AP427A - Compositions and methods for waste treatment. - Google Patents
Compositions and methods for waste treatment. Download PDFInfo
- Publication number
- AP427A AP427A APAP/P/1993/000598A AP9300598A AP427A AP 427 A AP427 A AP 427A AP 9300598 A AP9300598 A AP 9300598A AP 427 A AP427 A AP 427A
- Authority
- AP
- ARIPO
- Prior art keywords
- waste
- oxide
- arsenic
- calcium
- arsenate
- Prior art date
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 38
- 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 abstract description 38
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 34
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims abstract description 32
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940000489 arsenate Drugs 0.000 claims abstract description 20
- 239000000292 calcium oxide Substances 0.000 claims abstract description 15
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 15
- 239000011398 Portland cement Substances 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 12
- 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 claims abstract description 11
- 229940103357 calcium arsenate Drugs 0.000 claims abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000010881 fly ash Substances 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 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 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 235000013980 iron oxide Nutrition 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 239000001175 calcium sulphate Substances 0.000 claims abstract description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims abstract description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003801 milling Methods 0.000 claims abstract description 3
- 229910052752 metalloid Inorganic materials 0.000 claims description 25
- 150000002738 metalloids Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 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
- -1 halide salt Chemical class 0.000 claims description 15
- 230000000087 stabilizing effect Effects 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 235000010755 mineral Nutrition 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229960002594 arsenic trioxide Drugs 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 230000006641 stabilisation Effects 0.000 claims description 9
- 238000011105 stabilization Methods 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
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 231100001261 hazardous Toxicity 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 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
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 239000002901 radioactive waste Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 4
- 101000588924 Anthopleura elegantissima Delta-actitoxin-Ael1a Proteins 0.000 claims 1
- 240000007175 Datura inoxia Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 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 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims 1
- 229910003452 thorium oxide Inorganic materials 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000008393 encapsulating agent Substances 0.000 abstract description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 abstract 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 16
- 240000006909 Tilia x europaea Species 0.000 description 16
- 235000011941 Tilia x europaea Nutrition 0.000 description 16
- 239000004571 lime Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 229910017251 AsO4 Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 241000534944 Thia Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 159000000011 group IA salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 3
- 150000001255 actinides Chemical class 0.000 description 3
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
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- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910009112 xH2O Inorganic materials 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 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 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate 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
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- 238000005538 encapsulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- UWRBYRMOUPAKLM-UHFFFAOYSA-L lead arsenate Chemical compound [Pb+2].O[As]([O-])([O-])=O UWRBYRMOUPAKLM-UHFFFAOYSA-L 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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- OBJSERXHTZNJCR-UHFFFAOYSA-N 2-methoxyethylmercury(1+);trihydroxy(oxido)silane Chemical compound COCC[Hg+].O[Si](O)(O)[O-] OBJSERXHTZNJCR-UHFFFAOYSA-N 0.000 description 1
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- NOJZFNKPDQHPBQ-UHFFFAOYSA-N arsoric acid;methane Chemical class C.O[As](O)(O)=O NOJZFNKPDQHPBQ-UHFFFAOYSA-N 0.000 description 1
- 208000014347 autosomal dominant hyaline body myopathy Diseases 0.000 description 1
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- 239000010953 base metal Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052589 chlorapatite Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- VJTAZCKMHINUKO-UHFFFAOYSA-M chloro(2-methoxyethyl)mercury Chemical compound [Cl-].COCC[Hg+] VJTAZCKMHINUKO-UHFFFAOYSA-M 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical class [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000009375 geological disposal Methods 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- XMBWDFGMSWQBCA-NJFSPNSNSA-N iodane Chemical compound [129IH] XMBWDFGMSWQBCA-NJFSPNSNSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical group [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JITOKQVGRJSHHA-UHFFFAOYSA-M monosodium methyl arsenate Chemical compound [Na+].C[As](O)([O-])=O JITOKQVGRJSHHA-UHFFFAOYSA-M 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 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
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 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
- 238000005504 petroleum refining Methods 0.000 description 1
- 229940096826 phenylmercuric acetate Drugs 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 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
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000011084 recovery Methods 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
- 238000005067 remediation Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0463—Hazardous waste
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/06—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
- C01G28/023—Arsenates; Arsenites of ammonium, alkali or alkaline-earth metals or magnesium
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/45—Inorganic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Civil Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Methods for waste treatment and compositions of stabilized waste elements are provided, typically for the disposal of arsenical wastes.ARsenic trioxide waste produced as a by-product of metal extraction is slurried in water for from 6 to 24 hours with finely divided quicklime to produce nonvolatile calcium arsenate (111)an excess of cao stoichiometry with ag is used to sonsume secondary waste species such as sulphate, silicate and iron oxides. The precipitated arsenate is oven dried at 120 degree celsius and then calcined in air between 15 minutes to several hours at 1000 degree celsius to 500 degree celsius respectively to oxidize arsenate (111)to arsenate (v)as ca5(as04(3(oh)(an apattite)as the major arsenic immobilization phase, with minor arsenic incorporated in ca3(as04)2. Calcium sulphate anhydrate (sulphate immobilization)and calcium iron oxide (iron immobilization)are also produced. Tertiary immobilization is achieved milling or fracturing and incorporating the apatite an encapsulant consisting of ordinary portland cement and flyash. After curing for one month in steel drums in a water saturated atmosphere, the waste form is ready to be transported either to a repository or to used as landfill. Further security may be achieved at the back end of the process by lining the repository with ferric clays that will strongly absorb and adsorb heavy metal species which may escape
Description
Title: COMPOSITIONS AND METHODS FOR WASTE TREATMENT
Abstract
Methods for waste treatment end coapoaitiona of stabilized waata alamenta are provided, typically for tha disposal of ara<nleal waataa. Arsenic trloxida waste produced aa a byproduct of natal extraction la slurried in water for froa S to 24 hours with finely divided qulekllaa to produce nonvolatile calclua arsenate (III). An excess of CaO •tolchlooetry with Aj. la used to consume secondary waste apeoles auch a· sulphate, silicate and Iron oxidaa. The precipitated arsenate la oven dried et 12O°C end then calcined In air between 15 alnutes to several hour· at 1000°C to 500°C respectively to oxidize arsenate (III) to arsenate (V) as CajtΑβΟ4>3(ΟΗ) (an apatite) as the nsjor arsenic lneobilizatlon phase, with alnor arsenic Incorporated In Ca3(AeO4)2· Caloium sulphate anhydrate (sulphate lsmobillzatlon) and calclun iron oxide (iron immobilization) ere also produced. Tertiary Immobilization la achieved
Billing or fracturing and incorporating the apatite an encapaulant oonslatlng of ordinary Portland cement and flyash. After curing for one month In steel druas In · water saturated atmosphere, the waste form Is ready to be transported either to a repository or to used as landfill.
