CN102247967B - Harmless treatment process for arsenic-containing waste dangerous chemicals - Google Patents
Harmless treatment process for arsenic-containing waste dangerous chemicals Download PDFInfo
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- CN102247967B CN102247967B CN201010177806.XA CN201010177806A CN102247967B CN 102247967 B CN102247967 B CN 102247967B CN 201010177806 A CN201010177806 A CN 201010177806A CN 102247967 B CN102247967 B CN 102247967B
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- Prior art keywords
- arsenic
- cement
- treatment process
- harmless treatment
- waste
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 60
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 239000004568 cement Substances 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000007711 solidification Methods 0.000 abstract description 7
- 230000008023 solidification Effects 0.000 abstract description 7
- 238000002386 leaching Methods 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 229910017251 AsO4 Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 231100000331 toxic Toxicity 0.000 description 10
- 230000002588 toxic effect Effects 0.000 description 10
- 239000000383 hazardous chemical Substances 0.000 description 9
- 229940000488 arsenic acid Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002920 hazardous waste Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 4
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 4
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 4
- 229940103357 calcium arsenate Drugs 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 3
- YMTDUCWDMRDNBN-UHFFFAOYSA-N C(C=C1)=CC=C1NC1=CC=CC=C1.Cl.[AsH3] Chemical compound C(C=C1)=CC=C1NC1=CC=CC=C1.Cl.[AsH3] YMTDUCWDMRDNBN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910000070 arsenic hydride Inorganic materials 0.000 description 2
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 229940030341 copper arsenate Drugs 0.000 description 2
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- GIKLTQKNOXNBNY-OWOJBTEDSA-N lewisite Chemical compound Cl\C=C\[As](Cl)Cl GIKLTQKNOXNBNY-OWOJBTEDSA-N 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- HTSABAUNNZLCMN-UHFFFAOYSA-F paris green Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.CC([O-])=O.CC([O-])=O HTSABAUNNZLCMN-UHFFFAOYSA-F 0.000 description 2
- LVKZSFMYNWRPJX-UHFFFAOYSA-N phenylarsonic acid Chemical compound O[As](O)(=O)C1=CC=CC=C1 LVKZSFMYNWRPJX-UHFFFAOYSA-N 0.000 description 2
- UDHDFEGCOJAVRE-UHFFFAOYSA-N phenyldichloroarsine Chemical compound Cl[As](Cl)C1=CC=CC=C1 UDHDFEGCOJAVRE-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 2
- 229960003508 ponazuril Drugs 0.000 description 2
- 229940097322 potassium arsenite Drugs 0.000 description 2
- GVPLVOGUVQAPNJ-UHFFFAOYSA-M potassium;hydron;trioxido(oxo)-$l^{5}-arsane Chemical compound [K+].O[As](O)([O-])=O GVPLVOGUVQAPNJ-UHFFFAOYSA-M 0.000 description 2
- HEQWEGCSZXMIJQ-UHFFFAOYSA-M potassium;oxoarsinite Chemical compound [K+].[O-][As]=O HEQWEGCSZXMIJQ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RMGIDVSMSUGSLH-UHFFFAOYSA-N [As](=O)(O)(O)O.OC1=C(C=C(C(=O)C2=CC=CC=C2)C=C1)[N+](=O)[O-] Chemical compound [As](=O)(O)(O)O.OC1=C(C=C(C(=O)C2=CC=CC=C2)C=C1)[N+](=O)[O-] RMGIDVSMSUGSLH-UHFFFAOYSA-N 0.000 description 1
- AZEMRQLEAYWJJU-UHFFFAOYSA-N [As](=O)(O)(O)O.[N+](=O)([O-])C1=C(C(=O)C2=CC=CC=C2)C=CC=C1 Chemical compound [As](=O)(O)(O)O.[N+](=O)([O-])C1=C(C(=O)C2=CC=CC=C2)C=CC=C1 AZEMRQLEAYWJJU-UHFFFAOYSA-N 0.000 description 1
- JHBRXZPVASHKRT-UHFFFAOYSA-N [As](=O)(O)(O)O.[N+](=O)([O-])C1=CC=C(C(=O)C2=CC=CC=C2)C=C1 Chemical compound [As](=O)(O)(O)O.[N+](=O)([O-])C1=CC=C(C(=O)C2=CC=CC=C2)C=C1 JHBRXZPVASHKRT-UHFFFAOYSA-N 0.000 description 1
