WO1991017124A1 - New formulations for iron oxides dissolution - Google Patents
New formulations for iron oxides dissolution Download PDFInfo
- Publication number
- WO1991017124A1 WO1991017124A1 PCT/US1991/002922 US9102922W WO9117124A1 WO 1991017124 A1 WO1991017124 A1 WO 1991017124A1 US 9102922 W US9102922 W US 9102922W WO 9117124 A1 WO9117124 A1 WO 9117124A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- composition
- reductant
- metal oxide
- dissolution
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000004090 dissolution Methods 0.000 title claims abstract description 38
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 43
- 235000013980 iron oxide Nutrition 0.000 title description 24
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 title description 8
- 238000009472 formulation Methods 0.000 title 1
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 31
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 22
- 230000002285 radioactive effect Effects 0.000 claims description 21
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000002386 leaching Methods 0.000 claims description 17
- 239000000356 contaminant Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
- 229910052768 actinide Inorganic materials 0.000 claims description 5
- 150000001255 actinides Chemical class 0.000 claims description 5
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000012857 radioactive material Substances 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 238000005202 decontamination Methods 0.000 claims description 3
- 230000003588 decontaminative effect Effects 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- ZVMWSLVUYOLQMI-UHFFFAOYSA-L S(=O)(=O)([O-])S(=O)(=O)[O-].C=O.[Na+].[Na+] Chemical group S(=O)(=O)([O-])S(=O)(=O)[O-].C=O.[Na+].[Na+] ZVMWSLVUYOLQMI-UHFFFAOYSA-L 0.000 claims 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical group OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 claims 1
- 150000002429 hydrazines Chemical class 0.000 claims 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 claims 1
- 229940046817 hypophosphorus acid Drugs 0.000 claims 1
- 239000011133 lead Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 229910052598 goethite Inorganic materials 0.000 description 15
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000006698 induction Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 229910017852 NH2NH2 Inorganic materials 0.000 description 1
- 229910017912 NH2OH Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910002005 actinide nitrate Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000013759 synthetic iron oxide Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
- G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
- G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces
Definitions
- This invention was developed under contract from the DOE W-31-109-ENG-38.
- the present invention relates to a synergistic composition for dissolving metal oxides and in particular iron oxides.
- the dissolution of iron oxides is a very important technological process with applications in a number of different fields.
- Effective dissolution agents can be useful for (1) leaching of oxide ores in hydrometallurgy to recover metal values from the oxide ores; (2) removal of iron oxide contaminants from non-metallic materials such as minerals (e.g. kaolin and silica) , of importance for the glass and ceramic manufacturing industry; (3) stripping of metal ions from extraction solvents or from ion exchange resins; (4) cleaning of metals prior to subsequent processing (e.g. removal ⁇ f scale from a metal prior to rolling, anodizing, galvanizing or painting; (5) removal of deposits from equipment in contact with hot water or steam (e.g.
- radioactive materials including removal of a surface layer of oxides from steel equipment used for radioactive material processing or in nuclear plants, in order to facilitate the removal of radioactive contaminants (e.g. the actinide and lanthanide elements) present in or below the surface oxide layers by subsequent application of an appropriate complexing agent; leaching of radioactive sludge; and leaching of radioactive soil.
- radioactive contaminants e.g. the actinide and lanthanide elements
- GB-1229582 ((Albright & Wilson Mfg. Ltd.-1971)- U.S. 3634257 (1972) equivalent) describes the use of phosphonic acids to remove encrustations containing calcium carbonate or iron compounds from rigid surfaces, e.g. stills and boiler t u b e s . T h e p r e f e r r e d a c i d i s 1-hydroxyethylidene-l,1-diphosphonic acid, which can also be used with other scale removing acids and with ammonia.
- Albright & Wilson sells a product based on GB 1229582, BRIQUEST DP 13, for use as a railway carriage cleaner. It is described as a blend of BRIQUEST ADPA (1-hydroxyethylidene-l, 1-diphosphonic acid) and orthophosphoric acid specifically formulated for use with carriage-washing machines.
- BRIQUEST ADPA 1-hydroxyethylidene-l, 1-diphosphonic acid
- orthophosphoric acid specifically formulated for use with carriage-washing machines.
- Valverde N. and Wagner, C. , Ber. Bunsenges Physik. Chem. 80(4) (1976) 330 and Valverde N. , Ber. Bunsenges. Physik. Chem. 80(4) (1976) 333 describe experiments which show that the dissolution of iron oxide is accelerated by decreasing the redox potential and attribute this to reduction of Fe +3 in the oxide lattice to give the more soluble Fe +2 .
- Lu, Z. Y. and Muir, D. M. , Hydro etallurgy 21 (1988) 9 describes experiments in which an enhanced leaching rate of metal ferrites and iron oxides is found when HCl leaching solutions also contain Cu +1 or Sn +2 as reductants.