Further security nay be achieved at the back end of the process by lining the repository with ferric clays that will strongly absorb end adsorb heavy netal species which asy !
escape.
BAD ORIGINAL (56) Documents cited:
US 4691198 A
EP 0347240 A EP 0352096 A
APPLICANTS CONTINUED
2. TIMOTHY JOHN WHITE 3 Mi rani Court West Lakes Shore South Australia 5020 AUSTRALIA
INVENTORS CONTINUED
2. TIMOTHY JOHN WHITE 3 Mi rani Court West Lakes Shore South Australia 5020 AUSTRALIA
3. GREGORY FRANCIS EATON 1/11 Wingfield Avenue Crawley
Western Australia 6009 AUSTRALIA bad original btr lb bJ 11 = 31 PIZZEY 8, COrtPAlSY +61-7-83S2090 P.3
APO 0 0 4 2 7
COMPOSITIONS AND METHODS FOR WASTE TREATMENT This Invention relates to compositions and methods of waste treatment.
This invention has particular but not exclusive application to compositions and methods for immobilizing heavy metal and metalloid wastes in a form suitable for geological disposal, and for illustrative purposes reference will be made to such application. However, it is to be understood that this Invention could be used in other applications, such as stabilization of other metallic waste streams.
Metal and metalloid waste streams often contain metal salts which are highly toxic or form toxic oxyanions. For example, araenio containing waste streams present a significant toxio hazard in land fill or the like due to the high leachability of arsenates (III) and the III and V state oxides of arsenic. In the past it has been proposed to immobilize arsenic containing waste materials by encapsulation in Portland cement. The arsenic oxides thus encapsulated are of variable oxidation state and generally comprise a mixture of compounds with arsenic in the III and V states. It has been proposed to treat the waste stream with «2θ2 or °^ber oxidizing agents to oxidize arsenic III to less soluble and less toxio arsenic V.
_ : A typical waste stream containing high levels of arsenic ( 25 is the waste produced by metal extraction from ores or concentrates of arsenopyrites. In general, condensed arsenic f oxides are produced by pyrometallurglcal processes and are precipitated from a condensed gas stream. It has been proposed to mix the oxide directly with aqueous Portland cement slurry and cure the mixture in (generally) mild steel containment or directly into fill or into other containment. ·
The disadvantages of this process relates to the instability of the compositions to certain conditions encountered in land fill disposal, Including susceptibility to leaching at low and high pH, and poor mechanical properties. Such compositions typically have compressive strengths of about 10 MPa at an equivalent λβ2θ3 loading of 50 wt % compared with a
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AP 0 0 0 4 2 7 strength of 20 MPa for Portland cement par se when mixed with an equivalent amount of clean building sand, where the eforedeacribed HgOg oxidation process is used to reduce the solubility of the incorporated waste, the process becomes uneconomic.
Other prior art proposed methods for arsenic waste stream treatment include mixing arsenic III-V oxides with an excess, generally between 3000 to 5000 mol *, of slaked lime Ca(0H)2 In water slurry to form generally insoluble calcium sreenate (III) and calcium arsenate (V) precipitates having a general formula 0βχ(λβ0ς)η. However, the precipitates have proven to be of variable leachsbllity, probably due to the presence of a proportion of soluble compounds Including arsenic III compounds. Also, the compositions are acid labile particularly with respect to COg or carbonates in the presence of groundwater or water vapour.
Additionally, acidic arsenic III-V oxide containing waste streams have been mixed with 200 or more mole* of ferric (oxy hydroxide), than adjusted to pH 5 to pH Θ with slaked lime in water to form ferric oxyarsenic compounds comprising mixed arsenate (III) and arsenate (V). Again these compositions are acid labile although less than Cax(AsO4)n, and are subject to leeching in the presence of carbonate and/or bicarbonate and water.
Both of the foregoing processes are only useful for treatment of waste streams containing metals or metalloids forming oxyanions such as arsenic.
In general the prior art processes do not produce a volume reduced waste stream, that is, the prior art processes do not generally result in relatively dense stabilised waste products incorporating the waste species at high mole percentages by weight. In addition, they do not form thermodynamically stable mineral structures.
Tha existence of proportions of volatile arsenic compounds in araenio waste streams has generally prevented the use of calcining processes for incorporation of such wastes in thermodynamically stable mineral structures.
The present invention aims to substantially alleviate at
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AP 0 0 0 4 2 7 least one of the above disadvantages and to provide compositions and methods of waste treatment which will be reliable and efficient in use. Other objects and advantages of this invention will hereinafter become apparent.
