CN1095648A - 用于废物处理的组合物及方法 - Google Patents
用于废物处理的组合物及方法 Download PDFInfo
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- CN1095648A CN1095648A CN93119625A CN93119625A CN1095648A CN 1095648 A CN1095648 A CN 1095648A CN 93119625 A CN93119625 A CN 93119625A CN 93119625 A CN93119625 A CN 93119625A CN 1095648 A CN1095648 A CN 1095648A
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- Prior art keywords
- waste
- oxide
- arsenic
- stabilizing
- apatite
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- 239000002699 waste material Substances 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 44
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011575 calcium Substances 0.000 claims abstract description 33
- 239000004568 cement Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000010881 fly ash Substances 0.000 claims abstract description 5
- 229910052586 apatite Inorganic materials 0.000 claims description 34
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 31
- 229910052752 metalloid Inorganic materials 0.000 claims description 25
- 150000002738 metalloids Chemical class 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 230000000087 stabilizing effect Effects 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 239000000460 chlorine Chemical group 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 10
- 235000011007 phosphoric acid Nutrition 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011398 Portland cement Substances 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- -1 metalloid oxide anion halide salt Chemical class 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 230000003019 stabilising effect Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Chemical group 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000004715 keto acids Chemical class 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000002901 radioactive waste Substances 0.000 claims description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 claims 1
- 239000005864 Sulphur Chemical group 0.000 claims 1
- 239000002956 ash Substances 0.000 claims 1
- 230000002939 deleterious effect Effects 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- DNNLEMIRRGUGOZ-UHFFFAOYSA-N oxygen(2-);thorium(4+) Chemical class [O-2].[O-2].[Th+4] DNNLEMIRRGUGOZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 229910003452 thorium oxide Inorganic materials 0.000 claims 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229940000489 arsenate Drugs 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 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 abstract description 5
