EP2190584B1 - Processing rich ores using magnetic particles - Google Patents
Processing rich ores using magnetic particles Download PDFInfo
- Publication number
- EP2190584B1 EP2190584B1 EP08803482.2A EP08803482A EP2190584B1 EP 2190584 B1 EP2190584 B1 EP 2190584B1 EP 08803482 A EP08803482 A EP 08803482A EP 2190584 B1 EP2190584 B1 EP 2190584B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- magnetic
- process according
- group
- substance
- 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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- 239000006249 magnetic particle Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 claims description 78
- 239000000203 mixture Substances 0.000 claims description 77
- 239000000126 substance Substances 0.000 claims description 60
- 239000006185 dispersion Substances 0.000 claims description 33
- 230000002209 hydrophobic effect Effects 0.000 claims description 32
- 239000002270 dispersing agent Substances 0.000 claims description 30
- 230000005291 magnetic effect Effects 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 15
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000003776 cleavage reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000007017 scission Effects 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000005294 ferromagnetic effect Effects 0.000 claims description 2
- 235000013980 iron oxide Nutrition 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
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 239000002612 dispersion medium Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- -1 tripolyphosphate ions Chemical class 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 239000013543 active substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000001143 conditioned effect Effects 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004404 heteroalkyl group Chemical group 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229960004592 isopropanol Drugs 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000907663 Siproeta stelenes Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 229910052794 bromium 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
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 3
- YEEBCCODSASHMM-UHFFFAOYSA-M potassium;octoxymethanedithioate Chemical compound [K+].CCCCCCCCOC([S-])=S YEEBCCODSASHMM-UHFFFAOYSA-M 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052712 strontium Inorganic materials 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
- 239000012991 xanthate Substances 0.000 description 3
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052656 albite Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910052955 covellite Inorganic materials 0.000 description 2
- 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 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000010433 feldspar Substances 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
- 239000011553 magnetic fluid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052627 muscovite Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- SLCANKHLTWZHRV-ICFOKQHNSA-N (7z)-5,8-diethyl-7-hydroxyiminododecan-6-ol Chemical compound CCCCC(CC)C(O)C(=N/O)\C(CC)CCCC SLCANKHLTWZHRV-ICFOKQHNSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CROPCLKVTSNPEY-GHVJWSGMSA-N 2-[(E)-N-hydroxy-C-phenylcarbonimidoyl]-4-nonylphenol Chemical compound OC1=C(/C(/C2=CC=CC=C2)=N/O)C=C(C=C1)CCCCCCCCC CROPCLKVTSNPEY-GHVJWSGMSA-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
- 229910018072 Al 2 O 3 Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020710 Co—Sm Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide 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
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012455 biphasic mixture Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052948 bornite Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009852 extractive metallurgy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005021 gait Effects 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000002932 luster 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
- 239000000696 magnetic material Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005192 partition Methods 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 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
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical group CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- 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
Definitions
- the present invention relates to a process for separating at least one first substance from a mixture containing said at least one first substance and at least one second substance, wherein the first substance is first contacted with a surface-active substance for its hydrophobization, this mixture being further in contact with at least one magnetic particle is brought so that the magnetic particle and the hydrophobized first material attach and this agglomerate is separated from the at least one second material by the application of a magnetic field, and then the at least one first substance is preferably quantitatively separated from the magnetic particle, wherein Preferably, the magnetic particles can be recycled back into the process.
- the present invention relates to a method of enriching ores in the presence of gait.
- WO 02/0066168 A1 relates to a process for the separation of ores from mixtures containing them, in which suspensions or slurries of these mixtures are treated with particles which are magnetic and / or buoyant in aqueous solutions. After addition of the magnetic and / or buoyant particles, a magnetic field is applied so that the agglomerates are separated from the mixture.
- the degree of attachment of the magnetic particles to the ore and the strength of the bond is not sufficient to perform the process with sufficiently high yield and effectiveness.
- US 4,657,666 discloses a method for enrichment of ores where the ginger ore is reacted with magnetic particles to form agglomerates due to the hydrophobic interactions.
- the magnetic particles are rendered hydrophobic by treatment with hydrophobic compounds on the surface, so that a connection to the value ore takes place.
- the agglomerates are then separated from the mixture by 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 particles occurs in this process by destroying the surface-activating substance which has been applied to the ore in the form of the surface-activating solution.
- C 4 hydrophobizing agents for the ore are used in this process.
- US 4,834,898 discloses a method of separating nonmagnetic materials by contacting them with magnetic reagents encased in two layers of surfactants. US 4,834,898 further discloses that the surface charge of the non-magnetic particles to be separated may be affected by various types and concentrations of electrolyte reagents. For example, the surface charge is altered by the addition of multivalent anions, for example tripolyphosphate ions.
- WO 2007/008322 A1 discloses a magnetic particle hydrophobized on the surface for separating impurities from mineral substances by magnetic separation techniques.
- a dispersing agent selected from sodium silicate, sodium polyacrylate or sodium hexametaphosphate may be added to the solution or dispersion.
- an organic solvent is selected from the group consisting of 2-hydroxy-5-nonylbenzo-Phenoneoxime, 5,8-diethyl-7-hydroxydodecan-6-oxime and others with magnetic particles added to the organic solvent in this manner to magnetize.
- the magnetic particles may be coated with a polar surfactant. Suitable surfactants include anionic, cationic or amphoteric surfactants.
- This magnetized organic solvent is then added to an aqueous slurry of a metal cation-containing compound, for example, copper sulfate. Under the influence of a magnetic field, this biphasic mixture is stirred to transport the copper sulfate into the organic phase. Because magnetic particles are present in the organic phase, a faster separation of the phases succeeds.
- US 5,161,694 discloses a method for separating finely divided particles by selective hydrophobic coagulation. This process can be used to separate coal from mineral-containing mixtures. The method is based on the fact that the hydrophobic material, for example coal in an aqueous medium agglomerated by hydrophobic forces, and the agglomerates can then be separated in known ways.
- the stable magnetic fluids consist of finely divided superparamagnetic particles in a liquid dispersant and a sufficient amount for stabilization and property modification of a mixture of surfactants chemically bonded to the surface of the magnetic particles.
- the object of the present invention is to provide a method by which at least one first substance can be separated off efficiently from mixtures containing at least one first substance and at least one second substance. Furthermore, it is an object of the present invention to treat the first particles to be separated in such a way that the addition product between the magnetic particle and the first substance is sufficiently stable in order to ensure a high yield of first material during the separation.
- the method according to the invention preferably serves to separate at least one first, hydrophobic substance from a mixture comprising said at least one first, hydrophobic substance and at least one second, hydrophilic substance.
- hydrophobic means that the corresponding particle can be hydrophobized subsequently by treatment with the at least one surface-active substance. It is also possible that a per se hydrophobic particle is additionally rendered hydrophobic by treatment with the at least one surface-active substance.
- Hydrophobic in the context of the present invention means that the surface of a corresponding "hydrophobic substance” or a “hydrophobized substance” has a contact angle of> 90 ° with water against air.
- Hydrophobic in the context of the present invention means that the surface of a corresponding “hydrophilic substance” has a contact angle of ⁇ 90 ° with water to air.
- the at least one first substance is at least one hydrophobic metal compound or carbon
- the at least one second substance is preferably at least one hydrophilic metal compound.
- the at least one first substance to be separated off is preferably a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing Ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2 [CO 3 ]]), or of the noble metals and their compounds, to which a surface-active compound is selectively added Generation of hydrophobic surface properties can attach.
- a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing Ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2 [CO 3 ]]
- a surface-active compound is selectively added Generation of hydrophobic surface properties can attach.
- the at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic and hydroxide metal compounds, for example 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 , Al 2 O 3 , FeO (OH), FeCO 3 , Fe 2 O 3 , Fe 3 O 4 and other related minerals and mixtures thereof.
- oxidic and hydroxide metal compounds for example 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
- sulfidic ores which can be used according to the invention are selected, for example, from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper gravel) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite (copper luster) Cu 2 S and mixtures thereof.
- Suitable oxidic metal compounds which can be used 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 other related minerals and mixtures thereof.
- untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
- the mixture containing at least one first substance and at least one second substance in step (A) is in the form of particles having a size of 100 nm to 100 ⁇ m, see for example US 5,051,199 , In a preferred embodiment, this particle size is obtained by grinding. Suitable methods and devices are known to the person skilled in the art, for example wet milling in a ball mill.
- a preferred embodiment of the method according to the invention is characterized in that the mixture containing at least a first material and at least one second material before or during step (A) is ground to particles having a size of 100 nm to 100 microns.
- Preferably usable ore mixtures have a content of sulfidic minerals of at least 0.4 wt .-%, more preferably at least 10 wt.%, On.
- sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above. Additionally, in the mixtures sulphides of metals other than copper are also present, for example sulphides of iron; Lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 .
- 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 ), monacite ((La-Lu) PO 4 ).
- noble metals for example, Au, Pt, Pd, Rh, etc., preferably in a pure state.
- a typically used ore mixture which can be separated by the method according to the invention, has the following composition: about 30 wt .-% SiO 2 , about 10 wt .-% NA (Si 3 Al) O 8 , about 3 wt. -% Cu 2 S, about 1 wt .-% MoS 2 , balance chromium, iron, titanium and magnesium oxides.
- Step (A) of the method according to the invention comprises contacting the mixture containing at least a first substance and at least one second substance with at least one surface-active substance, if appropriate in the presence of at least one dispersing agent, wherein the surface-active substance binds selectively to the at least one first substance,
- surface-active substance means a substance which is capable of changing the surface of the particle to be separated in the presence of the other particles which are not to be separated in such a way that an attachment of a hydrophobic particle by hydrophobic interactions to Come.
- Surface-active substances which can be used according to the invention are deposited on the at least one first substance and thereby bring about a suitable hydrophobicity of the first substance.
- a in formula (I) is a linear or branched C 4 -C 12 -alkyl, very particularly preferably a linear C 4 - or C 8 -alkyl.
- optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
- a in formula (I) is preferably a linear or branched, preferably linear, C 8 -C 20 -alkyl. Furthermore, A is preferably a branched C 6 -C 14 -alkyl, wherein the at least one substituent, preferably having 1 to 6 carbon atoms, is preferably present in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl.
- Z in formula (I) is selected from the group consisting of anionic groups - (X) n -PO 3 2- , - (X) n -PO 2 S 2- , - (X) n - POS 2 2- , - (X) n -PPS 3 2- , - (X) n -PPS 2 - , - (X) n -POS - , - (X) n -PO 2- , - (X) n -PO 3 2- (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n -COS - , - (X) n -C (S) NHOH.
- n 2 in the abovementioned formulas, then two identical or different, preferably identical, groups A are bound to a group Z.