With the foregoing and other objects in view, this invention in one aspect resides broadly in a method of waste stabilization comprising the steps of:forming an oxide of a metal or metalloid component of said waste stream;
slurrying the oxide containing waste stream with an inorganic base or an inorganic oxyacld selected to form an insoluble precipitate with said oxide, and calcining said precipitate.
Preferably, the calcined precipitate has the metal or metalloid incorporated in its most stable oxidation state.
Preferably, the calcined precipitate comprises a stable mineral structure selected from one or more apatite, pyroohlore (Ai_202Og_7), perovskite (ABO3), hollandite (Αχ_ 2®8°16) or other stable form having its metal or metalloid components in their highest stable oxidation state. For example, for many heavy metals such as lead or metalloids such as arsenic, an apatite mineral structure is stable and preferred. Accordingly, in a further aspect this invention resides broadly in a method of stabilizing oxide wastes of metals or metalloids including the steps of:slurrying the waste material with a halide donor and a compound seleoted from an inorganic base or an oxyacid, said compound being selected such that a non-volatile metalloid oxyanion halide salt or a non volatile metal halo-oxyanlon salt ia formed respectively, and calcining said slurry to form an apatite crystal struoture or an analogue thereof.
In the foregoing context and hereinafter, the term metalloid oxide Includes oxides of hazardous elements, metalloids and metals which form oxyanions, such as arsenic, vanadium, sulphur, phosphorus, selenium, manganese and chromium. Metal oxide in the present context and nereinacter includes oxides of hazardous heavy metals which sre capable of forming
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AP 0 0 0 4 2 7 relatively Insoluble salts. Members of the latter group may aleo fall within the former. The term non-volatile in the context of the non-volatile metalloid oxyenion halide salt or a non volatile metal halo-oxyanion salt relates to the compounds having very low vapour pressures at the temperatures typically encountered during the calcining process.
Apatite structure in the present context is taken to be in aooordanoe with the definition of M. O'Keeffe and B.G.
Hyde. Although precise, the definition admits of small variations in structure and composition that will be expected in dealing with complex waste stream apatites. The structure is regarded ae an anion-stuffed alloy. The alloy part has the topology of the type MnjSigiDeg). For example in fluoroapatite CagiPOa^F, the CagPg cation array ie identical to the MngSlg type. The anions are then stuffed into the appropriate, usually tetrahedral interstices formed by the regular array of cations. Thus, all the oxygens forming the ΡΟ4 tetrahedra are in PCag tetrahedra of two types. The F eits in a 083 triangle (in hydroxyapatite the Ο ie in a Ca3H tetrahedra, while in chlorapatite the chlorine ie near the centre of a Cag octahedron). This description also readily explains the replacement of P043’ phosphate groups by 0032carbonate groups and SO42 sulphate groups as well ae instances on cationic non stoichiometry. Conversely, apatite structures having the general formula Aj(BO4)3X may show substitution or deviation in stoichiometry of the anions X and/or cations A.
Preferably, the process is adapted to the processing of cadmium, mercury and/or lead metal oxide wastes and ersenio, chromium, vanadium and/or selenium metalloid oxide wastes. Preferably, the slurrying step of processes in accordance with the present invention results in the production of one or both of two coexisting insoluble compounds. One has the general formula A5(BO4)3X where A - calcium, cadmium, mercury or lead, B - phosphorous, arsenic, chromium, vanadium, sulphur, carbon, silicon or selenium and X * fluorine, ahlorine or hydroxyl. The other has the general formula
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AP 0 0 0 4 2 7 *3(804)2* In the case of metals or metalloids such as arsenla, vanadium and chromium which form the anion radicals arsenate, vanadate or chromata the process involves reaction with an inorganic base, preferably CaO to promote the formation of non volatile ¢83(604)2 oompounde. In the case of other heavy metal waste streams which are compatible with thia form of processing for example, barium wastes, zinc wastes, mercury wastes and cadmium wastes, the process involves reaction with an inorganic oxyacld, preferably
K3PO4. in all cases, the waste forms are preferably tailored to ensure the crystallographic entrapment of the metals in highly insoluble apatites of the form or analogous minerals.
Preferably, the strong Inorganic base is selected from the alkaline earth basic oxides such as calcium oxide for processing of metalloid oxide wastes such as arsenic oxide containing wastes. For example, for processing wastes containing a predominance of arsenic oxide compounds the waste may be slurried with water and Inorganic base to provide a predominance of nonvolatile alkaline earth metal arsenates (111). Preferably the base is utilized in excess of stoichiometry to ensure the conversion to non volatile arsenates (III) and arsenates (V). Preferably, for arsenic waste treatment the alkaline earth or transition metal halide is selected from chlorides and fluorides to form non-volatile metal arsenate, the slurrying being preferably conducted In / the absence of acid species such as COg to maximize production of non volatile arsenate (III) compounds.
Preferably, the inorganic oxyacid is selected from the phosphorus oxyaclds. In instances where mixed wastes are to be processed, it may be desirable to combine the preferable lime and phosphoric acid processes. Alternatively, waste streams may be deliberately mixed to provide blended wastes treatable by combined lime and phosphoric acid procedures.
in practice it has been determined that for treatment of arsenical wastes to stable arsenate compounds, the commercial viability of the process may be determined by the reaction rate of the waste stream with the Inorganic base, preferably
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CaO. It has bean found that suitable reaction rates may be achieved by control of the slurrying temperature and control of the surface area and hence reactivity of the lime. The lime may be selected to be of surface area of greater than
0.5 m^/g and is preferably in the range 1.0 m^/g to greater than 2.0 m^/g. Such preferred reactivities may be produced, for example by moderate burning of calcium carbonate, overburning generally reducing the surface area to below 0.5 m^/g. Highly reactive limes may be produced by, for example, flesh calcining of calcium carbonate to limes having surface areas of about 2.0 m^/g.