- 229940103357 calcium arsenate Drugs 0.000 abstract description 5
- 238000004537 pulping Methods 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004571 lime Substances 0.000 description 17
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 15
- 235000011941 Tilia x europaea Nutrition 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 12
- 230000006641 stabilisation Effects 0.000 description 12
- 238000011105 stabilization Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910017251 AsO4 Inorganic materials 0.000 description 8
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical class O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 8
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 8
- 229960002594 arsenic trioxide Drugs 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 229910000413 arsenic oxide Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052935 jarosite Inorganic materials 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000010812 mixed waste Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910016586 Mn5Si3 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 2
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 2
- 229910052964 arsenopyrite Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- OGGXGZAMXPVRFZ-UHFFFAOYSA-N dimethylarsinic acid Chemical class C[As](C)(O)=O OGGXGZAMXPVRFZ-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000003546 flue gas Substances 0.000 description 2
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- 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
- 239000003673 groundwater Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
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- JCIIKRHCWVHVFF-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine;hydrochloride Chemical compound Cl.NC1=NC=NS1 JCIIKRHCWVHVFF-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- HBEPRLAIGBMXAH-UHFFFAOYSA-N ClC1=C(C=CC=C1)O.[Hg] Chemical compound ClC1=C(C=CC=C1)O.[Hg] HBEPRLAIGBMXAH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 208000014347 autosomal dominant hyaline body myopathy Diseases 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052589 chlorapatite Inorganic materials 0.000 description 1
