EP2841204B1 - Magnetic separation of particles including one-step-conditioning of a pulp - Google Patents
Magnetic separation of particles including one-step-conditioning of a pulp Download PDFInfo
- Publication number
- EP2841204B1 EP2841204B1 EP13722697.3A EP13722697A EP2841204B1 EP 2841204 B1 EP2841204 B1 EP 2841204B1 EP 13722697 A EP13722697 A EP 13722697A EP 2841204 B1 EP2841204 B1 EP 2841204B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- magnetic
- magnetic particle
- group
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002245 particle Substances 0.000 title claims description 29
- 238000007885 magnetic separation Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 103
- 239000000463 material Substances 0.000 claims description 98
- 239000000203 mixture Substances 0.000 claims description 93
- 239000006249 magnetic particle Substances 0.000 claims description 86
- 239000000126 substance Substances 0.000 claims description 66
- 239000006185 dispersion Substances 0.000 claims description 37
- 230000005291 magnetic effect Effects 0.000 claims description 30
- 239000002612 dispersion medium Substances 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003776 cleavage reaction Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 230000007017 scission Effects 0.000 claims description 10
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 235000013980 iron oxide Nutrition 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 230000005294 ferromagnetic effect Effects 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 2
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 claims description 2
- 229910052595 hematite Inorganic materials 0.000 claims 1
- 239000011019 hematite Substances 0.000 claims 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- -1 tripolyphosphate ions Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 241000907663 Siproeta stelenes Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052951 chalcopyrite Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052948 bornite Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052955 covellite Inorganic materials 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052590 monazite Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108091005950 Azurite Proteins 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002547 FeII Inorganic materials 0.000 description 1
- 229910002553 FeIII Inorganic materials 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910017713 NHx Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009852 extractive metallurgy Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 230000005661 hydrophobic surface Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FYHQYEVHSYHJHO-UHFFFAOYSA-N octoxymethanedithioic acid Chemical compound CCCCCCCCOC(S)=S FYHQYEVHSYHJHO-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 229910052954 pentlandite Inorganic materials 0.000 description 1
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 1
- HRANSTGHZSEXRW-UHFFFAOYSA-M potassium;dioctyl-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [K+].CCCCCCCCP([S-])(=S)CCCCCCCC HRANSTGHZSEXRW-UHFFFAOYSA-M 0.000 description 1
- ABCMVVZRRCUIBB-UHFFFAOYSA-M potassium;n,n-dioctylcarbamodithioate Chemical class [K+].CCCCCCCCN(C([S-])=S)CCCCCCCC ABCMVVZRRCUIBB-UHFFFAOYSA-M 0.000 description 1
- KZMAIULISOIRKM-UHFFFAOYSA-M potassium;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [K+].CCCCCCCCOP([O-])(=S)SCCCCCCCC KZMAIULISOIRKM-UHFFFAOYSA-M 0.000 description 1
- YEEBCCODSASHMM-UHFFFAOYSA-M potassium;octoxymethanedithioate Chemical compound [K+].CCCCCCCCOC([S-])=S YEEBCCODSASHMM-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- AAJRIJBGDLLRAE-UHFFFAOYSA-M sodium;butoxymethanedithioate Chemical compound [Na+].CCCCOC([S-])=S AAJRIJBGDLLRAE-UHFFFAOYSA-M 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C2201/00—Details of magnetic or electrostatic separation
- B03C2201/18—Magnetic separation whereby the particles are suspended in a liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C2201/00—Details of magnetic or electrostatic separation
- B03C2201/20—Magnetic separation whereby the particles to be separated are in solid form
Definitions
- the present invention relates to a process for separating at least one first material from a mixture comprising this at least one first material and at least one second material by contacting said mixture with at least one magnetic particle and at least one surface-modifying substance at the same time, so that the at least one first material, the at least one surface-modifying substance and the at least one magnetic particle become attached to one another, and by subsequently separating the addition product from the mixture by application of a magnetic field.
- the present invention relates to a process for the enrichment of ores in the presence of the gangue.
- WO 02/0066168 A1 relates to a process for separating ores from mixtures comprising these, in which suspensions or slurries of these mixtures are treated with particles which are magnetic and/or capable of floating in aqueous solutions. After addition of the magnetic particles and/or particles capable of floating, a magnetic field is applied so that the agglomerates are separated off from the mixture.
- a magnetic field is applied so that the agglomerates are separated off from the mixture.
- the extent to which the magnetic particles are bound to the ore and the strength of the bond is not sufficient for the process to be carried out with a satisfactorily high yield and effectiveness.
- US 4,657,666 discloses a process for the enrichment of ores, in which the ore present in the gangue is treated with magnetic particles, as a result of which agglomerates are formed due to the hydrophobic interactions.
- the magnetic particles are hydrophobized on the surface by treatment with hydrophobic compounds, so that attachment to the ore occurs.