- GJLMYPRLFGUSGI-UHFFFAOYSA-N [As](=O)(O)(O)O.[N+](=O)([O-])C=1C=C(C(=O)C2=CC=CC=C2)C=CC1 Chemical compound [As](=O)(O)(O)O.[N+](=O)([O-])C=1C=C(C(=O)C2=CC=CC=C2)C=CC1 GJLMYPRLFGUSGI-UHFFFAOYSA-N 0.000 description 1
- XBBAEVVIDHSGKC-UHFFFAOYSA-N [As].[Hg] Chemical compound [As].[Hg] XBBAEVVIDHSGKC-UHFFFAOYSA-N 0.000 description 1
- NWNHIPQZWXYHTJ-UHFFFAOYSA-N [Sb].[As](O)(O)(O)=O Chemical compound [Sb].[As](O)(O)(O)=O NWNHIPQZWXYHTJ-UHFFFAOYSA-N 0.000 description 1
- BOBIBDZOYYEEQF-UHFFFAOYSA-N [Sb].[As](O)(O)O Chemical compound [Sb].[As](O)(O)O BOBIBDZOYYEEQF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical compound [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- JMBNQWNFNACVCB-UHFFFAOYSA-N arsenic tribromide Chemical compound Br[As](Br)Br JMBNQWNFNACVCB-UHFFFAOYSA-N 0.000 description 1
- 229940077468 arsenic tribromide Drugs 0.000 description 1
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- BJTQUFONDOVFIJ-UHFFFAOYSA-N arsonooxyarsonic acid Chemical compound O[As](O)(=O)O[As](O)(O)=O BJTQUFONDOVFIJ-UHFFFAOYSA-N 0.000 description 1
- IDARKLQOQUZQOL-UHFFFAOYSA-N arsoric acid;mercury Chemical compound [Hg].O[As](O)(O)=O IDARKLQOQUZQOL-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- VNMKWLWVISBKGQ-UHFFFAOYSA-H barium(2+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O VNMKWLWVISBKGQ-UHFFFAOYSA-H 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- LQSFEOMOHFPNEB-UHFFFAOYSA-N dichloro(ethyl)arsane Chemical compound CC[As](Cl)Cl LQSFEOMOHFPNEB-UHFFFAOYSA-N 0.000 description 1
- IZGYEHWMAUNJHX-UHFFFAOYSA-N diiodo(phenyl)arsane Chemical compound I[As](I)C1=CC=CC=C1 IZGYEHWMAUNJHX-UHFFFAOYSA-N 0.000 description 1
- IHZDYHDJAVUIBH-UHFFFAOYSA-L disodium hydrogenarsenate Chemical compound [Na+].[Na+].O[As]([O-])([O-])=O IHZDYHDJAVUIBH-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229940071792 ferrous arsenate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- PRDPGWOYQAUJJB-UHFFFAOYSA-H iron(2+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O PRDPGWOYQAUJJB-UHFFFAOYSA-H 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- UWRBYRMOUPAKLM-UHFFFAOYSA-L lead arsenate Chemical compound [Pb+2].O[As]([O-])([O-])=O UWRBYRMOUPAKLM-UHFFFAOYSA-L 0.000 description 1
- JFOKPVUWYKONLQ-UHFFFAOYSA-L lead(2+);oxoarsinite Chemical compound [Pb+2].[O-][As]=O.[O-][As]=O JFOKPVUWYKONLQ-UHFFFAOYSA-L 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 1
- IMGNYAPMSDUASV-UHFFFAOYSA-K silver arsenate Chemical compound [Ag+].[Ag+].[Ag+].[O-][As]([O-])([O-])=O IMGNYAPMSDUASV-UHFFFAOYSA-K 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XCVRTGQHVBWRJB-UHFFFAOYSA-M sodium dihydrogen arsenate Chemical compound [Na+].O[As](O)([O-])=O XCVRTGQHVBWRJB-UHFFFAOYSA-M 0.000 description 1
- MNSRNEWGVNQDQV-UHFFFAOYSA-M sodium metaarsenate Chemical compound [Na+].[O-][As](=O)=O MNSRNEWGVNQDQV-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- APFTYZSAOLWHTM-UHFFFAOYSA-L strontium;oxoarsinite Chemical compound [Sr+2].[O-][As]=O.[O-][As]=O APFTYZSAOLWHTM-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- FOEYLTKIJNXAIO-UHFFFAOYSA-N trisilver;trioxidoarsane Chemical compound [Ag+].[Ag+].[Ag+].[O-][As]([O-])[O-] FOEYLTKIJNXAIO-UHFFFAOYSA-N 0.000 description 1
- LHBPLFWXEXNIJU-UHFFFAOYSA-H trizinc;trioxido(oxo)-$l^{5}-arsane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O LHBPLFWXEXNIJU-UHFFFAOYSA-H 0.000 description 1