- VJTAZCKMHINUKO-UHFFFAOYSA-M chloro(2-methoxyethyl)mercury Chemical compound [Cl-].COCC[Hg+] VJTAZCKMHINUKO-UHFFFAOYSA-M 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- MPUDNZRIAUQBRU-UHFFFAOYSA-K copper;chromium(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Cr+3].[Cu+2].[O-][As]([O-])([O-])=O MPUDNZRIAUQBRU-UHFFFAOYSA-K 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- VIJONEIFBHPTPR-UHFFFAOYSA-N dioxido(oxo)silane;2-methoxyethylmercury(1+) Chemical compound COCC[Hg]O[Si](=O)O[Hg]CCOC VIJONEIFBHPTPR-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
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- 229910000399 iron(III) phosphate Inorganic materials 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
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- 239000007791 liquid phase Substances 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- JITOKQVGRJSHHA-UHFFFAOYSA-M monosodium methyl arsenate Chemical compound [Na+].C[As](O)([O-])=O JITOKQVGRJSHHA-UHFFFAOYSA-M 0.000 description 1
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229940096826 phenylmercuric acetate Drugs 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
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- 150000008163 sugars Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
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Abstract
废物处理的方法和稳定的废物元素组合物,特别
适用含砷废物。As2O3废物在水中与CaO成浆6—
24小时,生成砷酸钙(III)。对于As过量的CaO用
于消耗其它废物。在120℃下烘干和在空气中煅烧
使砷酸盐(III)氧化成砷酸盐(V),主要为Ca5(AsO4)3
(OH)和少量为Ca3(AsO4)2。研磨或破碎及将其掺
入由普通水泥和粉煤灰组成的密封剂中,完成进一步
固定。最后使用铁粘土给容器加衬,由于铁粘土吸收
和吸附可能逸出的重金属,因而更加保证安全。
Description
本发明涉及用于废物处理的组合物及方法。
本发明具有特定的但并非唯一的组合物和方法的用途,所述组合物和方法以适于地质处理的形式稳定重金属和准金属废物,并且为说明起见,将做出上述用途的参考例。但是应当理解,本发明能用于其他方面,例如稳定其他金属废物流。
金属和准金属废物流常常含有高毒或形成高毒含氧阴离子的金属盐。由于砷酸盐(III)以及III和V价态的砷的氧化物具有高的可浸出性,因此在填埋或类似处理时,含砷废物流表现出相当有毒的危害性。过去,已经提出,通过将含砷废物材料密封于波特兰水泥中来稳定它的方法。这样密封的砷的氧化物是处于多种氧化物状态,并且它通常由具有III和V价砷的化合物的混合物构成。已经提出用H2O2或其他氧化剂处理废物流,使砷III氧化,以降低可溶性并降低有毒的砷V。
砷黄铁矿浓缩物或其矿的金属提取时产生的废物具有高含量的砷,它是一种典型废物流。通常,火冶工艺形成冷凝的砷的氧化物,并且它从冷凝气流中析出。已经提出,使该氧化物直接与波特兰水泥浆混合并使该混合物在低碳钢容器中固化,或直接充入或注入其他容器中。这种方法的缺点与组合物在填埋处理中遇到的某些条件下的不稳定性有关,包括在低和高PH值条件下浸出的敏感性,以及差的机械性能。上述组合物的抗压强度当As2O3加入量为50(重)%时通常为约10MPa,而波特兰水泥自己与等量清洁的建筑砂混合时其强度是20MPa。当用上述H2O2氧化方法降低混合废物的溶解度时,该方法变得不经济。
另一种用于处理砷废物流的已知方法包括:以水泥浆形式使砷III-V氧化物与过量的-通常位于3000~5000(摩尔)%之间一熟石灰Ca(OH)2混合,通常形成不可溶的砷酸钙(III)和砷酸钙(V)沉淀,其通式为Cax(AsO4)n。但是,已证明,大概是由于一定比例的包括砷III化合物的可溶化合物的存在,该沉淀物其可浸出性是可变化的。该组合物也是酸不稳定的,特别是在地下水或水蒸汽存在下它对于CO2或碳酸盐是不稳定的。