- the agglomerates are then separated off from the mixture by means of a magnetic field.
- the cited document also discloses that the ores are treated with a surface-activating solution of 1% sodium ethylxanthogenate before the magnetic particle is added.
- separation of ore and magnetic particle is effected by the destruction of the surface-activating substance which has been applied in the form of the surface-activating solution to the ore. Furthermore, in this process only C 4 -hydrophobising agents are used for the ore.
- US 4,834,898 discloses a process for separating off nonmagnetic materials by bringing them into contact with magnetic reagents which are enveloped by two layers of surface-modifying substances. US 4,834,898 also discloses that the surface charge of the nonmagnetic particles which are to be separated off can be influenced by various types and concentrations of electrolytes reagents. For example, the surface charge is altered by addition of multivalent anions, for example tripolyphosphate ions.
- WO 2007/008322 A1 discloses a magnetic particle which is hydrophobized on the surface for separating impurities from mineral substances by magnetic separation processes. According to WO 2007/008322 A1 , a dispersant selected from among sodium silicate, sodium polyacrylate and sodium hexametaphosphate can be added to the solution or dispersion.
- US 2011/240527 A1 and WO 2011/058039 A1 disclose processes for separating at least one first material from a mixture comprising this at least one first material and at least one second material by contacting said mixture with at least one magnetic particle and at least one surface-modifying substance in consecutive steps, so that the at least one first material, the at least one surface-modifying substance and the at least one magnetic particle become attached to one another, and by subsequently separating the addition product from the mixture by application of a magnetic field.
- WO2009/030669 A1 discloses a process for separating at least one first material from a mixture comprising this at least one first material and at least one second material, in which the first material is firstly brought into contact with a surface-modifying substance to hydrophobize it, this mixture is then brought into contact with at least one magnetic particle so that the magnetic particle and the hydrophobized first material become attached to one another and this agglomerate is separated from the at least one second material by application of a magnetic field.
- the at least one first material is subsequently separated, preferably quantitatively, from the magnetic particle, with the magnetic particle preferably being able to be recirculated to the process.
- This document does not disclose that the addition of magnetic particles prior to a surface-modifying substance or the addition of magnetic particles and a surface-modifying substance at the same time gives rise to certain advantages like accelerated agglomeration.
- a further object of the present invention is to treat the first particles to be separated off in such a way that the addition product of magnetic particle and first material is sufficiently stable to ensure a high yield of the first material in the separation.
- a further object is to provide a process for separating particles from a mixture comprising them and other particles, using magnetic particles to obtain magnetic agglomerates of particles to be separated and magnetic particles, wherein the agglomeration occurs faster and more evenly than in processes of the prior art.
- the process of the invention is employed for separating at least one first, hydrophobic material from a mixture comprising this at least one first, hydrophobic material and at least one second, hydrophilic material.
- hydrophobic means that the corresponding particle can subsequently be hydrophobized by treatment with the at least one surface-modifying substance.
- a particle which is hydrophobic per se prefferably be additionally hydrophobized by treatment with the at least one surface-modifying substance.
- hydrophobic means that the surface of corresponding "hydrophobic substances", and, respectively, of a “hydrophobized substance” has a contact angle with water against air of > 90°.
- hydrophilic means that the surface of corresponding “hydrophilic substance” has a contact angle with water against air of ⁇ 90°.
- the at least one first material is at least one hydrophobic metal compound or coal and the at least one second material is preferably at least one hydrophilic metal compound.
- the at least one hydrophobic metal compound is selected from the group consisting of sulfidic ores, oxidic ores, carbonate-comprising ores, noble metals in elemental form, compounds comprising noble metals and mixtures thereof.
- the present invention therefore relates to the process according to the present invention, wherein the at least one hydrophobic metal compound is selected from the group consisting of sulfidic ores, oxidic ores, carbonate-comprising ores, noble metals in elemental form, compounds comprising noble metals and mixtures thereof.
- the at least one hydrophilic metal compound is selected from the group consisting of oxidic metal compounds, hydroxidic metal compounds and mixtures thereof.
- the present invention therefore relates to the process according to the present invention, wherein the at least one hydrophilic metal compound is selected from the group consisting of oxidic metal compounds, hydroxidic metal compounds and mixtures thereof.
- Examples of the at least one first material to be separated off are preferably metal compounds selected from the group consisting of sufidic ores, oxidic and/or carbonate-comprising ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ] or malachite [Cu 2 [(OH) 2
- CO 3 ]], rare earth metals comprising ores like bastnaesite (Y, Ce, La)CO 3 F, monazite (RE)PO 4 (RE rare earth metal) or chrysocolla (Cu,Al) 2 H 2 Si 2 O 5 (OH) 4 ⁇ n H 2 O, noble metals in elemental form and their compounds to which a surface-modifying compound can become selectively attached to produce hydrophobic surface properties.
