, or piperazine-1,4-bisdithiocarboxylic acid sodium salt.
Examples of the polymeric flocculant used in the present invention include an acrylic acid polymer, an acrylamide polymer, and a dimethylaminoethyl methacrylate polymer. Among them, acrylic acid polymers are preferable in terms of flocculation property of heavy metal solids. As such a polymeric flocculant, a commercially available product is preferably used as it is.
Hereinafter, a method for producing a heavy metal-containing sludge, which is characterized by adding an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate to a heavy metal-containing wastewater, then adding a polymeric flocculant to produce a slurry, and then separating a solid component from the slurry, will be described.
Examples of the method for adding the alkali metal hydroxide or calcium hydroxide and the salt of dithiocarbamic acid to the heavy metal-containing wastewater include: the method of adding the solid matter or the aqueous solution to the heavy metal-containing wastewater is preferably a method of adding the aqueous solution in terms of excellent operability.
When the alkali metal hydroxide or calcium hydroxide and the salt of the dithiocarbamic acid are added to the wastewater containing the heavy metal, they may be added separately or they may be added after mixing them in advance. In the case of separate addition, it is preferable to add the alkali metal hydroxide or calcium hydroxide first in terms of pH adjustment described later.
In the present invention, the amount of the alkali metal hydroxide or calcium hydroxide to be added is not particularly limited, and is preferably added so that the pH of the heavy metal-containing wastewater is in the range of 6 to 11, more preferably in the range of 6 to 10, and still more preferably in the range of 6 to 8.
When a dithiocarbamate is added to a heavy metal-containing wastewater, the pH of the heavy metal-containing wastewater is preferably in a neutral to alkaline region (pH 6 to 14), more preferably in a neutral to weakly alkaline region (pH 6 to 11), and even more preferably in a neutral region (pH 6 to 8), from the viewpoint of suppressing the generation of hydrogen sulfide gas associated with the decomposition of the dithiocarbamate, and from the viewpoint of enabling the pH of the wastewater after the immobilization of the heavy metal to be discharged.
Therefore, it is preferable to add an alkali metal hydroxide or calcium hydroxide in an amount satisfying the above-mentioned preferable pH range, and then add a salt of dithiocarbamic acid to the heavy metal-containing wastewater in the preferable pH range.
In the present invention, the amount of the salt of dithiocarbamic acid to be added is not particularly limited, and is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 20 to 150 parts by mass, based on 100 parts by mass of the heavy metal contained in the heavy metal-containing wastewater.
After addition of the alkali metal hydroxide or calcium hydroxide and the salt of the dithiocarbamic acid to the waste water containing heavy metals, the addition mixture is preferably stirred, and the stirring time is usually selected from the range of several minutes to 2 hours.
When an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate are added to the heavy metal-containing wastewater, an additive such as an inorganic sulfide, a polyamine having a weight average molecular weight of 300 or more, a polyamine having 3 to 8 nitrogen atoms, or a hydroxyamino-carboxylic acid or a salt thereof may be separately added. By using such an additive, it is expected that the efficiency of producing the sludge containing heavy metals is improved, or the separation operation of the solid component (wet sludge) from the slurry, which will be described later, becomes easy.
The timing of addition of the additive may be before the addition of the salt of the dithiocarbamate, simultaneously with the addition of the salt of the dithiocarbamate, or after the addition of the salt of the dithiocarbamate.
Examples of the inorganic sulfide include sodium sulfide, sodium hydrosulfide, potassium sulfide, potassium hydrosulfide, calcium sulfide, calcium hydrosulfide, magnesium hydrosulfide, and ammonium sulfide.
Examples of the polyamine having a weight average molecular weight of 300 or more include a polyethyleneimine having a weight average molecular weight of 300 or more, a polyetheramine having a weight average molecular weight of 300 or more (a compound obtained by converting a terminal hydroxyl group into a primary amino group such as polypropylene glycol or polyethylene glycol), and the like.
Examples of the polyamine having 3 to 8 nitrogen atoms include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heptaethyleneoctamine.
Examples of the hydroxyamino carboxylic acid or a salt thereof include hydroxyethylethylenediaminetriacetic acid (HEDTA), diaminopropanetetraacetic acid (DPTA), hydroxyiminodisuccinic acid (HIDS), and a salt thereof.