此外,含酸性的砷III-V的氧化物的废物流已与200或更多的(摩尔)%铁(氧氢氧化合物)混合,随后在水中用熟石灰将PH值调至5~8,形成铁的含氧砷化合物,包括混合的砷酸盐(III)和砷酸盐(V),这种组合物也是酸不稳定的,尽管其低于Cax(AsO4)n,并且在碳酸盐和/或碳酸氢盐和水存在时,它浸出。
上述两种方法仅适于处理含有形成含氧阴离子的金属或准金属(例如砷)的废物流。
通常,已有方法不形成“体积减小”的废物流,即:已有方法通常不产生相对致密的稳定废物产物,即按重量计以高的摩尔百分数结合废物类。此外,它们不形成热力学稳定的矿结物。
砷废物流中存在的一定比例的挥发性砷化合物已经妨碍了使用煅烧方法,该方法用于以热力学稳定的矿物结构使所述废物结合。
本发明的目的在于至少基本上缓和上述一个缺点并且提供可以可靠和有效使用的用于废物处理的组合物及方法。本发明的其他目的和优点通过以后的描述将变得更加清楚。
考虑到上述的和其他的目的,本发明的一个方面更广泛地属于一种废物稳定的方法,它包括如下步骤:
使所述废物流的一种金属或准金属组分形成一种氧化物;
使含所述氧化物的废物流与一种无机碱或无机含氧酸形成泥浆,所述碱或酸的选择是用于与所述氧化物形成不可溶性的沉淀物;并且
煅烧所述的沉淀物。
煅烧后的沉淀物最好具有包含有最稳定氧化状态的金属或准金属。
煅烧后的沉淀物最好由一种稳定的矿结构形成,它选自:一种或多种磷灰石、烧绿石(A1-2B2O6-7)、钙钛矿(ABO3)、碱硬锰矿(A1-2B8O16)、或其他稳定形式,其金属或准金属组分处于其最高稳定氧化状态。例如,对于许多如铅那样的重金属或如砷那样的准金属,磷灰石矿结构是稳定的和优选的。因此,本发明再一方面概括地属于一种稳定金属或准金属的氧化物废物的方法,它包括如下步骤:
使废物材料和一种金属卤化物和选自无机碱或含氧酸的化合物形成泥浆,所述化合物的选择是使得分别形成一种非挥发性的准金属的含氧阴离子卤化物盐,或一种非挥发性的金属卤化一含氧阴离子盐,并且
煅烧所述的泥浆,以形成一种磷灰石晶体结构或其类似物。
在本文上下文中,术语“准金属氧化物”包括形成含氧阴离子的有害元素,准金属和金属,例如,砷、钒、硫、磷、锰、和铬的氧化物。在本文上下文中的“金属氧化物”包括:能够形成相对不可溶盐的有害重金属的氧化物。后一者的组分可能也落于前者中。本文中非挥发性准金属含氧阴离子卤化物盐或非挥发性金属卤物一含氧阴离子盐的术语“非挥发性”涉及在煅烧工艺过程中典型遇到的温度下具有非常低蒸汽压力的化合物。
本文中所用的“磷灰石结构”按照M·O′keeffe以及B·G·Hyde的定义。尽管精确地讲,对于复杂的废物流磷灰石时,预料这种定义允许在结构和组合物方面具有轻微的变化。这种结构被称作阴离子填充合金。该合金成分具有Mn5Si3(D88)类型的拓扑结构。例如在氟磷灰石Ca5(PO4)3F中,Ca5P3阳离子排列相同于Mn5Si3类型。阴离子随后被填充入合适的、通常为四面体的节间中,该节间由阳离子的规律排列形成。这样,形成PO4四面体所存的氧是在两种类型的PCa3四面体中。F位于一个Ca3三角形中(在羟基磷灰石中,O是位于Ca3H四面体中,而在氯磷灰石中,氯接近于Ca6八面体的中心)。这种描述也易于解释由CO3 2-碳酸根和SO4 2-硫酸根替代PO4 3-,以及在阳离子非化学计算方面作为实例。相反,具有通式A5(BO4)3X的磷灰石可以显示阴离子X和/或阳离子A化学计算中的替代或偏差。
该方法最好适于镉、汞、和/或铅的金属氧化物废物以及砷、铬、和/或硒准金属氧化物废物的处理。最好,按照本发明的方法的形成泥浆的步骤导致形成一种或两种两个共存的不可溶化合物。一种具有通式A5(BO4)3X,此处A=钙、镉、汞、或铅,B=磷、砷、铬、钒、硫、碳、硅、或硒,并且X=氟、氯、或羟基。另一种具有通式A3(BO4)2。在金属或准金属的情况下,例如砷、钒、和铬,它们形成阴离子根的砷酸盐、钒酸盐或铬酸盐,这种方法涉及与最好是CaO那样的无机碱的反应,以促进非挥发性Ca3(Bo4)2化合物的形成。在另一种与这种方法可相容的重金属废物流的情况下,例如钡废物、锌废物、汞废物和镉废物,该方法涉及与无机含氧酸最好是H3PO4的反应。在所有情况下,废物类型最好适于确保以高的不可溶的A5(PO4)3X形式的磷灰石或类似矿的结晶截留金属。
强无机碱最好选自碱土碱性氧化物,例如,用于处理含砷的氧化物废物的准金属氧化物废物的氧化钙。例如,对于处理主要含砷的氧化物化合物的废物时,废物可与水和无机碱形成泥浆,以便形成主要为非挥发性碱土金属的砷酸盐(III)。最好使用比化学计算过量的碱,以确保转化为非挥发性的砷酸盐(III)和砷酸盐(V)。对于砷废物处理时,碱土或过渡金属的卤化物最好选自氯化物和氟化物,以便形成非挥发性的金属的砷酸盐,最好在没有酸类如CO2存在的条件下完成成浆过程,以便最大限度地形成非挥发性砷酸盐(III)化合物。
无机含氧酸最好选自含氧 磷酸。在将要处理混合废物的情况下,可能希望合适地将优选的石灰和磷酸工艺结合起来。另一种选择是,可以使废物流仔细地混合,以便形成可结合石灰和磷酸工艺处理的混合废物。
实际上,对于将砷废物处理至稳定的砷酸盐化合物已经确定,工艺的工业生存性可通过废物流与无机碱最好是CaO的反应速度确定。已经发现,通过控制泥浆温度和表面积,从而控制石灰的反应速度,这样可实现合适的反应速度。石灰可以适用表面积大于0.5m2/g的石灰,并且最好是在1.0m2/g至大于2.0m2/g的范围内。例如通过使用中度焙烧的碳酸钙可形成这样的优选反应速度,而过度焙烧把表面积降低至低于0.5m2/g。例如通过将碳酸钙飘悬煅烧成表面积为约2.0m2/g的石灰,可以形成高度活性的石灰。