- rare earth metals comprising ores like bastnaesite (Y, Ce
- noble metals that may be present as at least first material are Au, Pt, Pd, Rh, etc., preferably in the native state or as sulphides, phosphides, selenides, tellurides or as alloys with bismuth, antimony and/or other metals.
- sulfidic ores which can be separated according to the invention are, for example, selected from the group of copper ores consisting of covellite CuS, molybdenum(IV) sulfide, chalcopyrite (cupriferous pyrite) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite (copper glass) Cu 2 S, pendlandite (Fe,Ni) 9 S 8 , and mixtures thereof.
- Suitable oxidic metal compounds which may be present as at least one second material according to the invention are preferably selected from the group consisting of silicon dioxide SiO 2 , silicates, aluminosilicates, for example feldspars, for example albite Na(Si 3 Al)O 8 , mica, for example muscovite KAl 2 [(OH,F) 2 AlSi 3 O 10 ], garnets (Mg, Ca, Fe II ) 3 (Al, Fe III ) 2 (SiO 4 ) 3 and further related minerals and mixtures thereof.
- untreated ore mixtures obtained from mines are preferably used as mixture comprising at least one first material and at least one second material in the process of the invention.
- the mixture comprising at least one first material and at least one second material in step (A) is in the form of particles having a size of from 100 nm to 100 ⁇ m, see for example US 5,051,199 . In a preferred embodiment, this particle size is obtained by milling. Suitable processes and apparatuses are known to those skilled in the art, for example wet milling in a ball mill.
- the mixture comprising at least one first material and at least one second material is therefore milled to particles having a size of from 100 nm to 100 ⁇ m before or during step (A) in a preferred embodiment of the process of the invention.
- Preferred ore mixtures have a content of sulfidic minerals of at least 0.4% by weight, particularly preferably at least 10% by weight.
- sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above.
- sulfide of metals other than copper for example, sulfides of iron, lead, zinc or molybdenum, i.e. FeS, FeS 2 , PbS, ZnS or MoS 2 , can also be present in the mixtures.
- oxidic compounds of metals and semimetals for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides/hydroxides/carbonates, and further salts, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 (CO 3 )]], barite (BaSO 4 ), monazite ((La-Lu)PO 4 ), spinels (Mg, Ca, Fe(II))(Fe(III), Al, Cr) 2 O 4 , can be present in the ore mixtures to be treated according to the invention.
- silicates or borates or other salts of metals and semimetals for example phosphates, sulfates or oxides/hydroxides/carbonates
- further salts for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2
- a typical ore mixture which can be separated by means of the process of the invention has the following composition: about 30% by weight of SiO 2 as an example of a preferred at least one second material, about 30% by weight of feldspar (e.g. Na(Si 3 Al)O 8 ), about 3% by weight of CuFeS 2 as an example of a preferred at least one first material, about 0,05% by weight of MoS 2 , balance chromium, iron, titanium and magnesium oxides.
- SiO 2 as an example of a preferred at least one second material
- feldspar e.g. Na(Si 3 Al)O 8
- CuFeS 2 as an example of a preferred at least one first material
- MoS 2 balance chromium, iron, titanium and magnesium oxides.
- Step (A) of the process can be conducted according to two alternative embodiments, the first embodiment of which is not covered by the claimed invention.
- step (A) comprises contacting of the mixture comprising at least one first material and at least one second material with at least one magnetic particle, if appropriate in the presence of at least one dispersant.
- step (A) only at least one magnetic particle is added in step (A), and at least one surface-modifying substance is added in step (C) of the process not covered by the claimed invention.
- step (A) comprises contacting of the mixture comprising at least one first material and at least one second material with at least one magnetic particle and at least one surface-modifying substance at the same time, so that the at least one first material, the at least one surface-modifying substance and the at least one magnetic particle become attached to one another, if appropriate in the presence of at least one dispersant.
- both, at least one magnetic particle and at least one surface active substance are added in step (A).
- step (C) of the process according to the present invention is not necessary and is preferably not conducted.
- At least one magnetic particle is added in step (A).
- At least one hydrophobic magnetic particle is added in step (A).
- the at least one magnetic particle is hydrophobized at the surface.
- the at least one magnetic particle is selected from the group consisting of magnetic metals, for example iron, cobalt, nickel and mixtures thereof, ferromagnetic alloys of magnetic metals, for example NdFeB, SmCo and mixtures thereof, magnetic iron oxides, for example magnetite, maghemite, cubic ferrites of the general formula (II) M 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 (II) where
- the at least one magnetic particle is magnetite or cobalt ferrite CO 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 where x ⁇ 1.
- Very preferably magnetite is used as at least one magnetic particle.
- magnetic particles are present in the size of 100 nm to 100 ⁇ m, particularly preferred 1 to 50 ⁇ m.