Temperature control is particularly appropriate when dealing with waste streams including a predominance of λβ2θ3, since the availability of the arsenic oxide for reaction is determined by its dissolution characteristics in aqueous media. In the case of arsenic oxide, the reaction kinetics is dominated by the variation of solubility of the oxide with temperature end hence availability of oxide for reaction with the lime. Whereas arsenic oxide is slightly soluble (<1 mg/1) at 30°C, solubility increases to 30 mg/1 at 60°C and 65 mg/1 at 90°C.
Additionally it has been determined that concurrent addition of alkaline salts of light metols such as sodium and potassium to the slurry/hydrometallurglcal stage results in more rapid reaction rates. Rapid reaction rates are achieved by increasing the solubility of the reactant by production of a reactive intermediate. The reaction of the intermediate in accordance with the foregoing results in regeneration of the alkaline salts. Preferably, the alkaline salt is selected from NaOH and/or KOH. The supernatant containing the alkaline salt in solution may be recycled after the precipitated arsenates are removed by filtration or centri fugation.
Preferably, the metal halide is selected from transition metal halidas in the case of metal oxide wastes, and is seleoted from alkaline earth metal halides in respect of metalloid oxide wastes. Alternatively, the halide may be sourced from a halide donor such as HjSiFg, wherein a portion
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(.
( of the oxyanions of the apatites of the formula AjiBO^gX may be substituted by a proportion of residual Si04 anions. Preferably, metal halide salts such aa calcium fluoride or calolum chloride are Incorporated on the basis of well established cryetallochamical principles to produce fluorine or ohlorine Chemical forms of the compounds.
Preferably the insoluble precipitate of non volatile intermediates is calcined under conditions controlled to maximize the production of insoluble mineral compounds of an apatite or other stable structure. If desired the precipitate may be dewatered or dried prior to calcining.
Preferably, relatively pure water is used in the hydrometallurgicel slurrying process. For example, distilled and/or demineralised water is preferably used. In remote localities, distilled water may produced from ground water using vacuum distillation or reverse osmosis. The water is preferably recycled from the dewatering of the precipitate, oven drying and/or calcination stages.
Whilet apatite structures are preferred, some waste elements are not amenable to apatite immobilization. In these cases, a polyphase collection of compounds may be required to stabilise the components of a waste stream. For example, antimony V will be stabilised as Ai_2B2°7-xxx pyrochlore type structures. Thallium I may be stabilised in
Ai-2b8°16 hollandlte type. Thorium will be stabilised as ThP207· A summary of the preferred principal host phase for various toxic metals is giva in Table 1 below. These phases are preferably chosen because they are mutually compatible and can be prepared under similar, oxidizing conditions. The summery does not exclude the possibility of some waste elements partitioning between two or more phases and indeed such complexity is expected, and may be beneficial in accommodating compositional variations in a given waste stream.
TABLE 1.
Structure Type A5(BO4)3X apatite
Waste Element
A-Ca,Pb,Cd,Hg,Ba,Sr, Lanthanides, Actinides; Β·Ρ,As,Cr,v,Sl,Se;
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P. 13 a1-2b2°7-xxx pyrocnlore
ABO3 perovsklte
AP 0 c 04 2 7
X«F,Cl,Br,I, OH
A«Ca,Sr,Pb,Cd,Bs,Sr, Lanthanides, Actinides; B-Sb,Ti,V,Cr,Se;
X-F, Cl, Br,I,OH,NH4
A-Tl,Hg, alkali, alkali aarth B-transition metals
A-alkali, alkali earths, lanthanides, actinides; B-transition metals
The calcined precipitate may be physically consolidated in cementitious materials that will facilitate transport of the waste form to its ultimate disposal site. Selection of the insoluble compound and cementitious substance will be determined with reference to the geochemical characteristics of the landfill or other environmental conditions of disposal. For example, the calcine may be coaolidlfled with cementitious materials Including ordinary Portland cement, high alumina cements and magnesia cements. A consideration in selection of the cementitious material is the mechanical strength of the solidified product, which may be determined by the waste loading of the aggregate. Preferably, the cementitious barrier ie seleoted with the disposal environment in mind. For example, in ecidic soils ordinary Portland cement is stable and may be selected for use as the solidification medium. In basic soils, magnesia and/or alumina based cements may be used.
If desired, a proportion of the cementitious material may be replaced with pozzolenic flyesh. This provides additional advantages on the consolidated waste material by consuming another cheap waste material and providing enhanced immobilization properties such as higher density, less porosity and greater resistance to attack by sulphate and chloride.
Processes in accordance with the present invention may be executed as batch or continuous processes. For example, continuous processing may be mo9t appropriate for large, central facilities. Mixing and blending may be integrated and be followed successively with a filtering step and a
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Ρ. 11 consolidation/extrusion step. The consolidation/extrusion step nay yield either bricks or aggregate. Where extrusion i« to be used, it may be desirable to mix the filtered product with either a water soluble or alcohol soluble polymer or bentonite clay to optimize the plastic properties of the powder. The aggregate/bricka may than be fed into either a rotary kiln or belt kiln.