当处理的废物流主要含有As2O3时,由于砷的氧化物对于反应的有效性是由其在水介质的溶解特性而确定的,因此,温度控制是特别合适的。在砷的氧化物的情况下,反应动力学是由随温度变化的该氧化物的溶解度控制的,并从而控制氧化物与石灰反应的有效性。而砷的氧化物在30℃时是微溶的(<1mg/L),而在60℃和90℃时其溶解度分别增至30mg/L至85mg/L。
此外,已经确定,将如钠和钾那样的轻金属的强碱盐同时加入泥浆/水冶阶段将形成更快的反应速度。通过形成活性中间体,增加反应物的溶解度,从而实现快速的反应速度。按照上述的,中间体的反应导致强碱盐的再生。强碱盐最好选自NaOH和/或KOH。通过过滤或离心法除去沉淀的砷酸盐后,溶液中含强碱盐的清液可被再循环。
在金属氧化物废物的情况下,金属卤化物最好选择过渡金属的卤化物,而对于准金属氧化物废物,最好选择碱土金属卤化物。另一种方案是,卤化物可来自一种卤化物给体,例如H2siF6,其中,分子式为A5(Bo4)3X的磷灰石的含氧阴离子的一部分可由一部分残留的sio4阴离子替代。最好,根据已很好建立的结晶化学原理混合如氟化钙或氯化钙那样的金属卤化物盐,以便形成氟或氯的A5(BO4)3X化学结构的化合物。
最好在受控条件下煅烧非挥发性的中间体的不可溶沉淀物,以便最大量地生产磷灰石或其他稳定结构的不可溶的无机化合物。如果希望的话,煅烧前可使沉淀物脱水或干燥。
在水冶成浆过程中最好使用相对纯净的水。例如,最好使用蒸馏和/或软化后的水。在偏远地区,通过真空蒸馏或反渗透法可由地下水生产蒸馏水。沉淀物的脱水、烘干干燥和/或煅烧阶段的水最好被再循环。
当优选磷灰石结构时,某些元素不适合于磷灰石稳定。在这些情况下,要求用化合物的多相收集物稳定废物流中的这些组分。例如,锑V作为A1-2B2O7-xXx烧绿石型结构将被稳定。铊1在A1-2B8O16碱硬锰矿型中可被稳定。钍作为ThP2O7将被稳定。下表1简要给出了用于各种有毒金属的主要优选的主体相。最好选择这些相,因为它们是相互相容的,并且能在相同的氧化条件下制备的。该简表不包括某些废物元素划分于两个或多个相之间的可能性,并且的确可以预期到这种复杂性,并且在一给定废物流中在适应组合物的变化方面可能是有益的。表1结构类型 废物元素A5(BO4)3x A=Ca、Pb、Cd、Hg、Ba、Sr、镧系元
素。磷灰石 锕系元素;B=P、As、Cr、V、Si、Se;
x=F、Cl、Br、I、OHA1-2B2O7-xXx A=Ca、Sr、Pb、Cd、Ba、Sr、镧系元
素。烧绿石 锕系元素;B=Sb、Ti、V、Cr、Se;
x=F、Cl、Br、I、OH、NH4A1-2B8O16 A=T1、Hg、碱、碱土类碱硬锰矿 B=过渡金属
ABO3 A=碱、碱土类、镧系元素、钙钛矿 锕系元素;
B=过渡元素
可用水泥材料以物理方法固化煅烧后的沉淀物,这将便于将废物输送至最终处理场地。根据填埋的地球化学特性和处理其他环境条件确定不可溶化合物及水泥物质的选择。例如,可用水泥材料固化该煅烧物,包括普通波特兰水泥、高铝水泥和镁氧水泥。选择水泥材料时应考虑固化后产物的机械强度,它可由加入的废物中的骨料确定。已认识到最好根据处理环境选择水泥屏障。例如,在酸性土壤在普通波特兰水泥是稳定的,并可选为固化介质。在碱性土壤中,可使用镁氧和/或铝质水泥。
如果希望的话,可用火山灰的粉煤灰替代一部分泥材料。其优点是通过消耗另一种便宜的废料固化废料,并且具有改进的加固性能烧,例如较大的密度、较低的孔隙率,并且较耐硫酸盐和氯化物的破坏。
可以分批或连续的工艺实现本发明的方法。例如,连续工艺最适于大的中心装置。可以结合混合和溶合步骤,并随之连续地进行过滤步骤、和固化/挤压步骤。固化/挤压步骤可形成块料或团粒。在使用挤时,希望使过滤后的产物与一种水溶性或乙醇可溶的聚合物或膨润土粘土混合,以优化颗粒的塑料性能。随后可将团粒/块料供入旋转窑或带式窑。
分批工艺最适于小型活动装置,它可在需要修补的小型工地使用。在此情况下,最好选用成块料的方法,然后在箱式窑中以盘式煅烧。
为更易于理解和实施本发明,下面将参照附图描述下述实施例,它说明了本发明的一个优选实旋方案,以此做为参考,其中:
图1示出了按照本发明方法稳定金矿开采作业中得到的三氧化二砷的流程图。
图2示出了按照本发明用于处理三氧化二砷时多屏障原理的各个层次。
图3示出了用于制备上述废物形式的一个流程图。
图4包括按照本发明形成的稳定废料形式的浸出数据。
实施例1
在本发明一个实施方案中,提取贵重金属的副产品三氧化二砷废物在水中与按照化学计算量的细碎的(接近50微米的颗粒尺寸)生石灰形成泥浆,形成非挥发性的砷酸钙(III)。由于上述废物不可避免地将含有少量的硫酸盐、硅酸盐和铁的氧化物,因此应加入足量的生石灰以消耗这些另外的废物类。根据生石灰的反应速度,6至24小时泥浆时间足以完全反应。成浆后,产物在120℃条件下烘干,在冷凝液中具有少量的砷损失,并随后在空气中煅烧。
对于脱水的沉淀物进行的煅烧时间和温度范围,从1000℃时15分钟至500℃的若干小时。在煅烧中,砷酸盐(III)被氧化成砷酸盐(V),它促进了作为主要的砷的稳定相的Ca5(AsO4)3(OH)的形成,而少量的砷结合于Ca3(AsO4)2中。另外的废物种类作为无水钙(硫酸盐稳定)和钙铁氧化物(铁稳定)结晶。
参照图1可以看出,初次水冶反应涉及三氧化二砷废物与生石灰以As2O3∶CaO=3∶5的比例成浆,以生成非挥发性的砷酸钙(III)。由于矿物废料除三氧化二砷外含有其他化合物,因此必须按照合适的化学计算比例将附加量的石灰加入其中,以确保这些少量种类废物的稳定。在二次煅烧工艺中,按照所示计算温度和时间煅烧泥浆,使其发生氧化和形成磷灰石。
通过研磨或破碎法破碎磷灰石(它是生物安全的),并将磷灰石混入由普通波特兰水泥和粉煤灰构成的水泥密封剂中,该密封剂可具有或没有烟硅石作为孔隙度和强度改进剂,从而完成第三阶段的稳定。在水中以1∶0.4~0.7的固体:水的比例使磷灰石一水泥混合物成浆,以完成上述过程。在水饱和的环境中在一钢转筒中固化一个月后,这种废物形式易于输送至容器或进行填埋。在工艺的后期用材料(即铁粘土)给该容器加以能强烈地吸收和吸附逸出的重金属类的衬里,可提供进一步的安全措施。