- Zinder, B. , Furrer, G. and Stomm, W. , Geochimica et Cosmochimica Acta 50 (1986) 1861 describes acceleration of the rate of alpha - FeOOH dissolution by NaN0 3 in the presence of ascorbic acid.
- Banwart, S. , Davies, S. and Strumm, W. , Colloids and Surfaces 39 (1989) 303 describes the use of oxalic acid and L-ascorbic acid to dissolve iron oxide and shows an advantage for using the two together.
- Metal oxides and metal salts are dissolved by treatment with aqueous solutions containing mixtures of di- or polyphosphonic acids and reducing agents, preferably sulfur based.
- the solution can contain corrosion inhibitors and pH adjusting agents.
- the mixtures according to the present invention produce dissolution rates which are substantially higher than those observed with either the acids or the reductants by themselves.
- HEDPA 1-hydroxyethylidene-l,l-diphosphonic acid
- Preferred reductants are the sulfur-based reducing agents such as sodium sulfite (Na 2 S0 3 ) and especially sodium formaldehyde sulfoxylate (SFS) and sodium dithionite (Na 2 S 2 0 4 ) .
- sulfur-based reducing agents such as sodium sulfite (Na 2 S0 3 ) and especially sodium formaldehyde sulfoxylate (SFS) and sodium dithionite (Na 2 S 2 0 4 ) .
- Corrosion inhibitors or pH adjustors can reduce corrosion problems.
- the inventive mixtures can be used especially to remove radioactive contaminants from equipment and tools used in handling and processing radioactive materials and in dissolving radioactive sludge and removing radioactive oxides and salts from contaminated soil where alternative methods are not readily available.
- the invention is based on the discovery that aqueous mixtures of di- or polyphosphonic acids and reducing agents produce unexpectedly high dissolution rates as compared with the rates obtained for acids or for reducing agents alone, or mixtures thereof in general.
- Reducing agents include sulfur-based reducing agents such as sulfurous acid, disulfurous acid, dithionous acid, hydroxymethylsulfinic acid (acid of SFS) , hydroxymethyl sulfonic acid, and their salts; phosphorous based reductants such as phosphorous acid, hypophosphorous acid and their salts; aldehyde or hydroxymethyl adducts thereof, such as formaldehyde, acetaldehyde, hydroxymethylsulfinic acid, hydroxymethyl sulfonic acid, or their salts, tetrakis(N,N,N' ,N'-hydroxymethyl)urea, and a tetrakis(hydroxymethylphosphonium) salt.
- Nascent hydrogen (produced in situ) and water soluble salts forming Cr +2 , V +2 and Cu +1 are further examples of reductants for use in the present invention.
- the synergistic effect is very pronounced in the case of di- or polyphosphonic acids mixed with sulfur-based reducing agents, and especially a combination of HEDPA and SFS. Very high rates were also observed for hydrogen produced in situ (by reaction of Zn in an acid media) . Both HEDPA and SFS by themselves produce very low dissolution rates, but when combined, very fast dissolution rates are obtained even at 25 degrees Centigrade. This permits safer, faster and easier processing while minimizing the risk of corrosion. Corrosion can be further inhibited using pH adjustors or usual corrosion inhibitors.
- a pH adjustor will normally be a basic substance.
- the acids will be at least partially converted to their salts.
- pH adjustors are, for example, alkali metal or alkaline earth metal hydroxides such as sodium, calcium or potassium hydroxide.
- alkali metal or alkaline earth metal hydroxides such as sodium, calcium or potassium hydroxide.
- pH adjusting agents that can be used to advantage include ammonium and various derivatives thereof e.g. alkyl, alkylene or alkanol derivatives.
- alkyl derivatives include a C 1 -C 3 alkyl amine and especially methyl amine, di- or tri-methyl amine.
- Alkylene derivatives include ethylene diamine and others corresponding to the alkyl compounds. Corresponding alkanol derivatives can also be used, including diethanol amine for example.
- radioactive materials e.g. oxides and salts of actinide and lanthanide elements
- the invention can be applied quite widely for removal or dissolution of metal oxides as noted above; for decontamination of radioactive metal surfaces there are few practical alternatives available. Control of corrosiveness as by pH adjusting agents or corrosion inhibitors may be particularly important in these uses, to avoid degrading difficult to replace parts and apparatus.
- the surface oxide coating containing the radioactive contaminants is removed.
- the best way to do this is to attack and dissolve the surface oxide coating directly.
- the surface oxide will in most cases be an iron oxide since most equipment is constructed from iron or iron-containing alloys.
- the radioactive contaminants may then be carried or washed into solution with the iron oxide, or complexed with reactants to take them into solutions.