- XHXZYMKBDDMBAO-UHFFFAOYSA-N trizinc;trioxidoarsane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-][As]([O-])[O-].[O-][As]([O-])[O-] XHXZYMKBDDMBAO-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a harmless treatment process of arsenic-containing waste chemicals, which comprises the following steps: 1) mixing the arsenic-containing waste with water, adding ferric salt or ferrous salt, and adjusting the pH value of the solution to be less than 2 by using nitric acid; then adding hydrogen peroxide to convert all the organic arsenic and trivalent As in the reaction system into AsO4 2-While making Fe2+All conversion to Fe3+(ii) a 2) Adjusting the pH value of the solution obtained in the step 1) to 9-10 by using calcium hydroxide to form arsenic-iron complex precipitate; 3) adding cement into the sediment and the waste liquid generated in the step 2) for solidification treatment to obtain a cement solidified body. The process provided by the invention organically integrates a chemical treatment technology and a cement curing technology, and the leaching toxicity concentration of arsenic of the obtained cement cured body is less than 5mg/L, thereby reaching the relevant national harmless standard.
Description
Technical field
The invention belongs to waste treatment processes technical field, relate in particular to a kind of harmless treatment process containing arsenic waste dangerous chemical.
Background technology
Cement solidification technology is to process the important means of heavy metal refuse and other nonmetal hazardous waste.By solidifying, harmful waste is fixed in a kind of fluid-tight matrix of inertia, refuse can change hazardous contaminant into low-solubility, low migration and the more stable material of hypotoxic physics and chemistry characteristic after overcuring is processed.
The mechanism that curing technology is stablized waste component is that Chemical bonding between refuse and coagulating agent, coagulating agent are to the physical inclusion of refuse, the acting in conjunction of coagulating agent hydrated product to absorption of refuse etc., make refuse change not charge of flowable solids into or form tight solid, change permeability, compressibility and the intensity of refuse.Hazardous waste can reach and alleviates or eliminate himself harmfulness after overcuring is processed, and can transport safely, and can carry out easily final disposal.
Cement is the most frequently used hazardous waste stabilizing agent.Because cement is a kind of cement inorganic material, after hydration reaction, can generate hard solidified cement body, thereby reach, reduce the object that in refuse, hazard component leaches.Cement adding rate is different and different according to processing type of waste, and its excursion can reach 5%～60%.
The curing technology that the cement of take is base material is for the treatment of the electroplating sludge containing different heavy metals (as cadmium, chromium, copper, lead, zinc etc.), also for the treatment of containing organic complex waste, as PCBs, grease, resin, asbestos etc.
At home, cement solidification technology is never successfully applied to containing arsenic waste dangerous chemical and processes, main cause is that pending material is containing arsenic rate high (conventionally more than 15%), + 3 valencys and+5 valency arsenic react the calcium arsenite or calcium arsenate (calcium arsenate belongs to toxic articles) the total arsenic in sulfuric acid-nitric acid digestion agent (< < solid waste Leaching leaching method sulfuric acid nitrate method > > (HJ/T299-2007)) of pH=3.20 ± 0.05 that generate and significantly leach with cement, innoxious standard far above 5mg/L, its subsequent treatment cannot reach the requirement of safety-health-environmental protection.