Batch processing may ba most appropriate for a small mobile unit that would service small sites requiring remediation. In thia case, bricking nay ba the preferred option, followed by tray calcination in a box kiln.
in order that this invention may be more readily understood and put into practical effect, reference will now ba made to the following examples and accompanying drawings whioh illustrate a preferred embodiment of the invention end wherein:FIG. 1 shows the flow sheet for Immobilization of arsenic trloxide derived during gold mining operations in accordance with the process of the present invention;
FIG. 2 shows the various levels of the multibarrier concept as applied to the disposal of arsenic trloxide in accordance with the present invention;
FIG. 3 illustrates a flow sheet for the preparation of such a waste form.
FIG. 4 comprises leach data in respect of stabilized waste forma produced in accordance with the present Invention.
EXAMPLE 1.
In one embodiment of this invention, arsenic trloxide waste produced ae a by-product of precious metal extraction was slurried in water with a quantity in excess of stolchlometrio of finely divided (approximately 50 micrometer particle size) quicklime to produce nonvolatile calcium arsenate (III). As such wastes Invariably contain lesser quantities of sulphate, silloate and iron oxides, sufficient excess quicklime is added to consume these secondary waste species. A slurry time of from 6 to 24 hours is sufficient for the reaction to be completed, depending on the reactivity
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1' of th· quicklime. After slurrying, the product was oven dried at 120°C with negligible loss of arsenic in the condensates and then calcined in air.
A range of calcination times and temperatures were 5 conducted on the dewatered precipitate, ranging from 15 minutes at 1000°C to several hours at 500°C. During firing the arsenate (III) is oxidized to arsenate (V), which promotes the formation of Cas(AsO4)g(OH) as the major arsenic immobilization phase, with minor arsenic incorporated in
Ca3(AsO4)2. Secondary waste species were crystallized aa calcium anhydrats (sulphate immobilization) and calcium iron oxide (iron immobilization).
Referring to FIG 1 it can be seen that the primary hydrometallurglcal reaction involves slurrying the areenia trioxide waste with quicklime in the ratio As203:CaO-3:5 to produce nonvolatile calcium arsenate (III). Because the mine waste contains compounds other than arsenic trioxide additional lime must be added in preferably stoichiometrio proportions to ensure stabilization of these minor species.
In the secondary calcination process, the slurry is firad for the temperatures and times shown so that the oxidation occurs and apatite is produced.
Tertiary immobilization is achieved by dividing the apatite by milling or fracturing, which is biologically safe, and incorporating the apatite in a cementitious encapsulant consisting of ordinary portland cement and flyash, with or without fume silica as a porosity and strength modifier.
Thia ia achieved by slurrying the apatite-cement mixture in water in a solid:water ratio of 1:0.4-0.7. After curing for one month in steel drums in a water saturated atmosphere, the waste form is ready to be transported either to a repository or to used as landfill. Further security may be achieved at the back end of the process by lining the repository with material (eg ferric clays) that will strongly absorb and adsorb heavy metal species which may escape.
FIG. 2 illustrates schematically a multibarrier waste immobilization regime as applied to calcium arsenate (V) apatite. The first level of immobilization is by
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II crystallization in the apatite. Additional stabilization is achieved by encapsulation of the insoluble compounds by a stable cementitious matrix which will inhibit dissolution. Should any portion of the arsenic dissolve it will be rapidly adsorbed by iron clays which will trap the arsenic and retard its dispersion into ths biosphere.
EXAMPLE 2.
Arsenlous waste from a base metal extraction is frequently placed in temporary storage in tailings dams. To minimise the concentration of solubilized arsenio in such dams an excess of lime is usually added to precipitate the waste as a calcium arsenate (III). These tailings dam slurries cannot be directly converted to an apatite because lime would be left in exaess. The presence of a substantial excess of lime is unsatisfactory as during hydration and through carbonation ths lime swells and destroys the physical integrity of the waste form.
To overcome this problem, the slurry is blended with areenio rich fume collected by precipitation in quantities
Just sufficient to consume the excess lime. The fume may contain lead and antimony in addition to arsenic. In addition, CaFj and/or CaCl2 are added to stabilise the haloapatite. The final apatite therefore would be rich in arsenic and lead, and contain minor antimony. Ths majority of the antimony partitions into a (Ca,jSb207_ X(F,C1,OH)X phase. FIC. 3 illustrates, in the form of a flow sheet, a waste stabilization process in accordance with this embodiment. FIG. 4 illustrates leach data obtained in a dynamic boiling water leach test carried out over a total of
11 days in respect of the apatite product of the process in accordance with this embodiment.
EXAMPLE 3.
BIOX* is a commercial biohydrometallurglcal process for tha recovery of gold from refractory sulphide ores. This process involves the bacterial oxidation of pyrlte/arsenopyrite sulphide concentrates to produce e liquor phase containing arsenic (V), ferric and sulphate ions,
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AP ο 0 0 4 2 7 according to the general aquations:
2FeAsS+702+2H20+H2S04 -* Fe2(S04)3+2H3AsO4
4FeS2+15O2+2H2O - 2Fe2(SO4)3+2H2SO4 The prooess can also be achieved by high pressures end temperatures without biological mediation.
To convert this waste to solid, the waste solution is first mixed with dilute phosphoric aoid to precipitate the iron aa iron orthophosphate end hence reduce the concentration of iron in tha waste stream.
3Fe2(S04)3+4H3P04+llH20 - 2Fe3(P04)28H20+9H2S04+502T
The remaining liquor of H3AsO4 and sulphuric acid is filtered and the reacted with quioklime and calcium fluoride CaF2 in stoichiometric quantity to yield arsenic (V) apatite and gypsum (calcium sulphate)
9CaO+6H3As04+CaF2+xH20 -* 2Ca5(As04)3F xH2O+9H2O
CaO+H2SO4+xH2O ·* CaSO4xH2O
This material le then dewatered and calcined in the usual way to remove water of crystallization to yield apatite and anhydrate and consolidate the product.