- Preferred counterions in these compounds are cations selected from the group consisting of hydrogen, NR 4 + with R being the same independently each other hydrogen and / or C 1 -C 8 alkyl, alkali or alkaline earth metals, in particular sodium or potassium before.
- Very particularly 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-octyl dithiophosphinate, sodium or potassium di -n-octyl dithiophosphate, and mixtures of these compounds.
- particularly preferred surface-active substances are mono-, di- and trithiols or 8-hydroxyquinolines, for example described in US Pat EP 1200408 B1 ,
- metal oxides for example FeO (OH), Fe 3 O 4 , ZnO etc.
- carbonates for example azurite (Cu (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 CO 3 ]]
- Particularly preferred surface-active substances octylphosphonic acid (OPS), (EtO) 3 Si-A, (MeO) 3 Si-A, with the abovementioned meanings for A.
- OPS octylphosphonic acid
- EtO EtO
- MeO 3 Si-A
- the surface-active substances used are not hydroxamates for modifying metal oxides used.
- particularly preferred surface-active substances are mono-, di- and trithiols or xanthates.
- Z is - (X) n -CS 2 - , - (X) n -PO 2 - or - (X) n -S - where X is O and n is 0 or 1 and one Cation selected from hydrogen, sodium or potassium.
- Very particularly preferred surface-active substances are 1-octanethiol, potassium n-octylxanthate, potassium-butylxanthate, octylphosphonic acid or a compound of the following formula (IV)
- step (A) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
- Step (A) can be carried out in bulk or in dispersion, preferably in suspension, particularly preferably in aqueous suspension.
- step (A) is carried out in bulk, ie in the absence of a dispersing agent.
- the mixture to be treated and the at least one above-mentioned surfactant are added and mixed together without additional dispersant in the appropriate amounts.
- Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill.
- step (A) is carried out in a dispersion, preferably in suspension.
- the dispersant all dispersants are suitable in which the mixture of step (A) is not completely soluble.
- Suitable dispersants for the preparation of the slurry or dispersion according to step (B) of the process of the invention are selected from the group consisting of water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
- the dispersant in step (A) is water.
- Step (A) of the process according to the invention is generally carried out at a temperature of 1 to 80 ° C, preferably at 20 to 40 ° C, more preferably at ambient temperature.
- the at least one above-mentioned surfactant is generally used in an amount sufficient to achieve the desired effect.
- the at least one surfactant is added in an amount of 0.01 to 5 wt .-%, each based on the total mixture to be treated.
- step (B) of the process of the invention comprises adding at least one dispersing agent to the mixture obtained in step (A) to obtain a dispersion
- step (A) if step (A) is carried out in bulk, the mixture obtained in step (A) contains at least one first substance and at least one second substance which has been modified on the surface with at least one surface-active substance.
- step (B) of the method according to the invention is carried out, i. at least one suitable dispersing agent is added to the mixture obtained in step (A) to obtain a dispersion.
- step (B) is not carried out. It is, however, also at of this embodiment, it is possible to carry out step (B), ie to add further dispersing agent to obtain a dispersion having a lower concentration.
- Suitable dispersants are all dispersants which have already been mentioned with respect to step (A).
- the dispersant in step (A) is water.
- step (B) either the mixture of substance from step (A) is thus converted into a dispersion, or the mixture already present in dispersion from step (A) is converted into a dispersion of lower concentration by adding dispersing agent.
- the amount of dispersant added in step (A) and / or step (B) may be selected according to the invention to give a dispersion which is readily stirrable and / or recoverable.
- the amount of mixture to be treated based on the total slurry or dispersion to 100 wt .-%, particularly preferably 0.5 to 10 wt .-%.
- step (B) is not carried out, but step (A) is carried out in aqueous dispersion, so that in step (A) directly a mixture in aqueous dispersion is obtained, which has the correct concentration to Step (C) of the method according to the invention to be used.
- step (B) of the process according to the invention can be carried out according to the invention by all methods known to the person skilled in the art.
- Step (C) of the process according to the invention comprises treating the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle, so that the at least one first substance rendered hydrophobic in step (A) to which the at least one above-mentioned surface active substance belongs Substance is attached, and attach at least one magnetic particle.
- the at least one magnetic particle is magnetite or cobalt ferrite Co 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 with x ⁇ 1.
- the magnetic particles used in step (C) of the process according to the invention are in a size of 100 nm to 100 .mu.m, more preferably 1 to 50 .mu.m before.
- the magnetic particles can be converted into the appropriate size by methods known to the person skilled in the art, for example by grinding.
- the particles produced by a precipitation reaction can be brought to this particle size by adjusting the reaction parameters (eg pH, reaction time, temperature).
- B is a linear or branched C 6 -C 18 -alkyl, preferably linear C 8 -C 12 -alkyl, very particularly preferably a linear one C 12 alkyl.
- optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, 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 equal to F, Cl, Br, I, 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 -PPS 3 2- , - (X) n -PPS 2 - , - (X) n -POS - , - (X) n -PO 2 - , - (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n n -CO 2 -
- n 2 in the abovementioned formulas, then two identical or different, preferably identical, groups B are bound to a group Y.
- Very particularly preferred hydrophobizing substances of the general formula (III) are alkyltrichlorosilanes (alkyl group having 6-12 carbon atoms), alkyltrimethoxysilanes (alkyl group having 6-12 carbon atoms), octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
- step (C) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
- the at least one magnetic particle is dispersed in a suitable dispersing agent.
- Suitable dispersants are all dispersants in which the at least one magnetic particle is not completely soluble.
- Suitable dispersants for dispersion according to step (C) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds and mixtures thereof, more preferably water. Particularly preferably, in step (C), the same dispersing agent is used as in step (B).
- the amount of dispersant for predispersing the magnetic particles may be selected according to the invention so as to obtain a slurry or dispersion which is readily stirrable and / or recoverable.
- the amount of mixture to be treated, based on the total slurry or dispersion is up to 60% by weight.
- the dispersion of the magnetic particles can be prepared by all methods known to the person skilled in the art.
- the magnetic particles to be dispersed and the corresponding amount of dispersing agent or dispersing agent mixture in a suitable reactor such as a glass reactor, combined and stirred with known in the art devices, for example in a glass pan with a mechanically operated paddle, for example at a temperature of 1 to 80 ° C, preferably at room temperature.
- the treatment of the dispersion from step (B) with at least one hydrophobic magnetic particle is generally carried out so that both components are combined by methods known to the person skilled in the art.
- a dispersion of the at least one magnetic particle is added to the mixture previously treated with at least one surfactant.
- the magnetic particle may be added in solid form to a dispersion of the mixture to be treated.
- both components are present in dispersed form.
- Step (C) is generally carried out at a temperature of 1 to 80 ° C, preferably 10 to 30 ° C.
- step (C) the at least one magnetic particle attaches to the hydrophobic substance of the mixture to be treated.
- the bond between the two components is based on hydrophobic interactions. There is generally no binding interaction between the at least one magnetic particle and the hydrophilic portion of the mixture, so that no attachment takes place between these components.
- step (C) addition products of the at least one hydrophobic substance and the at least one magnetic particle are thus present in the mixture in addition to the at least one hydrophilic substance.
- Step (D) of the process according to the invention comprises separating the addition product from step (C) from the mixture by applying a magnetic field.
- Step (D) may be carried out in a preferred embodiment by introducing a permanent magnet into the reactor in which the mixture from step (C) is located.
- a permanent magnet for example, the glass wall of the reactor.
- an electrically switchable magnet is used in step (D) which is magnetic only when an electric current flows. Suitable devices are known in the art.
- Step (D) of the process according to the invention may be carried out at any suitable temperature, for example 10 to 60 ° C.
- step (D) the mixture is preferably stirred continuously with a suitable stirrer, for example a Teflon stirring bar or a paddle stirrer.
- a suitable stirrer for example a Teflon stirring bar or a paddle stirrer.
- step (D) the adduct of step (C) may optionally be separated by any method known to those skilled in the art, for example by draining the liquid with the hydrophilic portion of the suspension from the bottom valve from the reactor used for step (D) or pumping it off held by the at least one magnet portions of the suspension through a hose.
- Step (E) of the process according to the invention comprises cleaving the separated addition product from step (D) in order to obtain the at least one first substance and the at least one magnetic particle separately.
- the cleavage in step (E) is not destructive, i. that the individual components present in the dispersion are not chemically changed.
- the cleavage according to the invention does not take place by oxidation of the hydrophobizing agent, for example to obtain the oxidation products or degradation products of the hydrophobizing agent.
- the splitting can be carried out by all methods known to those skilled in the art, which are suitable for splitting the addition product in such a way that the at least one magnetic particle can be recovered in reusable form.
- the cleaved magnetic particle is used again in step (C).
- the cleavage in step (E) of the process according to the invention is carried out by treating the addition product with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, reducing agents, surface-active compounds and mixtures thereof.
- suitable organic solvents are methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example Benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether, ketones, for example acetone, aromatic or aliphatic hydrocarbons, for example saturated hydrocarbons having, for example, 8 to 16 carbon atoms, for example dodecane and / or Shellsol®, diesel fuels and mixtures from that.
- the main components of the diesel fuel are predominantly alkanes, cycloalkanes and aromatic hydrocarbons having about 9 to 22 carbon atoms per molecule and a boiling range between 170 ° C and 390 ° C.
- step (D) is carried out by adding aqueous NaOH solution to a pH of 13, for example for the separation of OPS-modified Cu 2 S.
- the acidic compounds may be mineral acids, for example HCl, H 2 SO 4 , HNO 3 or mixtures thereof, organic acids, for example carboxylic acids.
- an oxidizing agent for example, H 2 O 2 can be used, for example, as a 30 wt.% Aqueous solution (perhydrol).
- For the separation of thiols modified Cu 2 S is preferably H 2 O 2 or Na 2 S 2 O 4 used.
- Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
- the addition product of hydrophobic substance and magnetic particle is cleaved with an organic solvent, particularly preferably with acetone and / or diesel. This process can also be supported mechanically. In a preferred embodiment, ultrasound is used to assist the cleavage process.
- the organic solvent is used in an amount sufficient to cleave as much of the entire addition product as possible. In a preferred embodiment, 20 to 100 ml of the organic solvent are used per gram of hydrophobic and magnetic particle cleavage product.
- the at least one first substance and the at least one magnetic particle are present as a dispersion in the cleavage reagent mentioned, preferably an organic solvent.
- the at least one magnetic particle is separated from the dispersion containing this at least one magnetic particle and the at least one first substance by a permanent or switchable magnet from the solution. Details of this separation are analogous to step (D) of the method according to the invention.
- the first material to be separated off preferably the metal compound to be separated, is separated from the organic solvent by distilling off the organic solvent.
- the first substance obtainable in this way can be purified by further methods known to the person skilled in the art.
- the solvent can, if appropriate after purification, be recycled back to the process according to the invention.