- the magnetic particles may be brought into the adequate size by processes known to the skilled artisan, for example by milling.
- the particles, obtained from precipitation reaction can be brought to the adequate particle size by setting up the reaction parameters (for example pH, reaction time, temperature).
- the at least one magnetic particle is hydrophobized at the surface by at least one hydrophobic compound.
- the hydrophobic compound is preferably selected from among compounds of the general formula (III) B-Y ( III), where
- B is a linear or branched C 6 -C 18 -alkyl, preferably linear C 8 -C 12 -alkyl, very particularly preferably a linear C 12 -alkyl.
- Heteroatoms which may be present according to the invention are selected from among N, O, P, S and halogens such as F, CI, Br and I.
- Y is selected from the group consisting of -(X) n -SiHal 3 , -(X) n -SiHHal 2 , -(X) n -SiH 2 Hal where Hal is F, CI, Br, I, -(X) n -Si(OR 1 ) 3-n wherein n is 1, 2 or 3 and R 1 is C 1 -C 6 -alkyl, and anionic groups such as -(X) n -SiO 3 3- ,-(X) n -CO 2 - , -(X) n -PO 3 2- , -(X) n -PO 2 S 2- , - (X) n -POS 2 2- , -(X) n -PS 3 2- , -(X) n -PS 2 -, -(X) n -POS - ,-(X) n -PO 2 - ,
- Very preferred hydrophobizing substances of general formula (III) are alkyltri-chlorosilane (alkyl group having 1 to 12 carbon atoms), alkyldialkoxysilane (alkyl group having 1 to 12 carbon atoms and alkoxy group having 1 to 6 carbon atoms), for example alkyldimethoxysilane (alkyl group having 1 to 12 carbon atoms), alkyltrialkoxysilane (alkyl group having 1 to 12 carbon atoms and alkoxy group having 1 to 6 carbon atoms), for example alkyltrimethoxysilane (alkyl group having 6 to 12 carbon atoms), octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
- alkyltrialkoxysilanes as hydrophobizing substances of general formula (III)
- a polymeric hydrophobic layer is obtained at the surface of the magnetic particle.
- the at least one magnetic particle is in general added in an amount that is high enough to have the complete amount of at least one first material embedded in agglomerates, preferably the at least one magnetic particle is added in excess.
- the at least one magnetic particle is added in an amount of 0.1 to 20% by weight, preferably 0.5 to 5% by weight, in each case based on the amount of the complete mixture to be treated with the process according to the present invention.
- step (A) of the process according to the present invention at least one surface-modifying substance is added.
- all surface-modifying substances can be used according to the present invention that are able to modify the surface of the at least one first material in a way that agglomeration with at least one magnetic particle is possible.
- a "surface-modifying substance” is a substance which is able to modify the surface of the particle to be separated off in the presence of the other particles which are not to be separated off in such a way that attachment of a hydrophobic particle by means of hydrophobic interactions occurs.
- Surface-modifying substances which can be used according to the invention become attached to the at least one first material and thereby produce a suitable hydrophobicity of the first material.
- A is a linear or branched C 2 -C 14 -alkyl, very particularly preferably a linear C 4 - or C 8 -alkyl.
- Heteroatoms which may be present according to the invention are selected from among N, O, P, S and halogens such as F, CI, Br and I.
- A is preferably a branched, C 2 -C 20 -alkyl, particularly preferably a branched C 6 -C 14 -alkyl, wherein preferably the at least one substituent, preferably having 1 to 6 carbon atoms, is attached in 2-position, for example 2-ethylhexyl and/or 2-propylheptyl.
- substituent preferably having 1 to 6 carbon atoms
- Corresponding compounds being substituted in 2-position are, for example, obtained using the Guerbet reaction that is known to the skilled artisan as one reaction step.
- compounds are applied, selected from the group consisting of xanthates A-O-CS 2 - , dialkyldithiophosphates (A-O) 2 -PS 2 - , dialkyldithio-phosphinates (A) 2 -PS 2 - , dialkyldithiocarbamates, alkyltrithiocarbamates, dithiophosphates and mixtures thereof, wherein A independently of one another is a linear or branched, preferably linear, C 6 -C 20 -alkyl, for example n-octyl, or a branched C 6 -C 14 -alkyl, wherein the branch is preferably located in 2-position, for example 2-ethylhexyl and/or 2-propylheptyl.
- these compounds preferably cations selected from the group consisting of hydrogen, NR 4 + with R being independently of one another hydrogen and/or C 1 -C 8 -alkyl, hydroxy-substituted C 1 -C 8 -alkyl or -heteroalkyl, like 2-hydroxy-ethyl HO-CH 2 CH 2 - or 2-hydroxy-ethoxy-ethyl HO-CH 2 CH 2 -O-CH 2 CH 2 -, alkali-or earth alkali metals, preferably sodium or potassium, are present.