When a polymeric flocculant is further added after an alkali metal hydroxide or calcium hydroxide and a salt of dithiocarbamic acid are added to wastewater containing heavy metals, the slurry can be produced by adding the polymeric flocculant. The slurry comprises: the heavy metal, the salt of the dithiocarbamate, and the polymer flocculant react with each other to precipitate a solid. By carrying out the production method of the present invention, heavy metals dissolved in wastewater are insolubilized, and therefore, the concentration of heavy metals in the wastewater can be reduced.
In the present invention, the amount of the polymeric flocculant to be added is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the heavy metal contained in the heavy metal-containing wastewater.
As the flocculant, inorganic flocculants such as an iron compound such as ferric chloride or ferrous sulfate, or an aluminum compound such as aluminum sulfate or polyaluminum chloride are known. The use of such an inorganic flocculant is not preferable because the content of valuable metals in the sludge containing heavy metals is lowered.
The heavy metal-containing sludge targeted by the present invention can be produced by adding a polymeric flocculant to obtain a slurry and separating the solid component from the slurry.
The method for separating the solid component from the slurry is not particularly limited, and examples thereof include: filtration, centrifugation, or a method of separating the solid component from the supernatant after settling (settling separation).
The solid content separated from the slurry by the above-described operation is a heavy metal-containing sludge in the present invention, and is referred to as wet sludge in examples and the like described later.
Further, the wet sludge is dried to produce a dried sludge. The dried sludge is also a heavy metal-containing sludge in the present invention.
In the production method of the present invention, the temperature of the heavy metal-containing wastewater, the temperature of the aqueous solution of the chemical, and the temperature of the slurry in the process of adding the chemical are preferably in the range of-10 to 40 ℃, more preferably in the range of 4 to 40 ℃.
The method for producing the heavy metal-containing sludge of the present invention may be carried out continuously or in a single manner (batch).
Examples
The present invention will be specifically described below, but the present invention is not to be construed as being limited by these examples.
(method of analyzing heavy Metal concentration)
The concentration of the heavy metal in the aqueous solution was measured using an ICP emission spectrophotometer (ICPE-9800, manufactured by Shimadzu corporation).
The amount of hydrogen sulfide GAS generated from the aqueous solution in the wastewater treatment was measured by a GAS detection tube 4LK manufactured by GAS TECH.
(method of defining and analyzing sludge)
Sludge obtained by treating wastewater containing heavy metals and performing solid-liquid separation is called wet sludge. The amount of wet sludge produced by treating 1L of heavy metal-containing wastewater and performing solid-liquid separation is referred to as wet sludge production [ g/L ].
Sludge (wet sludge) obtained by treating wastewater containing heavy metals and performing solid-liquid separation is heated and dried, and the sludge is called dry sludge. In this example, the wet sludge was heated at 105 ℃ for 2 hours to obtain a dried sludge. The amount of dry sludge produced by treating 1L of heavy metal-containing wastewater, separating the solid from the liquid, and then drying the treated wastewater is referred to as dry sludge production [ g/L ].
The water content (% by weight) of the wet sludge was calculated by the following calculation formula.
(1-amount of produced dry sludge [ g/L ]/amount of produced wet sludge [ g/L ]). Times.100
The content of heavy metals (wt%) in the dried sludge was calculated by the following calculation formula.
(heavy Metal concentration [ mg/L ] before wastewater treatment]Concentration of heavy metals [ mg/L ] after wastewater treatment])×10 -3 Production of dried sludge [ g/L]×100
(preparation of salt A of dithiocarbamic acid)
After 112g of piperazine (manufactured by Tosoh corporation) and 386g of pure water were mixed, 306g of 48 wt% potassium hydroxide (manufactured by Kishida Chemical Co., ltd.) and 196g of carbon disulfide (manufactured by Kishida Chemical Co., ltd.) were alternately added dropwise in 4 portions, respectively, under stirring at 25 ℃ in a nitrogen gas flow. Stirring was carried out for 1 hour to obtain an aqueous solution containing 40% by weight of a compound represented by the following formula (5) (piperazine-1,4-potassium bisdithiocarboxylate).
(preparation of salt B of dithiocarbamic acid)
159g of tetraethylenepentamine (made by Tosoh Corp.) and 331g of pure water were mixed, and 281g of 48 wt% sodium hydroxide (made by Kishida Chemical Co., ltd.) and 230g of carbon disulfide (made by Kishida Chemical Co., ltd.) were alternately added dropwise in 4 portions, respectively, under stirring at 25 ℃ in a nitrogen gas stream. Stirring was carried out for 1 hour to obtain an aqueous solution containing 40% by weight of a compound represented by the following formula (6).