- This mixture is charged with 1.506 g of magnetite which has been modified with dodecyltrichlorosilane (primary particle size: about 10 nm) in a 1 l stirred apparatus, with 580 ml of water and 0.1 g of dodecylamine (Alfa Aeser Lot: 10108955). offset and 45 min at 150 rev / min. mixed with a teflon stirring bar. Then a Co-Sm magnet (5 cm in height, 2 cm in length, 2 cm in width) was held on an outer wall of the stirring apparatus and another 30 min. at 150 rpm. touched. Thereafter, the water is removed via a hose, and the apparatus is dried for a further 10 minutes with a hot air blower. The sand, which is on the ground, is weighed back with 9.77 g. The residue on the magnet is 1.76 g (87% of the Cu 2 S used).
- the basin is then filled with 400 ml of acetone and for 30 min at 200 U / min. touched. Then, the acetone in which the Cu 2 S is a fine particle is drained through a tube and dried. This gives 1.59 g (79% Cu 2 S).
- Example 1 An analogous sand-Cu 2 S mixture is produced as in Example 1. Instead of 1-octanethiol, however, potassium butyl xanthate is used. The further experimental procedure is analogous to Example 1. The amount of sand on the ground is 9.64 g, the residue on Magnet 1.61 g (80.0% Cu 2 S). After separation of magnetic particles and ore by stirring in acetone, 1.44 g of Cu 2 S (71%) are obtained.
- the quartz content of the magnet is ⁇ 0.5% by weight.
- the assembly is flooded with 0.1 M NaOH solution, shaken gently and then the liquid is removed. After drying, 60% of the Cu 2 S are found again.
- 0.5 g of Pd-coated ZnO are dispersed in 10 ml of demineralized water, whereupon the solution turns gray. Subsequently, 0.5 g of thiol-modified Fe 3 O 4 are added and stirred vigorously. After 1 h, a Co / Sm magnet is held to the outer wall of the vessel, whereby the solution is largely clarified. The supernatant solution is decanted off from the magnetic components and the volatiles are removed in vacuo. There are found again 0.1 gg Pd-coated ZnO, ie the rest of the ZnO is magnetically separated from the mixture.
- the diesel phase is decanted off via a magnet in such a way that the magnetic components are retained.
- the diesel phase with the non-magnetic constituents is subjected to filtration, and then the solid residue is dried. There are recovered 0.98 g of solid which consists of 98% Cu 2 S.
- the content of Fe 3 O 4 is less than 0.01 g.
- Example 7 Processing of natural copper ore from Pelambres (Chile)
- the ore rock is comminuted dry in a hammer mill until 90% by weight of the ore in the fraction is less than 125 ⁇ m in size.
- Magnetic Pigment 345 (BASF SE) is treated with 0.5% by weight of octylphosphonic acid in aqueous solution for 30 minutes at room temperature (RT). The solid is filtered off, washed until the conductivity of about 50 .mu.S with hot water (50 ° C) and dried at 80 ° C in a vacuum.
- fraction A1 1 L separating material is passed through a series of stationary permanent magnets.
- the spout is collected as fraction A1.
- the portion held on the magnet is washed by moving the magnets with 1 L of water, collecting the discharged solid as fraction A2.
- the fraction R retained on the magnet and fractions A1 and A2 are analyzed for Cu, Fe and Mo content.
- 100 g of ore are conditioned in a vibrating mill (160 mL ZrO2 spheres, ⁇ 1.7-2.7 mm) with 60 mL water, 0.065 g potassium n-octyl xanthate and 0.04 g Shellsol D40 for 5 min.
- a suspension of 3 g of hydrophobized magnetite in 3 g of isopropanol is added to the grinding vessel and conditioned again for 5 min.
- the grinding suspension is separated from the grinding media, diluted to 1 L and subjected to the separation procedure (see above).
- the fraction R (6.4 g) contains all the magnetite used and 92.4% of the copper and 86.1% of the molybdenum.
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Description
Die vorliegende Erfindung betrifft ein Verfahren zum Abtrennen wenigstens eines ersten Stoffes aus einer Mischung enthaltend diesen wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff, wobei der erste Stoff zunächst zu seiner Hydrophobierung mit einer oberflächenaktiven Substanz in Kontakt gebracht wird, diese Mischung weiter in Kontakt mit mindestens einem Magnetpartikel gebracht wird, so dass sich der Magnetpartikel und der hydrophobisierte erste Stoff anlagern und dieses Agglomerat von dem wenigstens einen zweiten Stoff durch die Anwendung eines Magnetfeldes abgetrennt wird, und anschließend der wenigstens eine erste Stoff bevorzugt quantitativ von dem Magnetpartikel getrennt wird, wobei bevorzugt der Magnetpartikel wieder in den Prozess zurückgeführt werden kann.The present invention relates to a process for separating at least one first substance from a mixture containing said at least one first substance and at least one second substance, wherein the first substance is first contacted with a surface-active substance for its hydrophobization, this mixture being further in contact with at least one magnetic particle is brought so that the magnetic particle and the hydrophobized first material attach and this agglomerate is separated from the at least one second material by the application of a magnetic field, and then the at least one first substance is preferably quantitatively separated from the magnetic particle, wherein Preferably, the magnetic particles can be recycled back into the process.
Insbesondere betrifft die vorliegende Erfindung ein Verfahren zur Anreicherung von Werterzen in Gegenwart der Gangart.More particularly, the present invention relates to a method of enriching ores in the presence of gait.
Verfahren zum Abtrennen von Werterzen aus Mischungen enthaltend diese sind aus dem Stand der Technik bereits bekannt.Methods for separating ores from mixtures containing these are already known from the prior art.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren bereitzustellen, durch das wenigstens ein erster Stoff aus Mischungen enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff effizient abgetrennt werden können. Des Weiteren ist es eine Aufgabe der vorliegenden Erfindung, die abzutrennenden ersten Partikel so zu behandeln, dass das Anlagerungsprodukt zwischen magnetischem Partikel und erstem Stoff genügend stabil ist, um eine hohe Ausbeute an erstem Stoff bei der Abtrennung zu gewährleisten.The object of the present invention is to provide a method by which at least one first substance can be separated off efficiently from mixtures containing at least one first substance and at least one second substance. Furthermore, it is an object of the present invention to treat the first particles to be separated in such a way that the addition product between the magnetic particle and the first substance is sufficiently stable in order to ensure a high yield of first material during the separation.
Diese Aufgaben werden gelöst durch ein Verfahren zum Abtrennen wenigstens eines ersten Stoffes aus einer Mischung enthaltend diesen wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff, umfassend die folgenden Schritte:
- (A) Inkontaktbringen der Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff mit wenigstens einer oberflächenaktiven Substanz, gegebenenfalls in Gegenwart wenigstens eines Dispersionsmittels, wobei die oberflächenaktive Substanz an den wenigstens einen ersten Stoff anbindet,
- (B) gegebenenfalls Zugabe wenigstens eines Dispersionsmittels zu der in Schritt (A) erhaltenen Mischung, um eine Dispersion mit geeigneter Konzentration zu erhalten,
- (C) Behandeln der Dispersion aus Schritt (A) oder (B) mit wenigstens einem hydrophoben Magnetpartikel, so dass sich der wenigstens eine erste Stoff, an den die wenigstens eine oberflächenaktive Substanz angebunden ist, und der wenigstens eine Magnetpartikel anlagern,
- (D) Abtrennen des Anlagerungsproduktes aus Schritt (C) von der Mischung durch Anlegen eines magnetischen Feldes,
- (E) Spalten des abgetrennten Anlagerungsproduktes aus Schritt (D), um den wenigstens einen ersten Stoff und den wenigstens einen Magnetpartikel separat zu erhalten, wobei die oberflächenaktive Substanz eine Substanz der allgemeinen Formel (I)
A-Z (I) ist, worin
- A ausgewählt aus linearem oder verzweigtem C3-C30-Alkyl, C3-C30-Heteroalkyl, gegebenenfalls substituiertes C6-C30-Aryl, gegebenenfalls substituiertes C6-C30-Heteroalkyl, C8-C30-Aralkyl ist und
- Z eine Gruppe ist, mit der die Verbindung der allgemeinen Formel (I) an den wenigstens einen listen Stoff anbindet.
- (A) contacting the mixture containing at least a first substance and at least one second substance with at least one surface-active substance, if appropriate in the presence of at least one dispersing agent, wherein the surface-active substance binds to the at least one first substance,
- (B) optionally adding at least one dispersant to the mixture obtained in step (A) to obtain a dispersion of suitable concentration,
- (C) treating the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle so that the at least one first substance to which the at least one surface-active substance is attached and the at least one magnetic particle attach,
- (D) separating the adduct from step (C) from the mixture by applying a magnetic field,
- (E) cleaving the separated addition product from step (D) to obtain the at least one first substance and the at least one magnetic particle separately, the surface-active substance being a substance of the general formula (I)
AZ (I) is where
- A is selected from linear or branched C 3 -C 30 alkyl, C 3 -C 30 heteroalkyl, optionally substituted C 6 -C 30 aryl, optionally substituted C 6 -C 30 heteroalkyl, C 8 -C 30 aralkyl and
- Z is a group with which the compound of the general formula (I) binds to the at least one listed substance.
Das erfindungsgemäße Verfahren dient bevorzugt zum Abtrennen wenigstens eines ersten, hydrophoben Stoffes aus einer Mischung umfassend diesen wenigstens einen ersten, hydrophoben Stoff und wenigstens einen zweiten, hydrophilen Stoff.The method according to the invention preferably serves to separate at least one first, hydrophobic substance from a mixture comprising said at least one first, hydrophobic substance and at least one second, hydrophilic substance.
Im Rahmen der vorliegenden Erfindung bedeutet "hydrophob", dass das entsprechende Teilchen nachträglich durch Behandlung mit der wenigstens einen oberflächenaktiven Substanz hydrophobiert sein kann. Es ist auch möglich, dass ein an sich hydrophobes Teilchen durch Behandlung mit der wenigstens einen oberflächenaktiven Substanz zusätzlich hydrophobiert wird.In the context of the present invention, "hydrophobic" means that the corresponding particle can be hydrophobized subsequently by treatment with the at least one surface-active substance. It is also possible that a per se hydrophobic particle is additionally rendered hydrophobic by treatment with the at least one surface-active substance.