- Exceptionally preferred compounds of general formula (I) are selected from the group consisting of sodium- or potassium-n-octylxanthate, sodium- or potassium-butylxanthate, sodium- or potassium-di-n-octyldithiophosphinate, sodium- or potassium-di-n-octyldithiophosphate, sodium- or potassium-di-n-octyldithiocarbamates and mixtures of these compounds.
- particularly preferred surface-modifying substances are monothiols, dithiols and trithiols, or 8-hydroxyquinolines, for example as described in EP 1200408 B1 .
- metal oxides for example FeO(OH), Fe 3 O 4 , ZnO, etc.
- carbonates for example azurite [Cu(CO 3 ) 2 (OH) 21 , malachite [Cu 2 [(OH) 2 CO 3 ]
- particularly preferred surface-modifying substances are octylphosphonic acid (OPS), (EtO) 3 Si-A, (MeO) 3 Si-A, with the abovementioned meanings of A.
- particularly preferred surface-modifying substances are monothiols, dithiols and trithiols, xanthogenates or dithiophosphates.
- Z is -(X) n -CS 2 - , -(X) n -PS 2 - or -(X) n -S - where X is O and n is 0 or 1, and a cation is selected from among hydrogen, sodium, potassium and NH x (CH 2 CH 2 OH) 4-x , wherein x is 0, 1, 2, 3, or 4.
- the at least one surface-modifying substance is generally used in an amount which is sufficient to achieve the desired effect.
- the at least one surface-modifying substance is added in an amount of from 0.001 to 1% by weight, preferably 0.001 to 0.1% by weight in each case based on the total mixture to be treated.
- step (A) of the process which is not covered by the claimed invention
- the contacting of the mixture with at least one magnetic particle in step (A) of the process of the invention can be carried out by all methods known to those skilled in the art, for example in bulk or in dispersion, preferably in suspension.
- a dispersion of the at least one magnetic particle is added to the mixture.
- the at least one magnetic particle is dispersed in a suitable dispersion medium.
- Suitable dispersion media are all dispersion media in which the at least one magnetic particle is not completely soluble.
- Suitable dispersion media are for example selected from the group consisting of water, water-soluble organic compounds, for example alcohols having from 1 to 4 carbon atoms, particularly preferably water.
- the amount of dispersion medium for predispersing the magnetic particles can generally be selected so that a slurry or dispersion which is readily stirrable and/or conveyable is obtained.
- the amount of mixture to be treated based on the total slurry or dispersion is up to 100% by weight, preferably up to 60% by weight, for example 0.5 to 60% by weight, preferably 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight.
- the present invention preferably relates to the process according to the present invention, wherein the amount of mixture to be treated based on the total slurry or dispersion is up to 60% by weight, for example 20 to 60% by weight.
- the dispersion of the magnetic particles can be produced by all methods known to those skilled in the art.
- the magnetic particles to be dispersed and the appropriate amount of dispersion medium or mixture of dispersion media are combined in a suitable reactor, for example a stirring tank, and stirred by means of devices known to those skilled in the art, for example in a stirring tank by means of a magnetically operated propeller stirrer, for example at a temperature of from 1 to 80°C, preferably at room temperature.
- the contacting of the mixture with at least one magnetic particle and at least one surface-modifying substance at the same time is generally carried out by combining the components by methods known to those skilled in the art.
- this second embodiment of step (A) can be carried out in bulk or in dispersion, preferably in suspension.
- Suitable dispersion media are for example selected from the group consisting of water, water-soluble organic compounds, for example alcohols having from 1 to 4 carbon atoms, and mixtures thereof.
- the dispersion medium is water.
- a dispersion of the at least one magnetic particle and at least one surface-modifying substance is added to the mixture.
- the present invention therefore preferably relates to the process according to the present invention, wherein contacting of the mixture comprising at least one first material and at least one second material with at least one magnetic particle or with at least one magnetic particle and at least one surface-modifying substance at the same time in step (A) is achieved by addition of a mixture, preferably a dispersion, of least one magnetic particle and at least one surface-modifying substance.
- both embodiments of step (A) can be carried out in bulk, i.e. in the absence of a dispersion medium.
- the mixture to be treated and the at least one magnetic particle or at least one magnetic particle and the at least one surface-modifying substance are combined and mixed in the appropriate amounts without a further dispersion medium.
- Suitable mixing apparatuses are known to those skilled in the art, for example mills such as ball mills.
- Step (A) is generally carried out at a temperature of from 1 to 80 °C, preferably from 10 to 30 °C.
- the at least one magnetic particle becomes attached to the at least one first material that is more hydrophobic than the at least one second material by nature and that is further hydrophobized at its surface by the at least one surface-modifying substance.