(preparation of salt C of dithiocarbamic acid)
To 52.6g of sodium N, N-diethyldithiocarbamate trihydrate (manufactured by Fuji photo film and Wako pure chemical industries, ltd.) was added pure water to make the total amount to 100g, to obtain an aqueous solution containing 40 wt% of sodium N, N-diethyldithiocarbamate.
(polymeric flocculant)
ORFLOCK OA-23 (weak anionic polymer, polyacrylic polymer) manufactured by Organo corporation was used as the polymeric flocculant.
Example 1
1000mL of wastewater (pH 2, copper content 210 mg/L) from company A was put into a 2000mL beaker equipped with a vibration Tester (Jar Tester). Then, 11.5g of a 10% aqueous sodium hydroxide solution was added thereto while stirring at 150rpm, to adjust the wastewater from the aforementioned company A to pH8. Subsequently, 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the salt A of dithiocarbamic acid is 57 parts by mass with respect to 100 parts by mass of copper) was added, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 2g (0.95 parts by mass of the polymeric flocculant per 100 parts by mass of copper) of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in a series of treatment steps is less than 1ppm (the second definition of sixty-five items of the Japanese Industrial safety and health Act). The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 1.
Example 2
300mg of an aqueous solution containing 40% by weight of the compound represented by the above formula (6) (salt B of dithiocarbamic acid) (100 parts by mass relative to copper, 57 parts by mass of the salt B of a dithiocarbamate) was prepared in the same manner as in example 1, except that 300mg of an aqueous solution containing 40% by weight of the compound represented by the above formula (5) (the salt a of a dithiocarbamate) was added. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 1.
Example 3
The same operation as in example 1 was performed except that 300mg of an aqueous solution containing 40 wt% of sodium N, N-diethyldithiocarbamate (salt C of dithiocarbamic acid) (57 parts by mass of salt C of dithiocarbamic acid relative to 100 parts by mass of copper) was added instead of 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (salt a of dithiocarbamic acid). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 1.
Comparative example 1
A2000 mL beaker was set in a Jar shaker (Jar Tester), and 1000mL of wastewater (pH 2, copper concentration 210 mg/L) from company A was charged. Then, 11.5g of a 10% aqueous sodium hydroxide solution was added thereto while stirring at 150rpm to adjust the pH of the wastewater from the aforementioned company A to 8, followed by stirring at 150rpm for 1 hour. Subsequently, 2g of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as a polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 10 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 1.
Reference example 1
The same operation as in example 1 was carried out except that 1000mg of an aqueous solution of polyaluminum chloride (10% by weight in terms of alumina concentration) as an inorganic flocculant was additionally added before the addition of the polymeric flocculant. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 1.
[ Table 1]
Example 4
A stirrer was placed in an 8L vessel, and 6L of wastewater (pH 3, copper content 70 mg/L) from company B was charged. Next, 10.2g of a 10% aqueous sodium hydroxide solution was added thereto while stirring at 250rpm, whereby the wastewater from the aforementioned company B was adjusted to pH7. Subsequently, 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the salt A of dithiocarbamic acid is 29 parts by mass relative to 100 parts by mass of copper) and 12mg of polyethyleneimine (average molecular weight 1800) were added, and the mixture was stirred at 200rpm for 10 minutes. Subsequently, 12g of an aqueous ORFLOCK OA-23 solution (2.9 parts by mass of the polymeric flocculant per 100 parts by mass of copper) having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 100rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The supernatant 5L was transferred to another vessel, and the slurry 1L containing the remaining treated water and sludge was set in a table centrifuge (Seikagaku Seisakusho S700T) and centrifuged at 3800rpm for 20 minutes to separate the aqueous solution from the sludge (wet sludge). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 2.
Example 5
The same operation as in example 4 was carried out except that 12mg of polyethyleneimine (average molecular weight: 1800) was added instead of 12mg of polyethyleneimine (average molecular weight: 1 ten thousand). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 2.
Example 6
The same operation as in example 4 was carried out except that 12mg of polyethyleneimine (average molecular weight: 200 ten thousand) was added instead of 12mg of polyethyleneimine (average molecular weight: 1800). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 2.