Meaning containing arsenic waste dangerous chemical harmlessness disposing:
Waste dangerous chemical, refer to the hazardous chemical of being abandoned or abandoning by everyone without use, superseded, of poor quality, expired, to lose efficacy hazardous chemical, the hazardous chemical that the hazardous chemical of in accordance with the law being taken in administrative management activity by authorities such as public security, customs, quality inspection, industry and commerce, agricultural, security control, environmental protection and the public of reception submit.The < < Hazardous Waste List > > of country (2008) lists 498 kinds of preferential administrative class waste dangerous chemicals, containing arsenic class, (comprise 2-atoxylate, 3-atoxylate, Ponazuril, Ponazuril hydrogen sodium, phenyl dichloro arsenic, phenylarsonic acid, propyl group arsenic acid, anthraquinone-1-arsenic acid, hexichol (base) chloroarine, diphenylamine-arsine chloride, diiodo-phenylarsine, 4-dimethyl amino-azo-benzene-4 '-arsenic acid, methanearsonic acid, pyroarsenic acid, 2-chlorovinyldichloroarsine, arsenic acid, sodium metaarsenate, (4-hydroxyl-3-nitrobenzophenone) arsenic acid, arsenic triiodide, arsenic trifluoride, arsenic trichloride, arsenic tribromide, three oxidation (two) arsenic, arsenic, arsenic mercury, arsenic hydride, arsenic acid, barium arsenate, potassium dihydrogen arsenate, monosodium arsenate, calcium arsenate, mercuric arsenate, Macquer's salt, magnesium arsenate, natrium arsenicum, lead arsenate, diammonium hydrogen arsenate, disodium hydrogen arsenate, arsenic acid antimony, ferric arsenate, copper arsenate, zinc arsenate, ferrous arsenate, silver arsenate, (2-nitrobenzophenone) arsenic acid, (3-nitrobenzophenone) arsenic acid, (4-nitrobenzophenone) arsenic acid, barium arsenite, calcium arsenite, potassium arsenite, sodium arsenite, lead arsenite, strontium arsenite, arsenious acid antimony, iron arsenite, copper arsenite, zinc arsenite, silver arsenite, ethyl dichloroarsine, copper acetoarsenite etc.) 60 kinds, account for 12% of kind sum.
Severe poisonous chemicals refers to the chemicals with very violent toxic hazard, comprises artificial synthetic chemicals and composition thereof (containing agricultural chemicals) and natural toxin.< < severe poisonous chemicals register > > (2002 editions) includes 335 kinds altogether, wherein, containing 16 kinds of arsenic classes, comprises phenyl dichloro arsenic, diphenylamine-arsine chloride, 2-chlorovinyldichloroarsine, arsenic trichloride, three oxidation (two) arsenic, arsenic hydride, arsenic acid, calcium arsenate, copper arsenate, potassium arsenite, sodium arsenite, copper acetoarsenite etc.
The frequency that participates in International Operations along with China improves day by day, the importance of anti-terrorism work becomes increasingly conspicuous, in time, Safety destroy is discarded containing arsenic hazardous chemical toxic articles guarantee to eliminate respective environment hidden danger particularly, becomes the vital task of the departments of government such as various places public security, environmental protection.Yet compared with developed countries, China lacks really can realize the discarded technology containing arsenic hazardous chemical harmlessness disposing, up to now, the domestic destruction unit that not yet occurs possessing corresponding disposal qualification and actual disposing capacity.Most areas are deposited and are failed for many years to obtain Safety destroy and have great potential safety hazard containing arsenic toxic articles.
Summary of the invention
The object of the present invention is to provide a kind of harmless treatment process containing arsenic waste dangerous chemical, to realize containing arsenic toxic articles, destroy nearby, fill up the blank of correlation technique.