图2示意性地示出了用于砷酸钙(V)磷灰石的多屏障废物稳定方法。通过以磷灰石结晶以形成第一层次的稳定。通过可防止溶解的稳定的水泥基体封闭不可溶的化合物,以此实现进一步的稳定。假如任何部分的砷溶解,将由铁粘土快速地吸附它,即捕获它,并延迟了砷分散至物圈中。
实施例2
来自于碱金属提取的含砷废物时常临时贮藏于尾矿屏障中。为将在上述屏障中的稳定的砷的浓度降至最低,通常加入过量的石灰,使废物作为砷酸钙(III)沉淀。由于留下了多量的石灰,因此这些尾矿屏障泥浆不能被直接转化为磷灰石。相当过量的石灰的存在在水合作用过程中是不令人满意的,并且通过碳酸盐化作用,该石灰膨胀并破坏废物形式的自然完整性。
为克服上述问题,使泥浆与通过沉淀收集的富含砷的烟气混合,其量是恰好足以消耗过量的石灰。除去砷外该烟气可能还含有铅和锑。此外,加入CaF2和/或CaCl2,以稳定卤一磷灰石。因此最终的磷灰石富含砷和铅并含有少量的锑。大部分锑进入(Ca、Pb)1-1.5Sb2O7-x(F、Cl、OH)x相中。图3以流程图的形式示出了按照这种实施方案的废物稳定方法。图4示出了通过动态沸水浸出试验获得的浸出数据,它是对于按照本实施方案方法的磷灰石产物在11天内的数据。
实施例3
BIOX*是一个生物水冶工艺,用于从高熔点硫化物矿中回收金。这种工艺涉及黄铁矿/砷黄铁矿硫化物浓缩物的细菌氧化,按照下述反应通式形成含砷(V)、铁和硫酸根离子的液相:
为使废物转化为固体,首先使废物溶液与稀磷酸混合,使铁作为正磷酸铁沉淀,从而降低了废物流中铁的浓度。
过滤剩余的H3AsO4和硫酸液,并按照化学计算的量使之与生石灰和氟化钙CaF2反应,生成砷(V)磷灰石和石膏(硫酸钙):
实施例4
本工艺用于稳定生产汞杀菌剂时产生的汞废物,所述汞杀菌剂包括乙酸苯汞(PMA,Tag*)、氯化甲氧乙基汞和硅酸甲氧乙基汞(在欧洲的Ceresan*)、氯化乙基汞(在美国的Ceresan*)、氯酚羟基汞(Semesan*)、硝基苯酚羟基汞(Semean-Bel*)和双氰胺甲基汞(Pamagen*)。在此实施方案中,使用波长180nm的紫外光催化光氧化上述汞废物,使汞作为氧化物释出。可使用细碎的氧化钠和/或二氧化钛催化该反应。氧化汞残余物按照化学计算比例与稀磷酸氢酸和氟石成浆,形成具有磷灰石类型晶体结构和化学组合物(Hg9Ca)(PO4)6F2的复合物。在120℃下使该材料脱水并且随后最好在温度直至600℃煅烧之前使其固化。
*表示注册商标
实施例5
在氯化汞HgCl2的情况下,废物按化学计算比例与石灰和磷酸成浆,生成组合物(HgCa9)(PO4)Cl2的磷灰石。如上所述那样干燥和固结这种复合物并在不超过1000℃条件下煅烧。
实施例6
含有甲砷酸和卡可基酸的单钠(MSMA)和双钠(DSMA)盐的有机含砷除草剂也可以通过催化光氧化使其释出砷的氧化物。随后可用一般的方法处理该砷的氧化物。
实施例7
包括砷酸铅PbHAsO4和砷酸钙Ca3(AsO4)2以及CaHAsO4的无机砷的杀虫剂能被处理,形成(CaxPb1-x)(AsO4)3(F、Cl)类型的磷灰石。
实施例8
含有硫酸盐的五氧化二钒废催化剂是石油精炼和硫酸生产中产生的废物。可按照本发明通过使其与石灰和/或磷酸和卤化物盐按照化学计算成浆,将其处理为磷灰石Ca(V、PO4)3(F、Cl)和无水CaSO4的两相组合物。最好在1100℃下煅烧。
实施例9
在锌生产中,黄钾铁矾族的化合物MFe3(SO4)2(OH)6(在此M=H、Na、K、NH4、Ag、Pb)用于使铁沉淀。黄钾铁矾可能含有许多重金属,例如Pb、As、Ca和Hg。黄钾铁矾仅在低PH值(<3.2)下是稳定的,通过使用一种合适的碱升高PH值可使其释出这些重金属。在按照本发明用石灰和磷酸处理之前可通过蒸发来浓缩溶解的金属。
实施例10
铜-铬-砷酸盐(CCA)木材防腐剂由化合物硫酸铜(CuSO4·5H2O)、黄铬酸钠(Na2Cr2O7·2H2O)和五氧化二砷(As2O5·2H2O)构成。可通过使废物CCA与足量石灰和卤化物盐反应,形成Ca5(CrO4)3(F、Cl)和Ca5(AsO4)3(F,Cl)和亚砷酸氢铜CuHAsO3的磷灰石,以此来处理该废物。通过洗涤除去钠。
实施例11
碘-129是一种在该燃料消耗过程中产生的长期裂变的产物。它也具有高的挥发性。在溶解和/或回收油柱过程中,能够在废气流中容易地作为冷凝物收集到它。在这种形式中,它可溶解于稀磷酸中并与氧化铅反应,生产组合物Pb8(PO4)5I的磷灰石。
实施例12
在另一实施方案中,精炼糖时形成的分子式为NaPb2(CO3)2OH铅废物按照化学计算量与稀的正磷酸混合,形成高度不可溶的Pb5(PO4)3(OH),通过过滤将其与NaHCO3残余溶液分离。在120℃下烘干含Pb5(PO4)3(OH)沉淀物。在空气中在约400℃下煅烧干产物,以除去有机材料,例如残余的糖。
实施例13
当优选磷灰石结构时,某些废物元素不适于由磷灰石稳定。在这一实施方案中,来自砂采矿的含有高浓度钍的放射性废物,首先在浓硫酸中溶解,然后用磷酸处理,生成稳定和不溶性的ThP2O7。
实施例14
含有多于5(重)%氧化锑的废物全部能作为磷灰石稳定,但是过量的锑可以一种磷灰石的相容相的形式作为烧绿石结构Ca2Sb2O7-x(F、Cl、OH)x予以稳定。
上述工艺形成一种废物形式/相的集合物,其溶解特性低于现有的规章的范围,并且在整个地质时期能对重金属和准金属进行有效的稳定。废物体积被减小,根据废物流组合物的种类,处理材料的密度是在3~7g/cc范围内。当混合于波特兰水泥中时,熔渣和破碎的熔渣的骨料的强度是约20MPa。