Comparative example 2
A stirrer was placed in an 8L vessel, and 6L of wastewater (pH 3, copper content 70 mg/L) from company B was charged. Next, 10.2g of a 10% aqueous sodium hydroxide solution was added while stirring at 250rpm, the pH of the wastewater from the aforementioned company B was adjusted to 7, and the mixture was stirred at 200rpm for 10 minutes. Subsequently, 12g of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as a polymeric flocculant was added thereto, and the mixture was stirred at 100rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The supernatant 5L was transferred to another vessel, and the slurry 1L containing the remaining treated water and sludge was set in a table centrifuge (Seikagaku Seisakusho S700T) and centrifuged at 3800rpm for 20 minutes to separate the aqueous solution from the sludge (wet sludge). The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 2.
[ Table 2]
Example 7
A2000 mL beaker was set in a Jar shaker (Jar Tester), and 1000mL of wastewater (pH 1.5, copper concentration 500 mg/L) from company C was charged. Next, a 20% aqueous solution of sodium hydroxide was added while stirring at 150rpm, to adjust the wastewater from the aforementioned company C to pH9. Subsequently, 500mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (40 parts by mass of the salt A of dithiocarbamic acid per 100 parts by mass of copper) was added, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 2g (0.4 parts by mass of the polymeric flocculant per 100 parts by mass of copper) of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left standing for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of dry sludge produced, the water content of the wet sludge, and the copper content in the dry sludge are shown in table 3.
Examples 8 to 10
The same operation as in example 7 was carried out except that the kind and amount of the reagents to be added were changed to the conditions shown in table 3. In example 9, the salt a of dithiocarbamic acid was 64 parts by mass relative to 100 parts by mass of copper. The results are shown in Table 3. The amount of hydrogen sulfide gas generated in a series of treatment steps was 1ppm lower than the evaluation reference value for the working environment.
Comparative example 3
A2000 mL beaker was set in a Jar shaker (Jar Tester), and 1000mL of wastewater (pH 1.5, copper concentration 500 mg/L) from company C was charged. Next, a 20% aqueous solution of sodium hydroxide was added while stirring at 150rpm, to adjust the wastewater from the aforementioned company C to pH9. Subsequently, 500mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (salt A of dithiocarbamic acid) was added thereto, and the mixture was stirred at 150rpm for 10 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of dry sludge produced, the water content of the wet sludge, and the copper content in the dry sludge are shown in Table 3.
In the case where no polymeric flocculant is added, the copper concentration after treatment exceeds the standard wastewater value of 3mg/L (based on wastewater of Japanese Water pollution prevention method No. 3), the copper content is also low, and the water content of sludge is high.
Comparative examples 4 to 6 and reference example 2
The same operation as in example 7 was carried out except that the kind and amount of the reagent to be added were changed to the conditions shown in table 3. The results are shown in Table 3.
Comparative examples 4 to 6 are examples treated under conditions outside the scope of the claims of the present application. The concentration of the treated copper exceeds the standard value of the wastewater by 3mg/L. The moisture content of the wet sludge exceeded 90%, and the amount of wet sludge before drying was 2 times or more greater than 80% of the moisture content of the wet sludge in example 7.
Reference example 2 is an example in which calcium hydroxide was used instead of sodium hydroxide, but the copper concentration after treatment exceeded the wastewater reference value of 3mg/L, and the copper concentration in the dried sludge was also 20%, which was lower than that in example 7.
[ Table 3]
Example 11
A500 mL beaker was set in a Jar shaker (Jar Tester), and 300mL of wastewater (pH 1.0, copper concentration 1000 mg/L) from company D was charged. Next, while stirring at 150rpm, a 20% aqueous solution of sodium hydroxide was added to adjust the wastewater from the aforementioned company D to pH8. Subsequently, 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the amount of the salt A of dithiocarbamic acid is 40 parts by mass based on 100 parts by mass of copper) was added thereto, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 600mg of an ORFLOCK OA-23 aqueous solution having a concentration of 0.1 wt% as a polymeric flocculant (0.2 parts by mass of the polymeric flocculant per 100 parts by mass of copper) was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 4.
Comparative example 7 and reference example 3
The same operation as in example 11 was carried out except that the kind and amount of the reagent to be added were changed to the conditions shown in table 4. The results are shown in Table 4.
Comparative example 7 is an example in which dithiocarbamic acid was not used, but the copper concentration after treatment exceeded the standard wastewater value of 3mg/L, and the water content of the wet sludge was as high as 94%.
Reference example 3 is an example in which calcium hydroxide was used instead of sodium hydroxide, but the copper concentration after treatment exceeded the wastewater reference value of 3mg/L, and the copper concentration in the dried sludge was also as low as 9%.