Of the present inventionly solve by the following technical solutions above-mentioned technical problem:
A harmless treatment process containing arsenic waste chemicals, comprises the following steps:
1) will mix with water containing arsenic discarded object, add molysite or ferrous salt, then be less than 2 with the pH value of nitric acid regulator solution; Then add hydrogen peroxide, make organo-arsenic and trivalent As in reaction system all be converted into AsO
4 3-, make Fe simultaneously
2+all be converted into Fe
3+;
2) take calcium hydroxide regulating step 1) the pH value of gained solution is 9～10, forms arsenic iron complex precipitation;
3) to step 2) in add cement to be cured processing in the precipitation that produces and waste liquid, obtain solidified cement body.
Described step 1), in, the addition of water should be controlled at and can make to form the aqueous solution or suspension containing arsenic discarded object.
Preferably, step 1) in, the Fe element in described molysite or ferrous salt is more than or equal to 2.5:1 with the mol ratio that contains the As element in arsenic discarded object.Described ferrous salt can be ferrous sulfate, frerrous chloride or ferrous nitrate.
Preferably, step 1) in, the mass percent concentration of described hydrogen peroxide is 20%～30%; For guaranteeing that organo-arsenic and trivalent As in reaction system are all converted into AsO
4 3-, make Fe simultaneously
2+all be converted into Fe
3+, the H in hydrogen peroxide
2o
2be greater than 3:1 with the mol ratio that contains the As element in arsenic discarded object.
Preferably, step 3) in, the addition of described cement and the described mass ratio that contains arsenic discarded object are (3～5): 1.Curing processing described in the present invention adopts cement solidification treatment technology conventional in this area.
Technique provided by the present invention is organically integrated chemical disposal technology and cement solidification technology, by selecting specific pH condition, makes AsO
4 3-be converted into specific arsenic iron complex precipitation, then be cured processing formation solidified cement body.Finally make the Leaching concentration of the arsenic of obtained solidified cement body be less than 5mg/L, reached national relevant innoxious standard.
Compared with prior art, the present invention also has the following advantages:
1, whole industrial flow is safe and reliable, and except having when disposing organo-arsenic carbon dioxide discharge, without waste gas, discharge of wastewater, waste residue toxicity can be ignored, and amount send professional landfill yard direct landfill at least, and amount can be concentrated greatly and send arsenic refinement unit to recycle.
2, practical, can realize site disposal or destroy nearby in conjunction with portable chemical laboratory, avoid toxic articles uncertain security risk and a large amount of manpower and materials of saving in sending disposal transportation outside, eliminated the social safety hidden danger containing arsenic toxic articles completely.
Accompanying drawing explanation
Fig. 1 is the harmless treatment process schematic flow sheet containing arsenic waste dangerous chemical of the present invention.
The specific embodiment
The present invention selects the multiple mixture containing arsenic toxic articles as processing object, adopts chemical disposal-cement solidification technique to pass through respectively pilot scale and through engineering approaches application, and its implementation process is:
Embodiment 1 pilot process:
(1) process object
Suzhou Shang Mei international cosmetic Co., Ltd contains arsenic toxic articles: natrium arsenicum 300g, and arsenic trioxide 493g, sodium arsenite 250g, the total arsenic of original mixture leachate is higher than 50000mg/L.
(2) treatment process process
Process flow diagram is as shown in Figure 1:
In movable type reaction still, by above-mentioned, containing arsenic toxic articles mixture, be added to the water, add ferrous sulfate, form solution, make the mol ratio of Fe and As in solution be more than or equal to 2.5:1, again by nitric acid regulator solution pH value to being less than 2, then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 20%～30%) to carry out oxidation reaction; Wherein control the H in hydrogen peroxide
2o
2with the mol ratio 3:1 that contains the arsenic element in arsenic discarded object.Reaction was carried out after 1-2 hour, then to add calcium hydroxide regulator solution pH value be 9～10, now formed arsenic iron complex and precipitated.Gained precipitation is together added in 200L carbon steel tank with waste liquid, then add 4000g cement, be cured and process the stable solidified cement body of formation.