- the bond between the two components is based on hydrophobic interactions. There is generally no bonding interaction between the at least one magnetic particle and the hydrophilic component of the mixture, so that these components do not become attached to one another.
- addition products of the at least one first, hydrophobic material and the at least one magnetic particle are present alongside the at least one second, hydrophilic material in the mixture after the second embodiment of step (A) of the process according to the present invention.
- the optional step (B) of the process of the invention comprises addition of at least one dispersion medium to the mixture obtained in step (A) to give a dispersion having a suitable concentration.
- step (A) if step (A) is carried out in bulk, the mixture obtained in step (A) comprises at least one first material and at least second material, at least one magnetic particle and optionally at least one surface-modifying substance. If step (A) is carried out in bulk, step (B) of the process of the invention is preferably carried out, i.e. at least one suitable dispersion medium is added to the mixture obtained in step (A) in order to obtain a dispersion.
- step (B) is preferably not carried out. However, in this embodiment, too, it is possible to carry out step (B), i.e. to add further dispersion medium in order to obtain a dispersion having a lower concentration.
- Suitable dispersion media are all dispersion media which have been mentioned above in respect of step (A).
- the dispersion medium in step (B) is water.
- step (B) comprises either converting the mixture present in bulk from step (A) into a dispersion or converting the mixture which is already in dispersion from step (A) into a dispersion of lower concentration by addition of dispersion media.
- the amount of dispersion medium added in step (A) and/or step (B) can generally be selected so that a dispersion is obtained which is readily stirrable and/or conveyable.
- the amount of mixture to be treated based on the total slurry or dispersion is up to 100% by weight, preferably up to 60% by weight, for example 0.5 to 60% by weight, preferably 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight.
- the present invention preferably relates to the process according to the present invention, wherein the amount of mixture to be treated based on the total slurry or dispersion is up to 60% by weight, for example 20 to 60% by weight.
- step (B) is not carried out but instead step (A) is carried out in aqueous dispersion so that a mixture in aqueous dispersion having the correct concentration for use in step (C) of the process of the invention is obtained directly in step (A).
- step (B) of the process of the invention can, according to the invention, be carried out by all methods known to those skilled in the art.
- Step (C) of the process not covered by the claimed the invention comprises contacting of the mixture from step (A) or (B) with at least one surface active substance, if this has not been done in step (A), so that the at least one first material, the at least one surface-modifying substance and the at least one magnetic particle become attached to one another.
- Step (C) of the process not covered by the claimed invention is conducted, if at least one surface-modifying active substance is not added in step (A) of the process according to the present invention.
- a mixture comprising the at least one first material, the at least one second material, the at least one magnetic particle and optionally at least one dispersion medium, that is obtained in step (A) or (B), is introduced in step (C).
- the at least one surface-modifying substance that is added in step (C) of the process not covered by the claimed invention and preferred embodiments thereof can be selected from the group of compounds of general formula (I) as mentioned in respect of step (A) of the process according to the present invention.
- the at least one surface-modifying substance is generally used in an amount which is sufficient to achieve the desired effect.
- the at least one surface-modifying substance is added in step (C) of the process according to the present invention in an amount of from 0.001 to 1% by weight, preferably 0.001 to 0.1% by weight in each case based on the total mixture to be treated.
- Step (C) of the process not covered by the claimed invention can in general be conducted according to all methods that are known to the skilled artisan.
- the addition according to step (C) of the process according to the present invention can be conducted as mentioned in respect of step (A) of this process.
- Step (D) of the process comprises separation of the addition product from step (A), (B) or (C) from the mixture by application of a magnetic field.
- step (D) is the agglomerate that is obtained in step (A) or (C) containing at least one first material, at least one surface active substance and at least one magnetic particle.
- step (D) can be carried out with any magnetic equipment that is suitable to separate magnetic particles from dispersion, e. g. drum separators, high or low intensity magnetic separators, continuous belt type separators or others.
- Step (D) can be carried out by introducing a permanent magnet into the reactor in which the mixture from step (A), (B) or (C) is present.
- a dividing wall composed of nonmagnetic material for example the wall of the reactor, is present between permanent magnet and mixture to be treated.
- an electromagnet which is only magnetic when an electric current flows is used in step (D). Suitable apparatuses are known to those skilled in the art.
- the magnetic separation equipment allows to wash the magnetic concentrate while the separation with a dispersant, preferably water. This washing preferably allows removing inert material from the magnetic concentrate leading to higher grades of the valuables.
- step (D) is conducted continuously or semi-continuously, wherein preferably the mixture to be treated flows through a separator, preferably in dispersion.
- Flow velocities of the dispersion to be treated are in general adjusted to obtain an advantageous yield of magnetic agglomerates separated.
- flow velocities of the dispersion to be treated are 10 mm/sec. to 1000 mm/sec.