EXAMPLE 4
The procedure may be used to stabilise mercury wastes generated from mercurial fungicides including phenyl mercuric acetate (PMA, Tag*), methoxyethyl mercuric chloride and methoxyethyl mercury silicate (Ceresan* in Europe), ethyl mercuric chloride (Ceresan* in the US), hydroxy mercury chlorophenol (Semesan*), hydroxy mercury nitrophenol (Semeean Bel*) and methyl mercuric dicyandlamide (Panagen*). in this embodiment the mercury is liberated as an oxide by catalytic photooxidation of the mercurial using ultraviolet light of wavelength 180 nm. Finely divided sodium oxide and/or titania may be required to catalyze the reaction. The mercury oxide residue is slurried with dilute hydrophosphorlo ecid and fluorite in stoichiometric proportions to yield a compound possessing an apatite type crystal structure and having the chemical composition (HggCa)(P04)gF2. This material is dewatered at 120*C and then preferably *Regiatered Trade Mark
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AP 0 0 0 4 2 7 consolidated prior to firing at temperatures of up to 600*C. EXAMPLE 5.
In the case of mercuric chloride HgCl? the waste ie alurrled with lime and phosphoric acid in stoichiometric proportions to yield an apatite of composition (HgCag)(PO4)gCl2. This oompound is dried as before, consolidated and the fired at temperatures not exceeding 1000‘C.
EXAMPLE 6.
Organic arsenical herbicides Including the monoaodium (MSMA) and dlsodium (DSMA) salts of methane arsenic acid, and cacodylio acid may elso liberate arsenic oxide by catalytic photooxidation. The arsenic oxide can then be treated in the ueual way.
EXAMPLE 7.
Inorganic arsenic insecticides including lead arsenate PbHAsO4 and calcium arsenate Ca3(AsO4>2 and CaHAaO4 can be treated to produce apatites of the type (CaxPb^_
x)(As04)3(F,C1).
EXAMPLE 8.
Sulphate containing vanadium pentoxida spent catalysts are a waste generated during petroleum refining and sulphuric acid manufacture. These may be processed in accordance with the present invention to a two phase assemblage of an apatite (Ca)(V,PO4)3(F,Cl) and anhydrata CaSO4, by slurrying with lima and/or phosphoric acid and a halide salt in stoichiometric quantity. Firing is preferably to 1100*C.
EXAMPLE 9.
The Jarosite family of compounds MFe3(804)3( OH)g where M - H, Na, K, NH4, Ag, Pb are used as means of iron precipitation in zinc processing. The Jaroaites may also contain many heavy metals such as Pb, As, Cd and Hg.
Jarosite ia only stable at low pH(<3.2) and so these heavy metals may be released by raising the pH using a suitable ’93 4:09
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AP Γ. η o 4 2 7 base. The solubilised metals can then be concentrated by evaporation prior to treatment with lime end phosphoric acid in accordance with the present invention.
EXAMPLE 10.
Copper-chrome-arsenate (CCA) wood preservative* consist of the compounds copper sulphate (CuSOaBl^O), sodium dichromate (Na2Cr2072K20) and arsenic pentoxide (Α*2°5^Η2θ). Waste CCA may be treated by reaction with aufflatent lime and halide salt to form apatites of the form 085(0x04)3(7,01) and
Cas(Ae04)3(F, Cl) and Scheele’s green CUHASO3. Sodium ie removed by washing.
EXAMPLE 11.
Iodine-129 is a long lived fission product generated during consumption of nuclear fuel. It is also highly volatile. It can be readily collected ae a condensate in the off gas stream during dissolution and/or reprocessing of fuel rode. In this form it may be dissolved in dilute phosphoric acid and reacted with lead oxide to produce an apatite of composition PbgfPOjlgl.
EXAMPLE 12.
In another embodiment, lead bearing waste from sugar refining and having the formula NaPb2( 003)3011 was mixed with e stoichiometric quantity of dilute orthophosphoric acid to produce highly insoluble Pb5(PO4)3(011) that was separated from the NaHC03 residual solution by filtering. The
Pbg(704)3(OH) containing precipitate was then oven dried at 120vC. The dry product was calcined in air at about 400°C to remove organic materials such as residual sugars.
EXAMPLE 13.
Whist apatite structures are preferred, some waste elements are not amenable to apatite immobilization. In thia embodiment, radioactive wastes from sand mining containing high concentrations of thorium are digested in concentrated sulphuric acid, followed by treatment with phosphoric acid to
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AP 0 0 0 4 2 7 yield ThPjC^, which is stable and insoluble.
EXAMPLE 14.
Waste containing greater than 5 wt% antimony oxide cannot be stabilised all as apatite, but the excess antimony may be stabilized in an apatite compatible phase as a pyrochlore structure 062^6207_x(F,Cl,OH)x.
The foregoing procedures yield e waste form/phase assemblage whose dissolution characteristics are leas than current regulatory limits and which provides effective immobilization of the heavy metals and metalloids over geological times. The wastes are volume reduced, the density of the disposal material being in the region of 3 to 7 g/cc depending upon the waste stream composition. When incorporated in portland cement, the strength of the aggregate of clinker and fractured clinker is about 20MPa.
The preferred multibarrier treatment involves various barriers to prevent the movement of heavy metal species away from the waste site. The three barriers are the immobilization in an apatite phase, the cryetellochemlcal barrier provided by the cementitious material and the geologioal barrier provided by the burial 9ite. These three barrier levels may be selected in an integrated fashion so that a heavy metal immobilization system is designed whose reliability oan be guaranteed over geological times. For example, in the case of the arsenic mine waste, 50 wt% of the epatits could be consolidated with 25wtt ordinary Portland cement and 25wt% pozzolanic flyash. The waste form would have good mechanical strength (15 MPa) and be stable in an acidic geological setting.