"Hydrophob" bedeutet im Rahmen der vorliegenden Erfindung, dass die Oberfläche einer entsprechenden "hydrophoben Substanz" bzw. einer "hydrophobisierten Substanz" einen Kontaktwinkel von > 90° mit Wasser gegen Luft aufweist. "Hydrophil" bedeutet im Rahmen der vorliegenden Erfindung, dass die Oberfläche einer entsprechenden "hydrophilen Substanz" einen Kontaktwinkel von < 90° mit Wasser gegen Luft aufweist."Hydrophobic" in the context of the present invention means that the surface of a corresponding "hydrophobic substance" or a "hydrophobized substance" has a contact angle of> 90 ° with water against air. "Hydrophilic" in the context of the present invention means that the surface of a corresponding "hydrophilic substance" has a contact angle of <90 ° with water to air.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der wenigstens eine erste Stoff wenigstens eine hydrophobe Metallverbindung oder Kohle, und der wenigstens eine zweite Stoff ist bevorzugt wenigstens eine hydrophile Metallverbindung.In a preferred embodiment of the process according to the invention, the at least one first substance is at least one hydrophobic metal compound or carbon, and the at least one second substance is preferably at least one hydrophilic metal compound.
Somit ist der wenigstens eine abzutrennende erste Stoff bevorzugt eine Metallverbindung ausgewählt aus der Gruppe der sulfidischen Erze, der oxidischen und/oder carbonathaltigen Erze, beispielsweise Azurit [Cu3(CO3)2(OH)2], oder Malachit [Cu2[(OH)2[CO3]]), oder der Edelmetalle und deren Verbindungen, an die sich selektiv eine oberflächenaktive Verbindung unter Erzeugung von hydrophoben Oberflächeneigenschaften anlagern kann.Thus, the at least one first substance to be separated off is preferably a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing Ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2 [CO 3 ]]), or of the noble metals and their compounds, to which a surface-active compound is selectively added Generation of hydrophobic surface properties can attach.
Die wenigstens eine hydrophile Metallverbindung ist bevorzugt ausgewählt aus der Gruppe bestehend aus oxidischen und hydroxidischen Metallverbindungen, beispielsweise Siliziumdioxid SiO2, Silikate, Alumosilikate, beispielsweise Feldspate, beispielsweise Albit Na(Si3Al)O8, Glimmer, beispielsweise Muskovit KAl2[(OH,F)2AlSi3O10], Granate (Mg, Ca, FeII)3(Al, FeIII)2(SiO4)3, Al2O3, FeO(OH), FeCO3, Fe2O3, Fe3O4 und weitere verwandte Mineralien und Mischungen davon.The at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic and hydroxide metal compounds, for example 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 , Al 2 O 3 , FeO (OH), FeCO 3 , Fe 2 O 3 , Fe 3 O 4 and other related minerals and mixtures thereof.
Beispiele für erfindungsgemäß einsetzbare sulfidische Erze sind z.B. ausgewählt aus der Gruppe der Kupfererze bestehend aus Covellit CuS, Molybdän(IV)-sulfid, Chalkopyrit (Kupferkies) CuFeS2, Bornit Cu5FeS4, Chalkozyt (Kupferglanz) Cu2S und Mischungen davon.Examples of sulfidic ores which can be used according to the invention are selected, for example, from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper gravel) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite (copper luster) Cu 2 S and mixtures thereof.
Geeignete erfindungsgemäß einsetzbare oxidische Metallverbindungen sind bevorzugt ausgewählt aus der Gruppe bestehend aus Siliziumdioxid SiO2, Silikate, Alumosilikate, beispielsweise Feldspate, beispielsweise Albit Na(Si3Al)O8, Glimmer, beispielsweise Muskovit KAl2[(OH,F)2AlSi3O10], Granate (Mg, Ca, FeII)3(Al, FeIII)2(SiO4)3 und weitere verwandte Mineralien und Mischungen davon.Suitable oxidic metal compounds which can be used 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 other related minerals and mixtures thereof.
In dem erfindungsgemäßen Verfahren werden demnach bevorzugt unbehandelte Erzmischungen eingesetzt, welche aus Minenvorkommen gewonnen werden.Accordingly, untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens liegt die Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff in Schritt (A) in Form von Partikeln mit einer Größe 100 nm bis 100 µm vor, siehe beispielsweise
Beispiele für sulfidische Mineralien, die in den erfindungsgemäß einsetzbaren Mischungen vorliegen, sind die oben genannten. Zusätzlich können in den Mischungen auch Sulfide anderer Metalle als Kupfer vorliegen, beispielsweise Sulfide von Eisen; Blei, Zink oder Molybdän, d.h. FeS/FeS2, PbS, ZnS oder MoS2. Des Weiteren können in den erfindungsgemäß zu behandelnden Erzmischungen oxidische Verbindungen von Metallen und Halbmetallen, beispielsweise Silikate oder Borate oder andere Salze von Metallen und Halbmetallen, beispielsweise Phosphate, Sulfate oder Oxide/Hydroxide/Carbonate und weitere Salze vorliegen, beispielsweise Azurit [Cu3(CO3)2(OH)2], Malachit [Cu2[(OH)2(CO3)]], Baryt (BaSO4), Monacit ((La-Lu)PO4). Weitere Beispiele für den wenigstens einen ersten Stoff, der durch das erfindungsgemäße Verfahren abgetrennt wird, sind Edelmetalle. beispielsweise Au, Pt, Pd, Rh etc. bevorzugt im gediegenen Zustand.Examples of sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above. Additionally, in the mixtures sulphides of metals other than copper are also present, for example sulphides of iron; Lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 . Furthermore, in the ore mixtures to be treated according to the invention, 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 ), monacite ((La-Lu) PO 4 ). Further examples of the at least one first substance which is separated by the process according to the invention are noble metals. For example, Au, Pt, Pd, Rh, etc., preferably in a pure state.
Eine typischerweise eingesetzte Erzmischung, die mit dem erfindungsgemäßen Verfahren getrennt werden kann, hat die folgende Zusammensetzung: ca. 30 Gew.-% SiO2, ca. 10 Gew.-% NA(Si3Al)O8, ca. 3 Gew.-% Cu2S, ca. 1 Gew.-% MoS2, Rest Chrom-, Eisen-, Titan- und Magnesiumoxide.A typically used ore mixture, which can be separated by the method according to the invention, has the following composition: about 30 wt .-% SiO 2 , about 10 wt .-% NA (Si 3 Al) O 8 , about 3 wt. -% Cu 2 S, about 1 wt .-% MoS 2 , balance chromium, iron, titanium and magnesium oxides.
Die einzelnen Schritte des erfindungsgemäßen Verfahrens werden im Folgenden detailliert beschrieben:The individual steps of the method according to the invention are described in detail below:
Schritt (A) des erfindungsgemäßen Verfahrens umfasst das Inkontaktbringen der Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff mit wenigstens einer oben genannten oberflächenaktiven Substanz, gegebenenfalls in Gegenwart wenigstens eines Dispersionsmittels, wobei die oberflächenaktive Substanz selektiv an den wenigstens einen ersten Stoff anbindet,Step (A) of the method according to the invention comprises contacting the mixture containing at least a first substance and at least one second substance with at least one surface-active substance, if appropriate in the presence of at least one dispersing agent, wherein the surface-active substance binds selectively to the at least one first substance,
Geeignete und bevorzugte erste und zweite Stoffe sind oben genannt.Suitable and preferred first and second substances are mentioned above.
Im Rahmen der vorliegenden Erfindung bedeutet "oberflächenaktive Substanz" eine Substanz, die in der Lage ist, die Oberfläche des abzutrennenden Teilchens in Anwesenheit der anderen Teilchen, die nicht abgetrennt werden sollen, so zu ändern, dass eine Anlagerung eines hydrophoben Teilchens durch hydrophobe Wechselwirkungen zu Stande kommt. Erfindungsgemäß einsetzbare oberflächenaktive Substanzen lagern sich an den mindestens einen ersten Stoff an und bewirken dadurch eine geeignete Hydrophobizität des ersten Stoffes.In the context of the present invention, "surface-active substance" means a substance which is capable of changing the surface of the particle to be separated in the presence of the other particles which are not to be separated in such a way that an attachment of a hydrophobic particle by hydrophobic interactions to Come. Surface-active substances which can be used according to the invention are deposited on the at least one first substance and thereby bring about a suitable hydrophobicity of the first substance.
In einer besonders bevorzugten Ausführungsform ist A in Formel (I) ein lineares oder verzweigtes C4-C12-Alkyl, ganz besonders bevorzugt ein lineares C4- oder C8-Alkyl. Erfindungsgemäß gegebenenfalls vorhandene Heteroatome sind ausgewählt aus N, O, P, S und Halogenen wie F, Cl, Br und I.In a particularly preferred embodiment, A in formula (I) is a linear or branched C 4 -C 12 -alkyl, very particularly preferably a linear C 4 - or C 8 -alkyl. Optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
In einer weiteren bevorzugten Ausführungsform ist A in Formel (I) bevorzugt ein lineares oder verzweigtes, bevorzugt lineares, C8-C20-Alkyl. Weiterhin ist A bevorzugt ein verzweigtes C6-C14-Alkyl, wobei der wenigstens eine Substituent, bevorzugt mit 1 bis 6 Kohlenstoffatomen, bevorzugt in 2-Position, vorliegt, beispielsweise 2-Ethylhexyl und/oder 2-Propylheptyl.In a further preferred embodiment, A in formula (I) is preferably a linear or branched, preferably linear, C 8 -C 20 -alkyl. Furthermore, A is preferably a branched C 6 -C 14 -alkyl, wherein the at least one substituent, preferably having 1 to 6 carbon atoms, is preferably present in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl.
In einer weiteren besonders bevorzugten Ausführungsform ist Z in Formel (I) ausgewählt aus der Gruppe bestehend aus anionischen Gruppen -(X)n-PO3 2-, -(X)n-PO2S2-, - (X)n-POS2 2-, -(X)n-PS3 2-, -(X)n-PS2 -, -(X)n-POS-, -(X)n-PO2-, -(X)n-PO3 2- -(X)n-CO2 -, -(X)n-CS2 -, -(X)n-COS-, -(X)n-C(S)NHOH. -(X)n-S- mit X ausgewählt aus der Gruppe bestehend aus O, S, NH, CH2 und n = 0, 1 oder 2, mit gegebenenfalls Kationen ausgewählt aus der Gruppe bestehend aus Wasserstoff, NR4 + mit R gleich unabhängig voneinander Wasserstoff und/oder C1-C8-Alkyl, Alkali- oder Erdalkalimetallen. Die genannten Anionen und die entsprechenden Kationen bilden erfindungsgemäß neutral geladene Verbindungen der allgemeinen Formel (I).In a further particularly preferred embodiment, Z in formula (I) is selected from the group consisting of anionic groups - (X) n -PO 3 2- , - (X) n -PO 2 S 2- , - (X) n - POS 2 2- , - (X) n -PPS 3 2- , - (X) n -PPS 2 - , - (X) n -POS - , - (X) n -PO 2- , - (X) n -PO 3 2- (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n -COS - , - (X) n -C (S) NHOH. - (X) n -S - with X selected from the group consisting of O , S, NH, CH 2 and n = 0, 1 or 2, optionally with cations selected from the group consisting of hydrogen, NR 4 + with R equals independently of one another hydrogen and / or C 1 -C 8 -alkyl, alkali or alkaline-earth metals. The anions mentioned and the corresponding cations form neutral charged compounds of the general formula (I) according to the invention.