(3) experimental rig specification and size
Portable reaction still: 50L, material is double-deck Pyrex (GG17 material), configuration frequency control agitator 1 cover (250W), temperature-controlling system etc.
Solidification equipment: 200L carbon steel tank.
(4) test effect
By < < household refuse landfill sites, polluting control criterion > > GB16889-2008 detects, it is 0.07mg/L that solidified cement body leaches total arsenic concentration, meets the direct landfill requirement of household refuse landfill sites.
Embodiment 2 through engineering approaches application:
(1) process object
Wujiang green happy solid waste recycling disposal Co., Ltd is containing arsenic hazardous chemical, 15 tons, arsenic content (on average) 37.18%, leaching arsenic 29702mg/L.
(2) each processing unit technological parameter
Reaction tank: reaction tank is PP structure, is of a size of Φ 3.0m * 2.2m, dischargeable capacity 14m
3, configuring 1 agitating device, power is 7.5kW, above establishes exhaust system (air-introduced machine power is 5.5kW), divides into plate and frame filter press 1 cover (80m
2).
Solidify machine: two shaft pugmill mixer, productivity ratio 25m
3/ h.
Process flow diagram is as shown in Figure 1:
By above-mentioned, containing arsenic hazardous chemical 200kg, drop in reaction tank, add ferrous chloride aqueous solution, making the mol ratio of Fe and As in solution is 2.5:1, then by nitric acid regulator solution pH value to being less than 2, then add hydrogen peroxide (mass percent concentration of hydrogen peroxide is 30%) to carry out oxidation reaction; Wherein control the H in hydrogen peroxide
2o
2with the mol ratio of arsenic element containing in arsenic discarded object be 3:1.Reaction was carried out after 2 hours, then to add calcium hydroxide regulator solution pH value be 9～10, now formed arsenic iron complex and precipitated.Finally add again 900kg cement, in solidifying machine, be cured and process the stable solidified cement body of formation.
(3) through engineering approaches application treatment effect
By < < hazard waste landfill, polluting control criterion > > GB18598-2001 detects, it is 1.7mg/L that solidified cement body leaches total arsenic concentration, meets the direct landfill requirement of hazardous waste landfill.
(4) technical economic analysis
By engineering operation cost analysis (mainly taking five parts by labour cost, the electricity charge, medicament expense, laboratory fee, landfill forms), per ton is 71453 yuan (by 200kg/ days scales) containing the disposal cost of arsenic hazardous chemical.
Claims (4)
1. containing a harmless treatment process for arsenic waste chemicals, comprise the following steps:
1) will mix with water containing arsenic discarded object, add molysite or ferrous salt, then be less than 2 with the pH value of nitric acid regulator solution; Then add hydrogen peroxide, make organo-arsenic and trivalent As in reaction system all be converted into AsO
4 3-, make Fe simultaneously
2+all be converted into Fe
3+;
2) take calcium hydroxide regulating step 1) the pH value of gained solution is 9～10, forms arsenic iron complex precipitation;
3) to step 2) in add cement to be cured processing in the precipitation that produces and waste liquid, obtain solidified cement body.
2. the harmless treatment process containing arsenic waste chemicals as claimed in claim 1, is characterized in that step 1) in, the Fe element in described molysite or ferrous salt is more than or equal to 2.5:1 with the mol ratio that contains the As element in arsenic discarded object.
3. the harmless treatment process containing arsenic waste chemicals as claimed in claim 1, is characterized in that step 1) in, the H in described hydrogen peroxide
2o
2be greater than 3:1 with the mol ratio that contains the As element in arsenic discarded object.
4. the harmless treatment process containing arsenic waste chemicals as described in arbitrary claim in claim 1-4, is characterized in that step 3) in, the addition of described cement and the described mass ratio that contains arsenic discarded object are (3～5): 1.
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| CN107188292A (en) * | 2017-05-19 | 2017-09-22 | 山东国大黄金股份有限公司 | A kind of utilization silver extraction by cyanidation waste residue purifies the method containing arsenic waste solution |
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