[ Table 4]
Example 12
1000mL of wastewater (pH 2, copper content 210 mg/L) from company A was put into a 2000mL beaker equipped with a vibration Tester (Jar Tester). Then, 18.6g of a 5% calcium hydroxide aqueous solution was added while stirring at 150rpm, to adjust the pH of the wastewater from the aforementioned company A to 8. Subsequently, 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the salt A of dithiocarbamic acid is 57 parts by mass with respect to 100 parts by mass of copper) was added, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 2g (0.95 parts by mass of the polymeric flocculant per 100 parts by mass of copper) of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left standing for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
Example 13
The same operation as in example 12 was carried out except that the polymeric flocculant was not used. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
Example 14
The same operation as in example 12 was performed except that 300mg of an aqueous solution containing 40% by weight of the compound represented by the above formula (6) (the salt B of dithiocarbamic acid was 57 parts by mass relative to 100 parts by mass of copper) was added instead of 300mg of an aqueous solution containing 40% by weight of the compound represented by the above formula (5) (the salt a of dithiocarbamic acid). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
Example 15
The same operation as in example 12 was carried out except that 300mg of an aqueous solution containing 40% by weight of sodium N, N-diethyldithiocarbamate (salt C of dithiocarbamic acid) (57 parts by weight of salt C of dithiocarbamic acid relative to 100 parts by weight of copper) was added instead of 300mg of an aqueous solution containing 40% by weight of the compound represented by the above formula (5) (salt a of dithiocarbamic acid). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
Comparative example 8
1000mL of wastewater (pH 2, copper content 210 mg/L) from company A was put into a 2000mL beaker equipped with a vibration Tester (Jar Tester). Then, 18.6g of a 5% calcium hydroxide aqueous solution was added while stirring at 150rpm to adjust the pH of the wastewater from the aforementioned company A to 8, and then the mixture was stirred at 150rpm for 1 hour. Subsequently, 2g of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as a polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 10 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
Reference example 4
The same operation as in example 12 was carried out except that 1000mg of an aqueous solution of polyaluminum chloride (10% by weight in terms of alumina concentration) as an inorganic flocculant was additionally added before the addition of the polymeric flocculant. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 5.
[ Table 5]
Example 16
A stirrer was placed in an 8L vessel, and 6L of wastewater (pH 3, copper content 70 mg/L) from company B was charged. Then, 16.2g of a 5% calcium hydroxide aqueous solution was added thereto while stirring at 250rpm, to adjust the pH of the wastewater from the aforementioned company B to 7. Subsequently, 300mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the salt A of dithiocarbamic acid is 29 parts by mass relative to 100 parts by mass of copper) and 12mg of polyethyleneimine (average molecular weight 1800) were added, and the mixture was stirred at 200rpm for 10 minutes. Subsequently, 12g of an aqueous ORFLOCK OA-23 solution (2.9 parts by mass of the polymeric flocculant per 100 parts by mass of copper) having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 100rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The resulting mixture was set in a desk centrifuge (Seikagaku Kogyo S700T) and centrifuged at 3800rpm for 20 minutes to separate the aqueous solution and sludge. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 6.
Example 17
The same operation as in example 16 was carried out except that 12mg of polyethyleneimine (average molecular weight: 1800) was added instead of 12mg of polyethyleneimine (average molecular weight: 1 ten thousand). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 6.
Example 18
The same operation as in example 16 was carried out except that 12mg of polyethyleneimine (average molecular weight: 200 ten thousand) was added instead of 12mg of polyethyleneimine (average molecular weight: 1800). The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less as an evaluation reference value for working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 6.
Comparative example 9
A stirrer was placed in an 8L vessel, and 6L of wastewater (pH 3, copper content 70 mg/L) from company B was charged. Subsequently, 6.2g of a 5% calcium hydroxide aqueous solution was added while stirring at 250rpm, the pH of the wastewater from the aforementioned company B was adjusted to 7, and the mixture was stirred at 200rpm for 10 minutes. Subsequently, 12g of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as a polymeric flocculant was added thereto, and the mixture was stirred at 100rpm for 10 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 5 minutes. The supernatant 5L was transferred to another vessel, and the slurry 1L containing the remaining treated water and sludge was set in a table centrifuge (Seikagaku Seisakusho S700T) and centrifuged at 3800rpm for 20 minutes to separate the aqueous solution from the sludge (wet sludge). The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 6.