- the pH-value of the dispersion which is treated according to step (D) is in general neutral or weakly basic, being a pH-value of 6 to 13, preferably 8 to 12. In a preferred embodiment, no adjustment of pH-value of the dispersion obtained in step (A) or (B) is necessary.
- Step (D) of the process of the invention can be carried out at any suitable temperature, for example from 10 to 60 °C, preferably at ambient temperature.
- the mixture is preferably mixed by turbulent flow, and is preferably not additionally stirred.
- the magnetic agglomerates can be separated from the magnetic surface and/or the unit wherein magnetic separation is conducted according to the present invention by all methods known to those skilled in the art.
- the magnetic agglomerates are removed by flushing with a suitable dispersion medium.
- Suitable dispersion media have been mentioned above.
- water is used to flush the separated magnetic agglomerates.
- step (D) of the process the agglomerate of at least one first material that is to be separated according to the present invention, at least one surface-modifying substance and at least one magnetic particle is separated from the at least one second material.
- both fractions that are obtained are present as dispersions in at least one dispersion medium, preferably in water.
- Optional step (E) of the process of the invention comprises cleavage of the addition product which has been separated off in step (D) to obtain the at least one first material and the at least one magnetic particle separately.
- the cleavage in step (E) is carried out in a nondestructive manner, i.e. the individual components present in the dispersion are not changed chemically.
- the cleavage according to the invention is preferably not affected by oxidation of the hydrophobizing agent, for example to give the oxidation products or degradation products of the hydrophobizing agent.
- Cleavage can be carried out by all methods known to those skilled in the art which are suitable for cleaving the addition product in such a way that the at least one magnetic particle can be recovered in reusable form.
- the magnetic particle which has been cleaved off is reused in step (A) of the process according to the present invention.
- the cleavage in step (E) of the process of the invention is affected by treatment of the addition product with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidants, reducing agents, surface-active compounds and mixtures thereof.
- Examples of basic compounds which can be used according to the invention are aqueous solutions of basic compounds, for example aqueous solutions of alkali metal and/or alkaline earth metal hydroxides, for example KOH, NaOH, lime water, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 2 3 N, where the radicals R 2 are selected independently from the group consisting of C 1 -C 8 -alkyl which may optionally be substituted by further functional groups.
- aqueous solutions of basic compounds for example aqueous solutions of alkali metal and/or alkaline earth metal hydroxides, for example KOH, NaOH, lime water, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 2 3 N, where the radicals R 2 are selected independently from the group consisting of C 1 -C 8 -alkyl which may optionally be substituted by further functional groups.
- Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and/or zwitterionic surfactants.
- the cleavage is made by the use of biodegradable, preferably nonionic, surfactants with concentrations in the range of the critical micelle concentrations.
- the addition product of hydrophobic material and magnetic particle is cleaved by means of biodegradable nonionic surfactants, further preferably added in an amount slightly, for example up o 5%, more preferably up to 3%, above the critical micelle concentration of the surfactant.
- the at least one first material and the at least one magnetic particle are, according to the invention, present as dispersion in the abovementioned cleavage reagent, preferably in a mixture of water and surfactant.
- the at least one magnetic particle is separated from the dispersion comprising this at least one magnetic particle and the at least one first material by means of a permanent magnet or electromagnet. Details of the separation are analogous to step (D) of the process of the invention.
- the first material to be separated off preferably the metal compound to be separated off, is preferably separated from the dispersion medium by drying.
- the process according to the present invention comprises steps (A) second embodiment, (B) and (D), wherein particles or agglomerates are obtained comprising at least one magnetic particle and at least one metal.
- these particles or agglomerates are suitable for direct work-up without optional step (E) according to the present invention to obtain the at least one metal in pure form.
- step (F) further processing of the particles or of the agglomerate from step (D) or (E) via smelting, extracting and/or wet chemical refining.
- the magnetic particles or agglomerates obtained in step (D) preferably comprise iron comprising magnetic substances or magnetic particles in addition to at least one first material, being for example at least one precious metal. Because iron is essentially necessary for melting and/or smelting processes to obtain the at least one first material in pure or enriched form, the particles or agglomerates that are obtained in step (D) of the process according to the present invention can directly be treated in a smelting and/or melting process.
- step (F) is conducted according to the present invention after step (E).
- Smelting, extracting and/or wet chemical refining are conducted according to methods that are known to the skilled artisan.
- Figure 1 shows a diagram, wherein a process for separating valuables from the gangue of an ore according to the prior art, wherein surface-modifying substance and magnetite are added in two steps (diamonds, 1) is compared to the process according to the present invention, wherein surface-modifying substance and magnetite are added in one step (square, 2).
- the x-axis (4) shows time in minutes
- the y-axis (3) shows a value that is corresponding to the particle size in ⁇ m.
- the pulp having a solid content of 60 wt% is treated with octyl xanthate (400 g/t) and hydrophobic magnetite (3 wt%) in varying orders.