Bedeutet in den genannten Formeln n = 2, so liegen zwei gleiche oder unterschiedliche, bevorzugt gleiche, Gruppen A an eine Gruppe Z gebunden vor.If n = 2 in the abovementioned formulas, then two identical or different, preferably identical, groups A are bound to a group Z.
In einer besonders bevorzugten Ausführungsform werden Verbindungen eingesetzt, ausgewählt aus der Gruppe bestehend aus Xanthaten A-O-CS2 -, Dialkyldithiophosphaten (A-O)2PS2 -, Dialkyldithioposphinaten (A)2-PS2 - und Mischungen davon, wobei A unabhängig voneinander ein lineares oder verzweigtes, bevorzugt lineares, C8-C20-Alkyl, beispielsweise n-Octyl, oder ein verzweigtes C6-C14-Alkyl, wobei die Verzweigung bevorzugt in 2-Position vorliegt, beispielsweise 2-Ethylhexyl und/oder 2-Propylheptyl, ist. Als Gegenionen liegen in diesen Verbindungen bevorzugt Kationen ausgewählt aus der Gruppe bestehend aus Wasserstoff, NR4 + mit R gleich unabhängig voneinander Wasserstoff und/oder C1-C8-Alkyl, Alkali- oder Erdalkalimetallen, insbesondere Natrium oder Kalium, vor.In a particularly preferred embodiment, compounds selected from the group consisting of xanthates AO-CS 2 - , dialkyldithiophosphates (AO) 2 PS 2 - , dialkyldithioposphinates (A) 2 -PS 2 - and mixtures thereof, wherein A is independently a linear or branched, preferably linear, C 8 -C 20 -alkyl, for example n-octyl, or a branched C 6 -C 14 -alkyl, wherein the branching is preferably in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl , is. Preferred counterions in these compounds are cations selected from the group consisting of hydrogen, NR 4 + with R being the same independently each other hydrogen and / or C 1 -C 8 alkyl, alkali or alkaline earth metals, in particular sodium or potassium before.
Ganz besonders bevorzugte Verbindungen der allgemeinen Formel (I) sind ausgewählt aus der Gruppe bestehend aus Natrium- oder Kalium-n-octylxanthat, Natrium- oder Kalium-butylxanthat, Natrium- oder Kalium-di-n-octyldithiophosphinat, Natrium- oder Kalium-di-n-octyldithiophosphat, und Mischungen dieser Verbindungen.Very particularly 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-octyl dithiophosphinate, sodium or potassium di -n-octyl dithiophosphate, and mixtures of these compounds.
Für Edelmetalle, beispielsweise Au, Pd, Rh etc., sind besonders bevorzugte oberflächenaktive Substanzen Mono-, Di- und Trithiole oder 8-Hydroxychinoline, beispielsweise beschrieben in
Für Metalloxide, beispielsweise FeO(OH), Fe3O4, ZnO etc., Carbonate, beispielsweise Azurit (Cu(CO3)2(OH)2], Malachit [Cu2[(OH)2CO3]], sind besonders bevorzugte oberflächenaktive Substanzen Octylphosphonsäure (OPS), (EtO)3Si-A, (MeO)3Si-A, mit den oben genannten Bedeutungen für A. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden als oberflächenaktive Substanzen keine Hydroxamate zur Modifizierung von Metalloxiden eingesetzt.For metal oxides, for example FeO (OH), Fe 3 O 4 , ZnO etc., carbonates, for example azurite (Cu (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 CO 3 ]] Particularly preferred surface-active substances octylphosphonic acid (OPS), (EtO) 3 Si-A, (MeO) 3 Si-A, with the abovementioned meanings for A. In a preferred embodiment of the process according to the invention, the surface-active substances used are not hydroxamates for modifying metal oxides used.
Für Metallsulfide, beispielsweise Cu2S, MoS2, etc., sind besonders bevorzugte oberflächenaktive Substanzen Mono-, Di- und Trithiole oder Xanthogenate.For metal sulfides, for example Cu 2 S, MoS 2 , etc., particularly preferred surface-active substances are mono-, di- and trithiols or xanthates.
In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens bedeutet Z -(X)n-CS2 -, -(X)n-PO2 - oder -(X)n-S- mit X gleich O und n gleich 0 oder 1 und einem Kation ausgewählt aus Wasserstoff, Natrium oder Kalium. Ganz besonders bevorzugte oberflächenaktive Substanzen sind 1-Octanthiol, Kalium-n-oktylxanthat, Kalium-butylxanthat, Octylphosphonsäure oder eine Verbindung der folgenden Formel (IV)
Das Inkontaktbringen in Schritt (A) des erfindungsgemäßen Verfahrens kann durch alle dem Fachmann bekannte Verfahren geschehen. Schritt (A) kann in Substanz oder in Dispersion, bevorzugt in Suspension, besonders bevorzugt in wässriger Suspension, durchgeführt werden.The contacting in step (A) of the process according to the invention can be carried out by all methods known to the person skilled in the art. Step (A) can be carried out in bulk or in dispersion, preferably in suspension, particularly preferably in aqueous suspension.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird Schritt (A) in Substanz, d.h. in Abwesenheit eines Dispersionsmittels, durchgeführt.In one embodiment of the process according to the invention, step (A) is carried out in bulk, ie in the absence of a dispersing agent.
Beispielsweise werden die zu behandelnde Mischung und die wenigstens eine oben genannte oberflächenaktive Substanz ohne weiteres Dispersionsmittel in den entsprechenden Mengen zusammen gegeben und vermischt. Geeignete Mischungsapparaturen sind dem Fachmann bekannt, beispielsweise Mühlen, wie Kugelmühle.For example, the mixture to be treated and the at least one above-mentioned surfactant are added and mixed together without additional dispersant in the appropriate amounts. Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill.
In einer weiteren bevorzugten Ausführungsform wird Schritt (A) in einer Dispersion, bevorzugt in Suspension, durchgeführt. Als Dispersionsmittel sind alle Dispersionsmittel geeignet, in denen die Mischung aus Schritt (A) nicht vollständig löslich ist. Geeignete Dispersionsmittel zur Herstellung der Aufschlämmung oder Dispersion gemäß Schritt (B) des erfindungsgemäßen Verfahrens sind ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Verbindungen, beispielsweise Alkoholen mit 1 bis 4 Kohlenstoffatomen, und Mischungen davon.In a further preferred embodiment, step (A) is carried out in a dispersion, preferably in suspension. As the dispersant, all dispersants are suitable in which the mixture of step (A) is not completely soluble. Suitable dispersants for the preparation of the slurry or dispersion according to step (B) of the process of the invention are selected from the group consisting of water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
In einer besonders bevorzugten Ausführungsform ist das Dispersionsmittel in Schritt (A) Wasser.In a particularly preferred embodiment, the dispersant in step (A) is water.
Schritt (A) des erfindungsgemäßen Verfahrens wird im Allgemeinen bei einer Temperatur von 1 bis 80 °C, bevorzugt bei 20 bis 40 °C, besonders bevorzugt bei Umgebungstemperatur durchgeführt.Step (A) of the process according to the invention is generally carried out at a temperature of 1 to 80 ° C, preferably at 20 to 40 ° C, more preferably at ambient temperature.
Die wenigstens eine oben genannte oberflächenaktive Substanz wird im Allgemeinen in einer Menge eingesetzt, die ausreicht, um den gewünschten Effekt zu erzielen. In einer bevorzugten Ausführungsform wird die wenigstens eine oberflächenaktive Substanz in einer Menge von 0,01 bis 5 Gew.-% zugegeben, jeweils bezogen auf die gesamte zu behandelnde Mischung.The at least one above-mentioned surfactant is generally used in an amount sufficient to achieve the desired effect. In a preferred embodiment, the at least one surfactant is added in an amount of 0.01 to 5 wt .-%, each based on the total mixture to be treated.
Der optionale Schritt (B) des erfindungsgemäßen Verfahrens umfasst die Zugabe wenigstens eines Dispersionsmittels zu der in Schritt (A) erhaltenen Mischung, um eine Dispersion zu erhaltenThe optional step (B) of the process of the invention comprises adding at least one dispersing agent to the mixture obtained in step (A) to obtain a dispersion
Die in Schritt (A) erhaltene Mischung enthält in einer Ausführungsform, falls Schritt (A) in Substanz durchgeführt wird, wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff, der an der Oberfläche mit wenigstens einer oberflächenaktiven Substanz modifiziert worden ist. Wird Schritt (A) in Substanz durchgeführt, wird Schritt (B) des erfindungsgemäßen Verfahrens durchgeführt, d.h. wenigstens ein geeignetes Dispersionsmittel wird zu der in Schritt (A) erhaltenen Mischung zugegeben, um eine Dispersion zu erhalten.In one embodiment, if step (A) is carried out in bulk, the mixture obtained in step (A) contains at least one first substance and at least one second substance which has been modified on the surface with at least one surface-active substance. When step (A) is carried out in substance, step (B) of the method according to the invention is carried out, i. at least one suitable dispersing agent is added to the mixture obtained in step (A) to obtain a dispersion.
In der Ausführungsform, in der Schritt (A) des erfindungsgemäßen Verfahrens in Dispersion durchgeführt wird, wird Schritt (B) nicht durchgeführt. Es ist jedoch auch bei dieser Ausführungsform möglich, Schritt (B) durchzuführen, d.h. weiteres Dispersionsmittel zuzugeben, um eine Dispersion mit einer niedrigeren Konzentration zu erhalten.In the embodiment in which step (A) of the process according to the invention is carried out in dispersion, step (B) is not carried out. It is, however, also at of this embodiment, it is possible to carry out step (B), ie to add further dispersing agent to obtain a dispersion having a lower concentration.
Als geeignete Dispersionsmittel sind alle Dispersionsmittel geeignet, die bereits bezüglich Schritt (A) genannt worden sind. In einer besonders bevorzugten Ausführungsform ist das Dispersionsmittel in Schritt (A) Wasser.Suitable dispersants are all dispersants which have already been mentioned with respect to step (A). In a particularly preferred embodiment, the dispersant in step (A) is water.
In Schritt (B) wird somit entweder die in Substanz vorliegende Mischung aus Schritt (A) in eine Dispersion überführt, oder die bereits in Dispersion vorliegenden Mischung aus Schritt (A) wird durch Zugabe von Dispersionsmittel in eine Dispersion niedrigerer Konzentration überführt.In step (B), either the mixture of substance from step (A) is thus converted into a dispersion, or the mixture already present in dispersion from step (A) is converted into a dispersion of lower concentration by adding dispersing agent.