[ Table 6]
Example 19
1000mL of wastewater (pH 1.5, copper concentration 300 mg/L) from company C was put into a 2000mL beaker equipped with a vibration detector (Jar Tester). Then, while stirring at 150rpm, a 5% aqueous solution of calcium hydroxide was added, the wastewater from the aforementioned company C was adjusted to pH9. Subsequently, 500mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (67 parts by mass of the salt a of dithiocarbamic acid per 100 parts by mass of copper) was added, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 2g (0.67 parts by mass of the polymeric flocculant per 100 parts by mass of copper) of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left to stand for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 7.
Example 20 and comparative examples 10 to 11
The same operation as in example 19 was performed except that the kind and amount of the reagents to be added were changed to the conditions shown in table 7. In example 20, the salt a of dithiocarbamic acid was 107 parts by mass relative to 100 parts by mass of copper. The results are shown in Table 7.
Comparative examples 3 to 4 are examples in which treatment was carried out under conditions outside the scope of the claims of the present application, but the copper concentration after the treatment exceeded the standard wastewater value of 3mg/L.
[ Table 7]
Example 21
A500 mL beaker was set in a Jar Tester (Jar Tester), and 300mL of wastewater (pH 1.0, copper concentration 1000 mg/L) from company D was charged. Next, while stirring at 150rpm, a 5% calcium hydroxide aqueous solution was added to adjust the wastewater from the aforementioned company D to pH8. Subsequently, 1000mg of an aqueous solution containing 40 wt% of the compound represented by the above formula (5) (the amount of the salt A of dithiocarbamic acid is 133 parts by mass based on 100 parts by mass of copper) was added thereto, and the mixture was stirred at 150rpm for 10 minutes. Subsequently, 600mg (0.2 parts by mass of the polymeric flocculant per 100 parts by mass of copper) of an aqueous ORFLOCK OA-23 solution having a concentration of 0.1% by weight as the polymeric flocculant was added thereto, and the mixture was stirred at 50rpm for 5 minutes to obtain a slurry. After the stirring, the mixture was left standing for 10 minutes. The slurry was set in a bench centrifuge (Otsukusho Seiko S700T) and centrifuged at 3800rpm for 20 minutes to separate the sludge (wet sludge) from the aqueous solution. The amount of hydrogen sulfide gas generated in the series of treatment steps was 1ppm or less than the evaluation reference value for the working environment. The results of the copper concentration of the treated aqueous solution, the amount of produced dried sludge, and the copper content in the dried sludge are shown in table 8.
Comparative examples 12 to 13
The same operation as in example 21 was carried out except that the kind and amount of the reagent to be added were changed to the conditions shown in table 8. The results are shown in Table 8.
Comparative examples 12 to 13 were examples in which the dithiocarbamate was not used, but the copper concentration after the treatment exceeded the wastewater reference value of 3mg/L. In comparative example 13, the copper concentration of the sludge was as low as 9%.
[ Table 8]
Industrial applicability
The method for producing a sludge containing a heavy metal of the present invention can be used as a method for treating waste water discharged from a manufacturing plant of metal surface treatment, gold plating, printed circuit boards, electric/mechanical parts, automobiles, and the like.
Claims (5)
1. A method for producing a heavy metal-containing sludge, characterized by adding an alkali metal hydroxide or calcium hydroxide and a salt of a dithiocarbamate to a heavy metal-containing wastewater, then adding a polymeric flocculant to produce a slurry, and then separating a solid component from the slurry.
2. The method for producing a heavy metal-containing sludge according to claim 1, wherein the pH is adjusted to a range of 6 to 11 by adding an alkali metal hydroxide or calcium hydroxide to the heavy metal-containing wastewater, and then a salt of dithiocarbamic acid is added to produce a slurry, and then a solid component is separated from the slurry.
3. The method according to claim 1 or 2, wherein the heavy metal is copper, and the wastewater containing heavy metal is wastewater containing copper at a concentration of 20mg/L to 1500 mg/L.
4. The method according to any one of claims 1 to 3, wherein the salt of the dithiocarbamic acid is piperazine-1,4-potassium bisdithiocarboxylate, piperazine-1,4-sodium bisdithiocarboxylate, or a reaction product of tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide.
5. The method for producing a heavy metal-containing sludge according to any one of claims 1 to 4, wherein the alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
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| JP2021058653 | 2021-03-30 | ||
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| JP2021-058653 | 2021-03-30 |
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