- a further advantageous use for this technology is for the retrieval and treatment of high level nuclear waste, at present stored in single or double shell tanks at a number of nuclear sites. Many of these nuclear waste solutions have been neutralized in the tanks by addition of alkali, to reduce their corrosive power. This treatment has generated large amounts of radioactive sludge in the tanks. In order to retrieve and further process these wastes to concentrate the high level radioactive components and carry out permanent disposal, it will be necessary to leach and/or dissolve the sludge solids to release the radioactive metals into solution.
- a third use is in the leaching of radioactive or other metal (e.g. chromium) contaminants from contaminated soils. Leaching of soils is accomplished by heap leaching or by processing in tanks.
- radioactive or other metal e.g. chromium
- oxide ores as by heap leaching or in tanks
- removal of iron oxide contaminants from non-metallic materials such as minerals (e.g. kaolin and silica by batch processing in tanks)
- washing metals with the inventive composition prior to processing e.g. removal of scale from a metal prior to rolling, anodizing, galvanizing or painting
- flushing of pipes, boilers, and etc. for the removal of deposits from surfaces in contact with hot water or steam by pumping the mixture through the pipes
- cleaning or treatment of rusty bolts, nuts and connectors and (9) removal of stains (iron oxide related) from fabrics by solubilizing the iron oxide and washing it away.
- Radioactive synthetic Goethite samples containing 59 Fe at a level of 1.7 x 10 4 count per minute/ mg of dried solid were prepared and used for this and subsequent dissolution experiments.
- the dissolution experiments were performed by contacting in screw-cap glass tubes a weighed amount of radioactive Goethite (about 50 mg) with the dissolving medium at a volume-weight ratio of 40 (2 ml for 50 mg) .
- the size of the particles of iron oxide were estimated to be in the range of 60-120 mesh.
- the glass tubes containing the Goethite were thermally equilibrated in a heating bath and then the dissolving solution was added.
- the mixture in the glass tubes was agitated using a magnetic stirrer, to suspend the iron oxide in the dissolving medium. At various time intervals tubes were withdrawn from the bath; rapidly quenched by cooling; and thereafter centrifuged to remove the particles of Goethite for suspension.
- the iron levels in the supernatant solutions were measured by measuring the radioactivity of the supernatant solution with a gamma counter.
- First order rate constants and induction times for dissolution of the Goethite were calculated from the measurements by standard methods.
- Zn(H 2 ) indicates the use of hydrogen formed in situ by use of Zn in an acid medium. It is the nascent hydrogen that acts as the reductant.
- the first order rate constants were ⁇ 1.0 x 10 ⁇ 6 sec" 1 .
- Goethite samples were treated under mild temperature conditions of 25 degrees Centigrade with IM HEDPA and O.IM solutions of various reducing agents, using the procedures described in Example 1. The times for dissolution of the Goethite were measured and the times in minutes for dissolution of 10%, 50% and 90% of the solids were calculated. The results were as follows:
- Goethite samples were treated at 80 degrees Centigrade with O.IM HEDPA and 0.1 M solutions of various reducing agents, using the procedures described in Example 1. The times for dissolution of the Goethite were measured and the times in minutes for dissolution of 10%, 50% and 90% of the solids were calculated. The results were as follows:
- Example 6 Na 2 S 2 0 4 ⁇ 1 ⁇ 1 Although treatment under high temperature conditions as compared with Example 6, resulted in higher activities for all reactants, the surprisingly more active reductants in accordance with the condition of Example 6, maintained their comparatively higher activity under the more rigorous conditions of Example 7.
- Each sample was prepared by 1) oxidizing the surface with hydrogen peroxide; 2) heating a disc to a dull red heat for a few seconds in air; 3) depositing tracer level concentrations of one of the three actinides, as a nitrate salt, on the surface of the disc; and 4) heating the disc again to a dull heat for 10 seconds to insure that the actinide nitrate is converted to its oxide and to insure that the activity is driven into the oxide film on the surface of the steel discs.
- sample discs were then counted radiometrically using an internal proportional alpha counter to measure the quantity ⁇ f activity on each disc. These samples represent an extreme case with respect to difficulty in removing contamination.
- the discs were introduced into solutions of 1-hydroxyethylidene-l,l-diphosphonic acid (HEDPA) and SFS as shown in the following Table.
- the solutions were stirred with a magnetic stirrer. After the indicated predetermined period of time, the discs were rinsed with water, dried on a hot plate and recounted in the proportional alpha counter. The discs were then leached a second, and in some cases a third time, using the same procedure.
- Two series of experiments were performed, one at room temperature and the other at 70-80 degrees Centigrade. The results are tabulated below: Leaching Solution: IM HEDPA/O.IM SFS Room Temperature (about 25 degrees Centigrade)
- di- and polyphosphonic acids include di- and polyphosphonic acids.