A landfill of such geology could be excavated and lined with an iron bearing clay which would strongly absorb minor arsenate that may dissolve from the waste form Itself. Thue losses from arsenic from the near-field (waste form itself) and the far-fleld (liner and overpack) would be extremely low over extended times.
Further, since immobilization is provided according to well established chemical principles, the intrinsic long term
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AP o 0 0 4 2 7 leach resistance of the primary crystallochemical barrier can be determined. No other available technology offers this level of security, since immobilization technologies utilizing hitherto uncharacterized immobilization forms have unpredictable long term performance.
It will of course be realised that while the above has been given by way of illustrative example of this invention, all such and other modifications and variations thereto as would be apparent to persons skilled in the art are deemed to fell within the broad scope and ambit of this Invention as defined in the claims appended hereto.
Claims (21)
- THE CLAIMS DEFINING THE INVENTION ARB AS FOLLOWS:1. A method of waste stabilization comprising the steps of: forming an oxide of a metal or metalloid component of said waste stream;slurrying the oxide containing waste stream with an Inorganic base or an Inorganic oxyacid selected to form an insoluble precipitate with said oxide, and calcining said precipitate.
- 2. A method of waste stabilization according to Claim 1, wherein said calcined precipitate comprises a stable mineral structure selected from apatite, pyroohlore, hollandite and perovskite.
- 3. A method of stabilizing oxide wastes of metals or metalloids including the steps of:8lurrying the waste material with a halide donor and a compound selected from an inorganic base or an oxyacid, said compound being selected such that a non-volatile metalloid oxyanlon halide salt or a non volatile metal halo-oxyanion salt is formed respectively, and | calcining said slurry to form en apatite crystalI structure or an analogue thereof.i
- 4. A method of stabilizing oxide wastes according to Claim3, wherein said metalloid oxide includes oxides of hazardous elements, metalloids and metals which form oxyonions.i
- 5. A method of stabilizing oxide wastes according to Claim4, wherein said metalloid is selected from arsenic, vanadium, sulphur, phosphorus, manganese, selenium and chromium.II
- 6. A method of stabilizing oxide wastes according to Claim3, wherein said metal oxide includes oxides of hazardous heavy metals which are capable of forming relatively insoluble salts.15 SEP '93 4=1261 7 839 2090PAGE.019 bad originalSEP 15 '93 11'·45 PIZZEY & COMPANY +61-7-8392090P.20AP C· 0 0 4 2 7 x
- 7. λ method of stabilizing oxide wastes according to Claim 6, wherein said metal is selected from cadmium, mercury and lead.
- 8. λ method of stabilizing oxide wastes according to any one of the preceding Claims, wherein said calcined precipitate includes one or more of the minerals of the general formulae λςίΒΟ^βΧ and *3(604)2, where A calcium, cadmium, mercury or lead, B - phosphorous, arsenic, chromium, vanadium, sulphur, carbon, silicon or selenium and X fluorine, ahlorine or hydroxyl.
- 9. A method of stabilizing oxide wastes according to any one of the preceding Claims, wherein said strong inorganic base is seleoted from the alkaline earth basic oxides.
- 10. A method of stabilizing oxide wastes according to Claim9, wherein said oxide waste includes arsenic oxide containing waste, and wherein said inorganic base is calcium oxide.I
- 11. A method of stabilizing oxide wastes according claim 10, wherein the surface area of said calcium oxide is selected to 1 be in the range 1.0 m^/g to greater than 2.0 m^/g.
- 12. A method of stabilizing oxide wastes according to any one of the preceding Claims, wherein said inorganic oxyacid is seleoted from the phosphorus oxyacids.
- 13. A method of atabilizing oxide wastes according to Claim3, wherein said halide donor is selected from transition 1 metal halides in the case of metal oxide wastes, and is I selected from alkaline earth metel halides in respect of , metalloid oxide wastes.
- 14. A method of stabilizing oxide wastes according to Claim3, wherein said halide donor comprises I^SiFg such that said calcined precipitate comprises an apatite mineral of the general formula A5(B04)3F wherein A - calcium, cadmium,
- 15 SEP ’93 4:1261 7 839 2090PAGE .020BAD ORIGINALSEP 15 ' 93 11 = 45 PIZZEY & COMPANY +61-7-8392090 P.21AP o 0 0 4 2 7 meroury or lead, and B - phosphorous, arsenic, chromium, vanadium, sulphur, carbon, silicon or selenium, and wherein a portion of the oxyaniona of the apatite are substituted by a proportion of residual SiO4 anions.15. A method of stabilizing oxide wastes according to any one of the preceding Claims, wherein said calcined precipitate is further physically consolidated in cementitious materials.I
- 16. A method of stabilizing oxide wastes according to Claim 115, wherein said calcine is cosolidified with cementitious materials selected from portland cement, high alumina cements and magnesia cements.
- 17. A method of stabilizing oxide wastes according to Claim16, wherein a proportion of said cementitious material is replaoed with pozzolanic flyash.
- 18. A method of waste stabilization according to Claim 1, 1 wherein eald waste comprises radioactive wastes from sand mining containing high concentrations of thorium oxide, and including the steps of;dlgesting the waste with concentrated sulphuric acid; treating the digested waste with phosphoric acid; dewatering the precipitated ThP2O7, and calcining said precipitate.
- 19. Calcined mineral compounds and compositions comprising i ona or more of the minerals of the general formulae AgCBOjJgX and AgCBO^g, where A calcium, cadmium, mercury or lead, B- phosphorous, arsenic, chromium, vanadium, sulphur, carbon, silicon or selenium end X - fluorine, chlorine or hydroxyl.