Im Allgemeinen kann die Menge an Dispersionsmittel, zugegeben in Schritt (A) und/oder Schritt (B) erfindungsgemäß so gewählt werden, dass eine Dispersion erhalten wird, welche gut rührbar und/oder förderbar ist. In einer bevorzugten Ausführungsform beträgt die Menge an zu behandelnder Mischung bezogen auf die gesamte Aufschlämmung oder Dispersion bis 100 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%.In general, the amount of dispersant added in step (A) and / or step (B) may be selected according to the invention to give a dispersion which is readily stirrable and / or recoverable. In a preferred embodiment, the amount of mixture to be treated based on the total slurry or dispersion to 100 wt .-%, particularly preferably 0.5 to 10 wt .-%.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird Schritt (B) nicht durchgeführt, sondern Schritt (A) wird in wässriger Dispersion durchgeführt, so dass in Schritt (A) direkt eine Mischung in wässriger Dispersion erhalten wird, die die richtige Konzentration aufweist, um in Schritt (C) des erfindungsgemäßen Verfahrens eingesetzt zu werden.In a preferred embodiment of the process according to the invention, step (B) is not carried out, but step (A) is carried out in aqueous dispersion, so that in step (A) directly a mixture in aqueous dispersion is obtained, which has the correct concentration to Step (C) of the method according to the invention to be used.
Die Zugabe von Dispersionsmittel in Schritt (B) des erfindungsgemäßen Verfahrens kann erfindungsgemäß nach allen dem Fachmann bekannten Verfahren erfolgen.The addition of dispersant in step (B) of the process according to the invention can be carried out according to the invention by all methods known to the person skilled in the art.
Schritt (C) des erfindungsgemäßen Verfahrens umfasst das Behandeln der Dispersion aus Schritt (A) oder (B) mit wenigstens einem hydrophoben Magnetpartikel, so dass sich der wenigstens eine in Schritt (A) hydrophobierte erste Stoff, an den die wenigstens eine oben genannte oberflächenaktive Substanz angebunden ist, und der wenigstens eine Magnetpartikel anlagern.Step (C) of the process according to the invention comprises treating the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle, so that the at least one first substance rendered hydrophobic in step (A) to which the at least one above-mentioned surface active substance belongs Substance is attached, and attach at least one magnetic particle.
In Schritt (C) des erfindungsgemäßen Verfahrens können alle dem Fachmann bekannten magnetischen Substanzen und Stoffe eingesetzt werden. In einer bevorzugten Ausführungsform ist der wenigstens eine Magnetpartikel ausgewählt aus der Gruppe bestehend aus magnetischen Metallen, beispielsweise Eisen, Cobalt, Nickel und Mischungen davon, ferromagnetischen Legierungen von magnetischen Metallen, beispielsweise NdFeB, SmCo und Mischungen davon, magnetischen Eisenoxiden, beispielsweise Magnetit, Maghemit, kubischen Ferriten der allgemeinen Formel (II)
M2+ xFe2+ 1-xFe3+ 2O4 (II)
mit
- M
- ausgewählt aus Co, Ni, Mn, Zn und Mischungen davon und
- x
- ≤ 1,
M 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 (II)
With
- M
- selected from Co, Ni, Mn, Zn and mixtures thereof and
- x
- ≤ 1,
In einer besonders bevorzugten Ausführungsform der vorliegenden Anmeldung ist der wenigstens eine magnetische Partikel Magnetit oder Kobaltferrit Co2+ xFe2+ 1-xFe3+ 2O4 mit x ≤ 1.In a particularly preferred embodiment of the present application, the at least one magnetic particle is magnetite or cobalt ferrite Co 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 with x ≤ 1.
In einer bevorzugten Ausführungsform liegen die in Schritt (C) des erfindungsgemäßen Verfahrens eingesetzten Magnetpartikel in einer Größe von 100 nm bis 100 µm, besonders bevorzugt 1 bis 50 µm, vor. Die Magnetpartikel können vor Verwendung in Schritt (C) nach dem Fachmann bekannten Verfahren in die entsprechende Größe überführt werden, beispielsweise durch Mahlen. Weiter können die Partikel, hergestellt durch eine Fällungsreaktion, durch Einstellen der Reaktionsparameter (z. B. pH, Reaktionsdauer, Temperatur) auf diese Partikelgröße gebracht werden.In a preferred embodiment, the magnetic particles used in step (C) of the process according to the invention are in a size of 100 nm to 100 .mu.m, more preferably 1 to 50 .mu.m before. Before use in step (C), the magnetic particles can be converted into the appropriate size by methods known to the person skilled in the art, for example by grinding. Furthermore, the particles produced by a precipitation reaction can be brought to this particle size by adjusting the reaction parameters (eg pH, reaction time, temperature).
In einer weiteren bevorzugten Ausführungsform ist der wenigstens eine magnetische Partikel an der Oberfläche mit wenigstens einer hydrophoben Verbindung hydrophobiert. Bevorzugt ist die hydrophobe Verbindung ausgewählt aus Verbindungen der allgemeinen Formel (III)
B-Y (III),
worin
- B
- ausgewählt ist aus linearem oder verzweigtem C3-C30-Alkyl, C3-C30-Heteroalkyl, gegebenenfalls substituiertes C6-C30-Aryl, gegebenenfalls substituiertes C6-C30-Heteroalkyl, C6-C30-Aralkyl und
- Y
- eine Gruppe ist, mit der die Verbindung der allgemeinen Formel (III) an den wenigstens einen magnetischen Partikel anbindet.
BY (III),
wherein
- B
- is selected from linear or branched C 3 -C 30 alkyl, C 3 -C 30 heteroalkyl, optionally substituted C 6 -C 30 aryl, optionally substituted C 6 -C 30 heteroalkyl, C 6 -C 30 aralkyl and
- Y
- is a group with which the compound of the general formula (III) binds to the at least one magnetic particle.
In einer besonders bevorzugten Ausführungsform ist B ein lineares oder verzweigtes C6-C18-Alkyl, bevorzugt lineares C8-C12-Alkyl, ganz besonders bevorzugt ein lineares C12-Alkyl. Erfindungsgemäß gegebenenfalls vorhandene Heteroatome sind ausgewählt aus N, O, P, S und Halogenen wie F, Cl, Br und I.In a particularly preferred embodiment, B is a linear or branched C 6 -C 18 -alkyl, preferably linear C 8 -C 12 -alkyl, very particularly preferably a linear one C 12 alkyl. Optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
In einer weiteren besonders bevorzugten Ausführungsform ist Y ausgewählt aus der Gruppe bestehend aus -(X)n-SiHal3, -(X)n-SiHHal2, -(X)n-SiH2Hal mit Hal gleich F, Cl, Br, I, und anionischen Gruppen wie -(X)n-SiO3 3-, -(X)n-CO2 -, -(X)n-PO3 2-, -(X)n-PO2S2-, - (X)n-POS2 2-, -(X)n-PS3 2-, -(X)n-PS2 -, -(X)n-POS-, -(X)n-PO2 -, -(X)n-CO2 -, -(X)n-CS2 -, -(X)n-COS-, -(X)n-C(S)NHOH, -(X)n-S- mit X = O, S, NH, CH2 und n = 0, 1 oder 2, und gegebenenfalls Kationen ausgewählt aus der Gruppe bestehen aus Wasserstoff, NR4 + mit R gleich unabhängig voneinander Wasserstoff und/oder C1-C8-Alkyl, Alkali-, Erdalkalimetallen oder Zink, des Weiteren -(X)n-Si(OZ)3 mit n = 0, 1 oder 2 und Z = Ladung, Wasserstoff oder kurzkettiger Alkylrest.In a further particularly preferred embodiment, Y is selected from the group consisting of - (X) n -SiHal 3 , - (X) n -SiHHal 2 , - (X) n -SiH 2 Hal where Hal is equal to F, Cl, Br, I, 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 -PPS 3 2- , - (X) n -PPS 2 - , - (X) n -POS - , - (X) n -PO 2 - , - (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n -COS - , - (X) n -C (S) NHOH, - (X) n -S - with X = O, S, NH, CH 2 and n = 0, 1 or 2, and optionally cations selected from the group consisting of hydrogen, NR 4 + with R equal independently of one another hydrogen and / or C 1 -C 8 alkyl , Alkali metals, alkaline earth metals or zinc, furthermore - (X) n -Si (OZ) 3 with n = 0, 1 or 2 and Z = charge, hydrogen or short-chain alkyl radical.
Bedeutet in den genannten Formeln n = 2, so liegen zwei gleiche oder unterschiedliche, bevorzugt gleiche, Gruppen B an eine Gruppe Y gebunden vor.If n = 2 in the abovementioned formulas, then two identical or different, preferably identical, groups B are bound to a group Y.
Ganz besonders bevorzugte hydrophobierende Substanzen der allgemeinen Formel (III) sind Alkyltrichlorsilane (Alkylgruppe mit 6-12 Kohlenstoffatomen), Alkyltrimetoxysilane (Alkylgruppe mit 6-12 Kohlenstoffatomen), Octylphosphonsäure, Laurinsäure, Ölsäure, Stearinsäure oder Mischungen davon.Very particularly preferred hydrophobizing substances of the general formula (III) are alkyltrichlorosilanes (alkyl group having 6-12 carbon atoms), alkyltrimethoxysilanes (alkyl group having 6-12 carbon atoms), octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
Das Behandeln der Lösung oder Dispersion mit wenigstens einem hydrophoben Magnetpartikel in Schritt (C) des erfindungsgemäßen Verfahrens kann nach allen dem Fachmann bekannten Verfahren erfolgen.The treatment of the solution or dispersion with at least one hydrophobic magnetic particle in step (C) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
In einer bevorzugten Ausführungsform wird der wenigstens eine magnetische Partikel in einem geeigneten Dispersionsmittel dispergiert.In a preferred embodiment, the at least one magnetic particle is dispersed in a suitable dispersing agent.
Als geeignete Dispersionsmittel sind alle Dispersionsmittel geeignet, in denen der wenigstens eine Magnetpartikel nicht vollständig löslich ist. Geeignete Dispersionsmittel zur Dispergierung gemäß Schritt (C) des erfindungsgemäßen Verfahrens sind ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Verbindungen und Mischungen davon, besonders bevorzugt Wasser. Besonders bevorzugt wird in Schritt (C) das gleiche Dispersionsmittel eingesetzt wie in Schritt (B).Suitable dispersants are all dispersants in which the at least one magnetic particle is not completely soluble. Suitable dispersants for dispersion according to step (C) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds and mixtures thereof, more preferably water. Particularly preferably, in step (C), the same dispersing agent is used as in step (B).