- aminophosphonic acids such as aminotris(methylenephosphonic acid).
- the reductants include organic reductants, such as ascorbic acid and hydroquinone and inorganic reductants.
- Sulfur-based reductant such as sodium sulfite, sodium dithionite and sodium formaldehyde sulfoxylate show the greatest effect. Hydrogen formed in situ shows a similar strong effect.
- Acid concentrations can range up to the concentration of standard concentrated acid as manufactured, but are preferably in the 0.01-3M range.
- the reductant concentrations can range up to about 5M, but are preferably in the 0.001-0.3M range.
- the ratio of acid to reductant is preferably at least 0.5, more preferably at least 5 and most preferably at least 10.
- the treatment temperatures can range from ambient up to the reflux temperature of the treatment solution, but preferably in the ambient to 80 degrees Centigrade range. Treatment at ambient temperature is especially preferred.
- the inventive composition for decontaminating hand tools or other small pieces of equipment which may have been contaminated such as by use in a nuclear power plant, it is possible simply to dip the equipment or tools into a container of a composition in accordance with the present invention. Alternatively, the composition can be sprayed onto the surface or rubbed on with a suitable applicator.
- a contact time of several minutes should be used.
- a contact time of 10 minutes up to about 1 hour is preferable. This can be determined by measuring the residual radiation of the tools to be sure that they are properly decontaminated. As shown in Example 8 above, even with baked- in contaminants, substantial reduction in contamination is possible after 1 hour although some samples were treated for up to 24 hours.
- a composition in accordance with the present invention is circulated through the pipes or other equipment to be decontaminated for a sufficient time to accomplish the required results. Spraying or applying with a suitable applicator may also be used. If equipment is being decontaminated, the level of radiation can be measured to determine when the treatment is sufficient. The removal of scale or other iron oxide deposits can be determined by inspection or, in extreme cases where there is clogging, by a reduction in the back pressure on the materials being pumped through the system.
- Removal of iron oxide contaminants can be done using usual equipment to leach contaminants from many types of materials. Heap leaching of soil or ore can be practiced, for example.
- the treatment of radioactive sludge can also be accomplished by leaching the sludge with the inventive materials although usual precautions necessary for handling such materials must be applied.
- Leaching can be accomplished by heap-leaching or batch processing methods such as are usual in metal value recovery operations used in the mining industry.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU9192016380A RU2096499C1 (en) | 1990-04-30 | 1991-04-26 | Mixture for dissolving metal oxides and dissolving method |
CA002081767A CA2081767C (en) | 1990-04-30 | 1991-04-26 | Formulations for iron oxides dissolution |
JP3509827A JP3014448B2 (en) | 1990-04-30 | 1991-04-26 | Metal oxide dissolving agent |
EP91909854A EP0527908B1 (en) | 1990-04-30 | 1991-04-26 | New formulations for iron oxides dissolution |
DE69130019T DE69130019T2 (en) | 1990-04-30 | 1991-04-26 | Novel compositions for dissolving iron oxides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US07/516,436 US5078894A (en) | 1990-04-30 | 1990-04-30 | Formulations for iron oxides dissolution |
US516,436 | 1990-04-30 |
Publications (1)
Publication Number | Publication Date |
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WO1991017124A1 true WO1991017124A1 (en) | 1991-11-14 |
Family
ID=24055582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1991/002922 WO1991017124A1 (en) | 1990-04-30 | 1991-04-26 | New formulations for iron oxides dissolution |
Country Status (8)
Country | Link |
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US (2) | US5078894A (en) |
EP (1) | EP0527908B1 (en) |
JP (1) | JP3014448B2 (en) |
AT (1) | ATE169892T1 (en) |
CA (1) | CA2081767C (en) |
DE (1) | DE69130019T2 (en) |
RU (1) | RU2096499C1 (en) |
WO (1) | WO1991017124A1 (en) |
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FR2695839A1 (en) * | 1992-09-23 | 1994-03-25 | Commissariat Energie Atomique | Reducing decontaminating gel and its use for the surface decontamination in particular of nuclear installations. |
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Publication number | Publication date |
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EP0527908A1 (en) | 1993-02-24 |
RU2096499C1 (en) | 1997-11-20 |
JPH05507305A (en) | 1993-10-21 |
ATE169892T1 (en) | 1998-09-15 |
CA2081767A1 (en) | 1991-10-31 |
US5587142A (en) | 1996-12-24 |
EP0527908B1 (en) | 1998-08-19 |
EP0527908A4 (en) | 1993-04-14 |
US5078894A (en) | 1992-01-07 |
DE69130019T2 (en) | 1999-04-08 |
CA2081767C (en) | 2001-06-05 |
JP3014448B2 (en) | 2000-02-28 |
DE69130019D1 (en) | 1998-09-24 |
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