优选的多屏障处理涉及各种防止重金属从废物场所移动离开的屏障。三屏障是以磷灰石相的稳定屏障,通过水泥材料提供的结晶化学屏障和通过掩埋现场提供的地质屏障。以一种完整的方式选择这三个屏障层,使得所设计的重金属稳定系统在整个地质时期其可靠性能得到保证。例如,在砷矿废物的情况下,能用25(重)%的普通波特兰水泥和25(重)%的火山灰的粉煤灰固化50(重)%的磷灰石。这种废物形式具有好的机械强度(15Mpa),并且在酸性地质条件下是稳定的。
这种地质填埋可被挖掘,并且可用一种能强烈地吸收少量的可能从废物形式中溶解的砷酸盐的铁类粘土作为衬里。这样,在长时期内,从近区域(废物形式自身)和远区域(衬里和第二层包装外密封层)砷的漏失是极低的。
此外,因为按照成熟的化学原理提供稳定,因此可以确定主要的结晶化学屏障的固有的长期浸出阻力。没有其他可得到的技术能提供这种安全水平,这是因为至今为止所使用的没有特殊的稳定形式的稳定技术具有无法预言的长期性能。
当然应当认识到,上面以实施例的形式描述了本发明,而所有上述的以及本专业普通技术人员容易做出的其他变型和变化应落入本发明的广义的精神和范围内,本发明的范围由所附权利要求书界定。
Claims (21)
1、一种稳定废物的方法,包括如下步骤:
使所述废物流的一种金属或准金属组分形成一种氧化物;
使含所述氧化物的废物流与一种无机碱或无机含氧酸形成泥浆,所述碱或酸的选择是用于与所述氧化物形成不可溶性的沉淀物;并且
煅烧所述的沉淀物。
2、如权利要求1所述的稳定废物的方法,其特征在于:所述煅烧后的沉淀物包括一种稳定的矿结构,它选自:磷灰石、烧绿石、碱硬锰矿、和钙钛矿。
3、一种用于稳定金属或准金属的氧化物废物的方法,包括如下步骤:
使废物材料和一种卤化物给体和选自无机碱或含氧酸的化合物形成泥浆,所述化合物的选择是使得分别形成一种非挥发性的准金属的氧化物阴离子卤化物盐,或一种非挥性的金属卤化一氧化阴离子盐;并且
煅烧所述的泥浆,以形成一种磷灰石晶体结构或其类似物。
4、如权利要求3所述的稳定氧化物废物的方法,其特征在于:所述准金属的氧化物包括可形成含氧阴离子的有害元素、准金属和金属的氧化物。
5、如权利要求4所述的稳定氧化物废物的方法,其特征在于:所述准金属选自砷、钒、硫、磷、锰、硒、和铬。
6、如权利要求3所述的稳定氧化物废物的方法,其特征在于:所述的金属氧化物包括能形成相对不可溶性盐的有害金属的氧化物。
7、如权利要求6所述的稳定氧化物废物的方法,其特征在于:所述金属选自镉、汞和铅。
8、如上述任一权利要求所述的稳定氧化物废物的方法,其特征在于:所述煅烧后的沉淀物包括一种或多种通式为A5(Bo4)3x和A3(Bo4)2的矿,其中A=钙、镉、汞、或铅,B=磷、砷、铬、钒、硫、碳、硅、或硒,并且x=氟、氯、或羟基。
9、如上述任一权利要求所述的稳定氧化物废物的方法,其特征在于:所述强无机碱选自碱土类碱性氧化物。
10、如权利要求9所述的稳定氧化物废物的方法,其特征在于:所述氧化物废物包括含砷的氧化物的废物,并且其中无机碱是氧化钙。
11、如权利要求10所述的稳定氧化物废物的方法,其特征在于:所述氧化钙的表面积是在从1.0m2/g至大于2.0m2/g的范围内选择。
12、如上述任一权利要求所述的稳定氧化物废物的方法,其特征在于:所述无机含氧酸选自含氧的磷酸。
13、如权利要求3所述的稳定氧化物废物的方法,其特征在于;所述卤化物给体在金属氧化物废物的情况下是选自过渡金属的卤化物,而准金属氧化物废物的情况下是选自碱土金属的卤化物。
14、如权利要求3所述的稳定氧化物废物的方法,其特征在于:所述卤化物给体由H2SiF6构成,使得所述煅烧的沉淀物由通式为A5(Bo4)3F的磷灰石矿构成,其中,A=钙、镉、汞或铅,并且B=磷、砷、铬、钒、硫、碳、硅或硒,并且其中由一部分残余的SiO4阴离子取代一部分磷灰石的含氧阴离子。
15、如上述任一权利要求所述的稳定氧化物废物的方法,其特征在于:进一步用水泥材料以物理方法固化所述的煅烧后的沉淀物。
16、如权利要求15所述的稳定氧化物废物的方法,其特征在于:用选自波特兰水泥、高铝水泥和镁氧化水泥的水泥材料固化所述的煅烧物。
17、如权利要求16所述的稳定氧化物的废物的方法,其特征在于:用火山灰的粉煤灰替代部分水泥材料。
18、如权利要求1所述的稳定废物的方法,其特征在于:所述废物由来自砂采矿的含有高浓度钍氧化物的放射性废物构成,并且它包括如下步骤:
用浓硫酸溶解所述废物
用磷酸处理溶解的废物;
使沉淀的ThP2O7脱水;并且
煅烧所述的沉淀物。
19、煅烧的矿物化合物和组合物包括:通式为A5(Bo4)3X和A3(Bo4)2的一种或多种矿,其中A=钙、镉、汞、或铅,B=磷、砷、铬、钒、硫、碳、硅、或硒,并且X=氟、氯、或羟基。
20、基本根据前述所附实施例1至14和附图1至4限定的稳定废物和方法。
21、基本根据前述所附实施例1至14和附图1-14限定的煅烧的矿物化合物和组合物。
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US5347073A (en) * | 1993-04-28 | 1994-09-13 | Air Products And Chemicals, Inc. | Fixation of heavy metals, mercury recovery and dioxins destruction in municipal solid waste incinerator ash |
-
1993
- 1993-09-14 TW TW82107550A patent/TW261602B/zh active