- 20. A method of waste stabilization substantially as hereinbefore defined with reference to any one of the accompanying examples 1 to14 or any one of figures 1 to 4 of the accompanying drawings. jI15 SEP '93 4:1361 7 839 2090PAGE.021BAD ORIGINALSEP 15 '93 11 = 46 PIZZEY & COMPANY +61-7-8392390P.22AP 0 0 0 4 2 7
- 21. Calcined mineral compounds or compositions substantially as hereinbefore defined with reference to any one of the accompanying examples 1 to 14 or any one of figures 1 to 4 of the accompanying drawings.DATED THIS 16th DAY OF September 1993ISHER CORMACK & BOTHA ratent Agents for the Applicants15 SEP '93 4:1461 7 839 2090PAGE .022BAD ORIGINAL &AP Ο Ο Ο 4 2 71/3AS2O3 WasteQuicklimeCaCI2- SLURRY s.w = 1:2.5 N2 atmosphereTypical Mine Waste arsenolite anhydrate calciumarsenate iron silicate free silicateCALCINE between 600°C/5hr to 1200°C/15 minTypical product Insoluble Arsenates calcium arsenate apatite (johnbaumite) tricalcium arsenate (As-merrillite) anhydrate calcium iron oxide minor calcium and iron silicatesGRIND100 meshFlyash25wt%Stabilized Arsenate 50wt%Ordinary Portland Cement 25wt%SLURRY------CUREs.w= 1:0.4-0.7 Drums 1 monthFigure 1.DAD ORIGINALAP 0 0 0 4 2 72/3Figure 2. ' mmol/mm2 /dayFigure 4.BAD ORIGINAL £AP Ο Ο Ο 4 2 73/3Figure 3.bad original £SEP 15 '93 11=47 PIZZEY & COMPANY +61-7-8392090P.23 ‘ AP ο 0 0 4 2 7ABSTRACTMethods for waste treatment and compositions of stabilized waste elements are provided, typically for the dlspoeal of arsenical wastes. Arsenic trioxide waste produced as a byproduct of metal extraction is slurried in water for from 6 to 24 hours with finely divided quicklime to produce nonvolatile calcium arsenate (III). An excess of CaO stoichiometry with Aj. is used to consume secondary waste speoles such as sulphate, silicate and iron oxides. The precipitated arsenate is oven dried at 120°C and then oalcined in air between 15 minutes to several hours at 1000°C to 500°C respectively to oxidize arsenate (III) to arsenate (V) as Caj(Aa04)3(011) (an apatite) as the major arsenic immobilization phase, with minor arsenic Incorporated in Ca3(AaO4)2> Calcium sulphate anhydrate (sulphateImmobilization) and calcium iron oxide (iron immobilization) are also produced. Tertiary immobilization ia achieved milling or fracturing and Incorporating the apatite an ancapaulant consisting of ordinary Portland cement and j flyash. After curing for one month in steel drums in a ( water saturated atmosphere, the waste form is ready to be transported either to a repository or to used as landfill. Further security may be achieved at the back end of the process by lining the repository with ferric clays that will strongly absorb and adsorb heavy metal species which may escape.J
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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AUPL483792 | 1992-09-22 | ||
AUPM007493 | 1993-07-21 |
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AP9300598A0 AP9300598A0 (en) | 1994-01-31 |
AP427A true AP427A (en) | 1995-11-08 |
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APAP/P/1993/000598A AP427A (en) | 1992-09-22 | 1993-09-21 | Compositions and methods for waste treatment. |
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US (1) | US5649894A (en) |
EP (1) | EP0695224B1 (en) |
JP (1) | JPH08501249A (en) |
CN (1) | CN1095648A (en) |
AP (1) | AP427A (en) |
CA (1) | CA2145310A1 (en) |
DE (1) | DE69331469T2 (en) |
ID (1) | ID1043B (en) |
MY (1) | MY107766A (en) |
TW (1) | TW261602B (en) |
WO (1) | WO1994006575A1 (en) |
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- 1993-09-21 JP JP50761394A patent/JPH08501249A/en active Pending
- 1993-09-21 DE DE69331469T patent/DE69331469T2/en not_active Expired - Fee Related
- 1993-09-21 US US08/403,924 patent/US5649894A/en not_active Expired - Fee Related
- 1993-09-21 EP EP19930920615 patent/EP0695224B1/en not_active Expired - Lifetime
- 1993-09-21 AP APAP/P/1993/000598A patent/AP427A/en active
- 1993-09-21 ID ID936698A patent/ID1043B/en unknown
- 1993-09-21 WO PCT/AU1993/000489 patent/WO1994006575A1/en active IP Right Grant
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- 1993-09-22 CN CN93119625A patent/CN1095648A/en active Pending
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Also Published As
Publication number | Publication date |
---|---|
WO1994006575A1 (en) | 1994-03-31 |
DE69331469D1 (en) | 2002-02-21 |
TW261602B (en) | 1995-11-01 |
MY107766A (en) | 1996-06-15 |
EP0695224A4 (en) | 1997-07-23 |
EP0695224B1 (en) | 2002-01-16 |
US5649894A (en) | 1997-07-22 |
CA2145310A1 (en) | 1994-03-31 |
ID1043B (en) | 1996-10-28 |
AP9300598A0 (en) | 1994-01-31 |
DE69331469T2 (en) | 2002-08-29 |
EP0695224A1 (en) | 1996-02-07 |
JPH08501249A (en) | 1996-02-13 |
CN1095648A (en) | 1994-11-30 |
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