- Treatment is conducted in a beaker under stirring using an inertly coated paddle mixer.
- the pulp is diluted to a solid content of 15 wt% und is separated magnetically. Results in respect of recovery and grade of copper and molybdenum are shown in table 1. Table 1 Examples No.
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Drying Of Gases (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paper (AREA)
- Hard Magnetic Materials (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12165162 | 2012-04-23 | ||
PCT/EP2013/058245 WO2013160219A1 (en) | 2012-04-23 | 2013-04-22 | Magnetic separation of particles including one-step-conditioning of a pulp |
Publications (2)
Publication Number | Publication Date |
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EP2841204A1 EP2841204A1 (en) | 2015-03-04 |
EP2841204B1 true EP2841204B1 (en) | 2022-04-13 |
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ID=48444331
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Application Number | Title | Priority Date | Filing Date |
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EP13722697.3A Active EP2841204B1 (en) | 2012-04-23 | 2013-04-22 | Magnetic separation of particles including one-step-conditioning of a pulp |
Country Status (9)
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EP (1) | EP2841204B1 (es) |
CN (1) | CN104271247B (es) |
AP (1) | AP2014008061A0 (es) |
AU (1) | AU2013254846B2 (es) |
CA (1) | CA2869226C (es) |
CL (1) | CL2014002864A1 (es) |
EA (1) | EA201491892A1 (es) |
PE (1) | PE20142381A1 (es) |
WO (1) | WO2013160219A1 (es) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0091923B1 (en) | 1981-10-26 | 1987-03-04 | W.S.R. Pty. Ltd. | Magnetic flotation |
GB8726857D0 (en) | 1987-11-17 | 1987-12-23 | Fospur Ltd | Froth floatation of mineral fines |
US4834898A (en) | 1988-03-14 | 1989-05-30 | Board Of Control Of Michigan Technological University | Reagents for magnetizing nonmagnetic materials |
DE19936472A1 (de) | 1999-08-03 | 2001-02-15 | Stn Atlas Elektronik Gmbh | Haftvermittler |
NO312373B1 (no) | 2000-06-29 | 2002-04-29 | Kjell Birkeland | Veggkonstruksjon, s¶rlig for en oppbevaringsboks til verdisaker, samt anvendelse av en slik veggkonstruksjon somsidevegger i en oppbevaringsboks |
WO2007000020A1 (en) | 2005-06-29 | 2007-01-04 | Compumedics Limited | Sensor assembly with conductive bridge |
PL2190584T3 (pl) * | 2007-09-03 | 2013-11-29 | Basf Se | Przerób wartościowych rud z użyciem cząstek magnetycznych |
KR20110095934A (ko) * | 2008-12-11 | 2011-08-25 | 바스프 에스이 | 광물 찌꺼기로부터의 광석의 부화 |
PL2498913T3 (pl) * | 2009-11-11 | 2014-08-29 | Basf Se | Sposób zwiększania efektywności w procesie rozdziału rud za pomocą hydrofobowych cząstek magnetycznych przez ukierunkowane doprowadzanie energii mechanicznej |
EA201390789A1 (ru) * | 2010-11-29 | 2013-12-30 | Басф Се | Магнитное извлечение ценных компонентов из шлакового материала |
-
2013
- 2013-04-22 AP AP2014008061A patent/AP2014008061A0/xx unknown
- 2013-04-22 WO PCT/EP2013/058245 patent/WO2013160219A1/en active Application Filing
- 2013-04-22 PE PE2014001784A patent/PE20142381A1/es active IP Right Grant
- 2013-04-22 AU AU2013254846A patent/AU2013254846B2/en not_active Ceased
- 2013-04-22 EP EP13722697.3A patent/EP2841204B1/en active Active
- 2013-04-22 CN CN201380021534.6A patent/CN104271247B/zh not_active Expired - Fee Related
- 2013-04-22 EA EA201491892A patent/EA201491892A1/ru unknown
- 2013-04-22 CA CA2869226A patent/CA2869226C/en active Active
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2014
- 2014-10-23 CL CL2014002864A patent/CL2014002864A1/es unknown
Also Published As
Publication number | Publication date |
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AP2014008061A0 (en) | 2014-11-30 |
WO2013160219A1 (en) | 2013-10-31 |
CN104271247A (zh) | 2015-01-07 |
CL2014002864A1 (es) | 2014-12-19 |
EP2841204A1 (en) | 2015-03-04 |
PE20142381A1 (es) | 2015-01-30 |
CA2869226C (en) | 2020-03-10 |
CN104271247B (zh) | 2017-10-27 |
AU2013254846B2 (en) | 2017-12-07 |
CA2869226A1 (en) | 2013-10-31 |
AU2013254846A1 (en) | 2014-10-23 |
EA201491892A1 (ru) | 2015-04-30 |
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