- 1993-09-20 MY MYPI93001903A patent/MY107766A/en unknown
- 1993-09-21 ID ID936698A patent/ID1043B/id unknown
- 1993-09-21 AP APAP/P/1993/000598A patent/AP427A/en active
- 1993-09-21 US US08/403,924 patent/US5649894A/en not_active Expired - Fee Related
- 1993-09-21 JP JP50761394A patent/JPH08501249A/ja active Pending
- 1993-09-21 CA CA 2145310 patent/CA2145310A1/en not_active Abandoned
- 1993-09-21 WO PCT/AU1993/000489 patent/WO1994006575A1/en active IP Right Grant
- 1993-09-21 EP EP19930920615 patent/EP0695224B1/en not_active Expired - Lifetime
- 1993-09-21 DE DE1993631469 patent/DE69331469T2/de not_active Expired - Fee Related
- 1993-09-22 CN CN93119625A patent/CN1095648A/zh active Pending
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100494782C (zh) * | 2005-12-02 | 2009-06-03 | 中国科学院地理科学与资源研究所 | 一种砷富集植物蜈蚣草的安全焚烧方法 |
CN102247967A (zh) * | 2010-05-18 | 2011-11-23 | 上海复拓环境技术有限公司 | 一种含砷废弃危险化学品的无害化处理工艺 |
CN102247967B (zh) * | 2010-05-18 | 2014-10-08 | 上海复拓环境技术有限公司 | 一种含砷废弃危险化学品的无害化处理工艺 |
CN102657925A (zh) * | 2012-04-12 | 2012-09-12 | 广东省生态环境与土壤研究所 | 基于粘土的重金属热固化剂及其固化重金属的方法 |
CN102657925B (zh) * | 2012-04-12 | 2018-01-05 | 广东省生态环境技术研究所 | 基于粘土的重金属热固化剂及其固化重金属的方法 |
CN104072093A (zh) * | 2014-06-30 | 2014-10-01 | 张家港格林台科环保设备有限公司 | 一种含砷的氧化物建筑材料的制备及砷脱附液的回收应用 |
CN111662049B (zh) * | 2019-03-07 | 2021-03-19 | 北京万之悦科技发展有限公司 | 一种高强水泥基放射性废物固化固定材料 |
CN111662049A (zh) * | 2019-03-07 | 2020-09-15 | 北京万之悦科技发展有限公司 | 一种高强水泥基放射性废物固化固定材料 |
CN110279975A (zh) * | 2019-07-23 | 2019-09-27 | 哈德逊(苏州)水技术有限公司 | 垃圾焚烧飞灰固化剂 |
CN112499919A (zh) * | 2020-01-09 | 2021-03-16 | 中国铝业股份有限公司 | 一种铜冶炼污泥的处理方法 |
CN112499919B (zh) * | 2020-01-09 | 2022-07-26 | 中国铝业股份有限公司 | 一种铜冶炼污泥的处理方法 |
CN111681798A (zh) * | 2020-04-30 | 2020-09-18 | 中国辐射防护研究院 | 一种小型核设施退役现场放射性废水处理装置 |
CN113172071A (zh) * | 2021-04-16 | 2021-07-27 | 中冶长天国际工程有限责任公司 | 一种基于固废、高含水矿的协同处置工艺 |
CN116947452A (zh) * | 2023-06-08 | 2023-10-27 | 常州大学 | 一种玻璃粉包覆垃圾焚烧飞灰造粒制砖方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0695224B1 (en) | 2002-01-16 |
AP427A (en) | 1995-11-08 |
AP9300598A0 (en) | 1994-01-31 |
MY107766A (en) | 1996-06-15 |
EP0695224A4 (en) | 1997-07-23 |
US5649894A (en) | 1997-07-22 |
JPH08501249A (ja) | 1996-02-13 |
EP0695224A1 (en) | 1996-02-07 |
ID1043B (id) | 1996-10-28 |
DE69331469T2 (de) | 2002-08-29 |
TW261602B (zh) | 1995-11-01 |
DE69331469D1 (de) | 2002-02-21 |
CA2145310A1 (en) | 1994-03-31 |
WO1994006575A1 (en) | 1994-03-31 |
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