Im Allgemeinen kann die Menge an Dispersionsmittel zum Vordispergieren der Magnetpartikel erfindungsgemäß so gewählt werden, dass eine Aufschlämmung oder Dispersion erhalten wird, welche gut rührbar und/oder förderbar ist. In einer bevorzugten Ausführungsform beträgt die Menge an zu behandelnder Mischung bezogen auf die gesamte Aufschlämmung oder Dispersion bis 60 Gew.-%.In general, the amount of dispersant for predispersing the magnetic particles may be selected according to the invention so as to obtain a slurry or dispersion which is readily stirrable and / or recoverable. In a preferred embodiment, the amount of mixture to be treated, based on the total slurry or dispersion, is up to 60% by weight.
Die Dispersion der Magnetpartikel kann erfindungsgemäß nach allen dem Fachmann bekannten Verfahren hergestellt werden. In einer bevorzugten Ausführungsform werden die zu dispergierenden Magnetpartikel und die entsprechende Menge Dispersionsmittel bzw. Dispersionsmittelgemisch in einem geeigneten Reaktor, beispielsweise einem Glasreaktor, zusammengegeben und mit dem Fachmann bekannten Vorrichtungen gerührt, beispielsweise in einer Glaswanne mit einem mechanisch betriebenen Flügelrührer, beispielsweise bei einer Temperatur von 1 bis 80 °C, bevorzugt bei Raumtemperatur.According to the invention, the dispersion of the magnetic particles can be prepared by all methods known to the person skilled in the art. In a preferred embodiment, the magnetic particles to be dispersed and the corresponding amount of dispersing agent or dispersing agent mixture in a suitable reactor, such as a glass reactor, combined and stirred with known in the art devices, for example in a glass pan with a mechanically operated paddle, for example at a temperature of 1 to 80 ° C, preferably at room temperature.
Das Behandeln der Dispersion aus Schritt (B) mit wenigstens einem hydrophoben Magnetpartikel geschieht im Allgemeinen so, dass beide Komponenten durch dem Fachmann bekannte Methoden zusammengegeben werden. In einer bevorzugten Ausführungsform wird eine Dispersion des wenigstens einen magnetischen Partikels zu der zuvor mit wenigstens einer oberflächenaktiven Substanz behandelten Mischung gegeben. In einer weiteren Ausführungsform kann der magnetische Partikel in fester Form zu einer Dispersion der zu behandelnden Mischung gegeben werden. In einer weiteren bevorzugten Ausführungsform liegen beide Komponenten in dispergierter Form vor.The treatment of the dispersion from step (B) with at least one hydrophobic magnetic particle is generally carried out so that both components are combined by methods known to the person skilled in the art. In a preferred embodiment, a dispersion of the at least one magnetic particle is added to the mixture previously treated with at least one surfactant. In a further embodiment, the magnetic particle may be added in solid form to a dispersion of the mixture to be treated. In a further preferred embodiment, both components are present in dispersed form.
Schritt (C) wird im Allgemeinen bei einer Temperatur von 1 bis 80 °C, bevorzugt 10 bis 30 °C durchgeführt.Step (C) is generally carried out at a temperature of 1 to 80 ° C, preferably 10 to 30 ° C.
In Schritt (C) lagert sich der wenigstens eine magnetische Partikel an den hydrophoben Stoff der zu behandelnden Mischung an. Die zwischen den beiden Komponenten bestehende Bindung basiert auf hydrophoben Wechselwirkungen. Zwischen dem wenigstens einen magnetischen Partikel und dem hydrophilen Anteil der Mischung findet im Allgemeinen keine bindende Wechselwirkung statt, so dass zwischen diesen Komponenten keine Anlagerung stattfindet. Nach Schritt (C) liegen somit in der Mischung Anlagerungsprodukte des wenigstens eine hydrophoben Stoffes und des wenigstens einen magnetischen Partikels neben dem wenigstens einen hydrophilen Stoff vor.In step (C), the at least one magnetic particle attaches to the hydrophobic substance of the mixture to be treated. The bond between the two components is based on hydrophobic interactions. There is generally no binding interaction between the at least one magnetic particle and the hydrophilic portion of the mixture, so that no attachment takes place between these components. After step (C), addition products of the at least one hydrophobic substance and the at least one magnetic particle are thus present in the mixture in addition to the at least one hydrophilic substance.
Schritt (D) des erfindungsgemäßen Verfahrens umfasst das Abtrennen des Anlagerungsproduktes aus Schritt (C) von der Mischung durch Anlegen eines magnetischen Feldes.Step (D) of the process according to the invention comprises separating the addition product from step (C) from the mixture by applying a magnetic field.
Schritt (D) kann in einer bevorzugten Ausführungsform durchgeführt werden, indem ein Dauermagnet in den Reaktor eingebracht wird, in dem sich die Mischung aus Schritt (C) befindet. In einer bevorzugten Ausführungsform befindet sich zwischen Dauermagnet und zu behandelnder Mischung eine Trennwand aus nicht magnetischem Material, beispielsweise die Glaswand des Reaktors. In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird in Schritt (D) ein elektrisch schaltbarer Magnet eingesetzt, der nur dann magnetisch ist, wenn ein elektrischer Strom fließt. Geeignete Vorrichtungen sind dem Fachmann bekannt.Step (D) may be carried out in a preferred embodiment by introducing a permanent magnet into the reactor in which the mixture from step (C) is located. In a preferred embodiment, between the permanent magnet and the mixture to be treated, there is a partition of non-magnetic material, for example, the glass wall of the reactor. In a further preferred embodiment of the method according to the invention, an electrically switchable magnet is used in step (D) which is magnetic only when an electric current flows. Suitable devices are known in the art.
Schritt (D) des erfindungsgemäßen Verfahrens kann bei jeder geeigneten Temperatur durchgeführt werden, beispielsweise 10 bis 60 °C.Step (D) of the process according to the invention may be carried out at any suitable temperature, for example 10 to 60 ° C.
Während Schritt (D) wird die Mischung bevorzugt permanent mit einem geeigneten Rührer, beispielsweise einem Teflonrührbalken oder einem Flügelrührer, gerührt.During step (D), the mixture is preferably stirred continuously with a suitable stirrer, for example a Teflon stirring bar or a paddle stirrer.
In Schritt (D) kann das Anlagerungsprodukt aus Schritt (C) gegebenenfalls durch alle dem Fachmann bekannten Verfahren abgetrennt werden, beispielsweise durch Ablassen der Flüssigkeit mit dem hydrophilen Anteil der Suspension aus dem Bodenventil aus dem für Schritt (D) benutzten Reaktor oder Abpumpen der nicht durch den mindestens einen Magneten festgehaltenen Anteile der Suspension durch einen Schlauch.In step (D), the adduct of step (C) may optionally be separated by any method known to those skilled in the art, for example by draining the liquid with the hydrophilic portion of the suspension from the bottom valve from the reactor used for step (D) or pumping it off held by the at least one magnet portions of the suspension through a hose.
Schritt (E) des erfindungsgemäßen Verfahrens umfasst das Spalten des abgetrennten Anlagerungsproduktes aus Schritt (D), um den wenigstens einen ersten Stoff und den wenigstens einen Magnetpartikel separat zu erhalten. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt das Spalten in Schritt (E) nicht zerstörerisch, d.h. dass die in der Dispersion vorliegenden Einzelkomponenten chemisch nicht verändert werden. Beispielsweise erfolgt die erfindungsgemäße Spaltung nicht durch Oxidation des Hydrophobierungsmittels, beispielsweise unter Erhalt der Oxidationsprodukte oder von Abbauprodukten des Hydrophobierungsmittels.Step (E) of the process according to the invention comprises cleaving the separated addition product from step (D) in order to obtain the at least one first substance and the at least one magnetic particle separately. In a preferred embodiment of the process according to the invention, the cleavage in step (E) is not destructive, i. that the individual components present in the dispersion are not chemically changed. For example, the cleavage according to the invention does not take place by oxidation of the hydrophobizing agent, for example to obtain the oxidation products or degradation products of the hydrophobizing agent.
Das Spalten kann nach allen dem Fachmann bekannten Verfahren erfolgen, die dazu geeignet sind, das Anlagerungsprodukt derart zu spalten, dass der wenigstens eine magnetische Partikel in wieder einsetzbarer Form zurück gewonnen werden kann. In einer bevorzugten Ausführungsform wird der abgespaltene Magnetpartikel wieder in Schritt (C) eingesetzt.The splitting can be carried out by all methods known to those skilled in the art, which are suitable for splitting the addition product in such a way that the at least one magnetic particle can be recovered in reusable form. In a preferred embodiment, the cleaved magnetic particle is used again in step (C).
In einer bevorzugten Ausführungsform erfolgt das Spalten in Schritt (E) des erfindungsgemäßen Verfahrens durch Behandlung des Anlagerungsproduktes mit einer Substanz ausgewählt aus der Gruppe bestehend aus organischen Lösungsmitteln, basischen Verbindungen, sauren Verbindungen, Oxidationsmitteln, Reduktionsmitteln, oberflächenaktiven Verbindungen und Mischungen davon.In a preferred embodiment, the cleavage in step (E) of the process according to the invention is carried out by treating the addition product with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, reducing agents, surface-active compounds and mixtures thereof.
Beispiele für geeignete organische Lösungsmittel sind Methanol, Ethanol, Propanol, beispielsweise n-Propanol oder iso-Propanol, aromatische Lösungsmittel, beispielsweise Benzol, Toluol, Xylole, Ether, beispielsweise Diethylether, Methyl-t-butyl-ether, Ketone, beispielsweise Aceton, aromatische oder aliphatische Kohlenwasserstoffe, beispielsweise gesättigte Kohlenwasserstoffe mit beispielsweise 8 bis 16 Kohlenstoffatomen, beispielsweise Dodecan und/oder Shellsol®, Dieselkraftstoffe und Mischungen davon. Die Hauptbestandteile des Dieselkraftstoffes sind vorwiegend Alkane, Cycloalkane und aromatische Kohlenwasserstoffe mit etwa 9 bis 22 KohlenstoffAtomen pro Molekül und einem Siedebereich zwischen 170 °C und 390 °C.Examples of suitable organic solvents are methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example Benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether, ketones, for example acetone, aromatic or aliphatic hydrocarbons, for example saturated hydrocarbons having, for example, 8 to 16 carbon atoms, for example dodecane and / or Shellsol®, diesel fuels and mixtures from that. The main components of the diesel fuel are predominantly alkanes, cycloalkanes and aromatic hydrocarbons having about 9 to 22 carbon atoms per molecule and a boiling range between 170 ° C and 390 ° C.
Beispiele für erfindungsgemäß einsetzbare basische Verbindungen sind wässrige Lösungen basischer Verbindungen, beispielsweise wässrige Lösungen von Alkali- und/oder Erdalkalihydroxiden, beispielsweise KOH, NaOH, Kalkmilch, wässrige Ammoniaklösungen, wässrige Lösungen organischer Amine der allgemeinen Formel R2 3N, wobei R2 unabhängig voneinander ausgewählt ist aus der Gruppe bestehend aus C1-C8-Alkyl, gegebenenfalls substituiert mit weiteren funktionellen Gruppen. In einer bevorzugten Ausführungsform erfolgt Schritt (D) durch Zugabe von wässriger NaOH-Lösung bis zu einem pH-Wert von 13, beispielsweise für die Abtrennung von mit OPS modifiziertem Cu2S. Die sauren Verbindungen können mineralische Säuren sein, beispielsweise HCl, H2SO4, HNO3 oder Mischungen davon, organische Säuren, beispielsweise Carbonsäuren. Als Oxidationsmittel kann beispielsweise H2O2 eingesetzt werden, beispielsweise als 30 gew.%ige wässrige Lösung (Perhydrol). Für die Abtrennung von mit Thiolen modifiziertem Cu2S wird bevorzugt H2O2 oder Na2S2O4 eingesetzt.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, milk of lime, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 2 3 N, where R 2 is independently of one another is selected from the group consisting of C 1 -C 8 alkyl, optionally substituted with further functional groups. In a preferred embodiment, step (D) is carried out by adding aqueous NaOH solution to a pH of 13, for example for the separation of OPS-modified Cu 2 S. The acidic compounds may be mineral acids, for example HCl, H 2 SO 4 , HNO 3 or mixtures thereof, organic acids, for example carboxylic acids. As an oxidizing agent, for example, H 2 O 2 can be used, for example, as a 30 wt.% Aqueous solution (perhydrol). For the separation of thiols modified Cu 2 S is preferably H 2 O 2 or Na 2 S 2 O 4 used.
Beispiele für erfindungsgemäß einsetzbare oberflächenaktive Verbindungen sind nichtionische, anionische, kationische und/oder zwitterionische Tenside.Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
In einer bevorzugten Ausführungsform wird das Anlagerungsprodukt aus hydrophoben Stoff und magnetischem Teilchen mit einem organischen Lösungsmittel, besonders bevorzugt mit Aceton und/oder Diesel, gespalten. Dieser Vorgang kann auch mechanisch unterstützt werden. In einer bevorzugten Ausführungsform wird Ultraschall zur Unterstützung des Spaltungsvorgangs eingesetzt.In a preferred embodiment, the addition product of hydrophobic substance and magnetic particle is cleaved with an organic solvent, particularly preferably with acetone and / or diesel. This process can also be supported mechanically. In a preferred embodiment, ultrasound is used to assist the cleavage process.
Im Allgemeinen wird das organische Lösungsmittel in einer Menge verwendet, die ausreicht, um möglichst das gesamte Anlagerungsprodukt zu spalten. In einer bevorzugten Ausführungsform werden 20 bis 100 ml des organischen Lösungsmittels pro Gramm zu spaltendem Anlagerungsprodukt aus hydrophobem Stoff und magnetischem Partikel verwendet.In general, the organic solvent is used in an amount sufficient to cleave as much of the entire addition product as possible. In a preferred embodiment, 20 to 100 ml of the organic solvent are used per gram of hydrophobic and magnetic particle cleavage product.
Erfindungsgemäß liegt nach der Spaltung der wenigstens eine erste Stoff und der wenigstens eine Magnetpartikel als Dispersion in dem genannten Spaltungsreagenz, bevorzugt einem organischen Lösungsmittel, vor.According to the invention, after cleavage, the at least one first substance and the at least one magnetic particle are present as a dispersion in the cleavage reagent mentioned, preferably an organic solvent.
Der wenigstens eine Magnetpartikel wird aus der Dispersion enthaltend diesen wenigstens einen Magnetpartikel und den wenigstens einen ersten Stoff durch einen permanenten oder schaltbaren Magneten von der Lösung abgetrennt. Details dieses Abtrennens sind analog zu Schritt (D) des erfindungsgemäßen Verfahrens.The at least one magnetic particle is separated from the dispersion containing this at least one magnetic particle and the at least one first substance by a permanent or switchable magnet from the solution. Details of this separation are analogous to step (D) of the method according to the invention.
Bevorzugt wird der abzutrennende erste Stoff, bevorzugt die abzutrennende Metallverbindung, von dem organischen Lösungsmittel durch Abdestillieren des organischen Lösungsmittels getrennt. Der so erhältliche erste Stoff kann durch weitere, dem Fachmann bekannte Verfahren gereinigt werden. Das Lösungsmittel kann, gegebenenfalls nach Aufreinigung, wieder in das erfindungsgemäße Verfahren zurückgeführt werden.Preferably, the first material to be separated off, preferably the metal compound to be separated, is separated from the organic solvent by distilling off the organic solvent. The first substance obtainable in this way can be purified by further methods known to the person skilled in the art. The solvent can, if appropriate after purification, be recycled back to the process according to the invention.
Eine Mischung aus 10,0 g Seesand (Bernd Kraft GmbH; mit Salzsäure gereinigt; Charge 1046306), 2,02 g Cu2S (Pulver, 325 mesh; Aldrich Lot 01516LD-416) und 1,7 Gew.-% 1-Octanthiol (98 %ig, z. Synthese von Merck; Charge S20709716) wird in einer Planetenkugelmühle (500 mL Achatbehälter mit 50 Achatkugeln (Ø = 10 mm) 30 min bei 200 U/min. miteinander vermahlen. Die Mischung wird anschließend im Vakuumtrockenschrank (p < 100 mbar) für 16 h bei 50 °C getrocknet.A mixture of 10.0 g of sea sand (Bernd Kraft GmbH, purified with hydrochloric acid, Lot 1046306), 2.02 g of Cu 2 S (powder, 325 mesh, Aldrich Lot 01516LD-416) and 1.7% by weight of 1- Octanethiol (98%, eg synthesis by Merck, batch S20709716) is ground together in a planetary ball mill (500 ml agate container with 50 agate balls (Ø = 10 mm) for 30 min at 200 rpm.) The mixture is then placed in a vacuum drying oven ( p <100 mbar) for 16 h at 50 ° C dried.
Dieses Gemisch wird mit 1,506 g Magnetit, der mit Dodecyltrichlorsilan modifiziert worden ist (primäre Partikelgröße: ca. 10 nm), in eine 1 L Rührapparatur gegeben, mit 580 mL Wasser und 0,1 g Dodecylamin (Fa. Alfa Aeser Lot: 10108955) versetzt und 45 min bei 150 U/min. mit einem Teflonrührbalken vermengt. Anschließend wir ein Co-Sm-Magnet (5 cm Höhe, 2 cm Länge, 2 cm Breite) an eine Außenwand der Rührapparatur gehalten und noch weitere 30 min. bei 150 U/min. gerührt. Danach wird das Wasser über einen Schlauch entfernt, und die Apparatur noch für 10 min mit einem Heißluftgebläse getrocknet. Der Sand, der sich auf dem Boden befindet, wird mit 9,77 g zurückgewogen. Der Rückstand am Magneten beträgt 1,76 g (87% des eingesetzten Cu2S).This mixture is charged with 1.506 g of magnetite which has been modified with dodecyltrichlorosilane (primary particle size: about 10 nm) in a 1 l stirred apparatus, with 580 ml of water and 0.1 g of dodecylamine (Alfa Aeser Lot: 10108955). offset and 45 min at 150 rev / min. mixed with a teflon stirring bar. Then a Co-Sm magnet (5 cm in height, 2 cm in length, 2 cm in width) was held on an outer wall of the stirring apparatus and another 30 min. at 150 rpm. touched. Thereafter, the water is removed via a hose, and the apparatus is dried for a further 10 minutes with a hot air blower. The sand, which is on the ground, is weighed back with 9.77 g. The residue on the magnet is 1.76 g (87% of the Cu 2 S used).
Anschließend wird das Becken mit 400 mL Aceton aufgefüllt und für 30 min bei 200 U/min. gerührt. Dann wird das Aceton, in dem sich das Cu2S als feine Partikel befindet, über einen Schlauch abgelassen und getrocknet. Man erhält 1,59 g (79% Cu2S).The basin is then filled with 400 ml of acetone and for 30 min at 200 U / min. touched. Then, the acetone in which the Cu 2 S is a fine particle is drained through a tube and dried. This gives 1.59 g (79% Cu 2 S).
Es wird eine analoge Sand-Cu2S-Mischung wie in Beispiel 1 hergestellt. Anstelle von 1-Octanthiol wird aber Kaliumbutylxanthat verwendet. Die weitere Versuchsführung erfolgt analog Beispiel 1. Die Menge Sand am Boden beträgt 9,64 g, der Rückstand am Magneten 1,61 g (80,0 % Cu2S). Nach dem Trennprozess von Magnetpartikel und Werterz durch Rühren in Aceton werden 1,44 g Cu2S (71%) erhalten.An analogous sand-Cu 2 S mixture is produced as in Example 1. Instead of 1-octanethiol, however, potassium butyl xanthate is used. The further experimental procedure is analogous to Example 1. The amount of sand on the ground is 9.64 g, the residue on Magnet 1.61 g (80.0% Cu 2 S). After separation of magnetic particles and ore by stirring in acetone, 1.44 g of Cu 2 S (71%) are obtained.
Eine Mischung von 1,00 g Cu2S (Fluka, 99%) und 28,00 g Quarz (Euroquarz, Microsil Typ S8) wird mit 0,03 g Octylphosphonsäure (Rhodia; 80%) in 30 mL Wasser für 1 h miteinander vermahlen. Gleichzeitig werden 3,00 g Magnetit (Magnetpigment S0045, BASF, d50 = 2 µm) für 1 h mit einer Suspension aus 0,015 g Octylphosphonsäure und 15 mL Wasser miteinander verrührt. Beide Suspensionen werden in 500 mL Wasser miteinander vermengt, für 1 h verrührt und magnetisch getrennt. Der Quarzgehalt am Magneten ist ≤ 0,5 Gew.-%. Anschließend wird die Anordnung mit 0,1 M NaOH-Lösung geflutet, gelinde geschüttelt und anschließend wird die Flüssigkeit abgeführt. Nach Trocknung werden 60% des Cu2S wieder gefunden.A mixture of 1.00 g of Cu 2 S (Fluka, 99%) and 28.00 g of quartz (Euroquartz, Microsil Type S8) is combined with 0.03 g of octylphosphonic acid (Rhodia, 80%) in 30 mL of water for 1 h ground. At the same time, 3.00 g of magnetite (magnetic pigment S0045, BASF, d 50 = 2 μm) are stirred together for 1 h with a suspension of 0.015 g of octylphosphonic acid and 15 ml of water. Both suspensions are mixed together in 500 ml of water, stirred for 1 h and separated magnetically. The quartz content of the magnet is ≤ 0.5% by weight. Subsequently, the assembly is flooded with 0.1 M NaOH solution, shaken gently and then the liquid is removed. After drying, 60% of the Cu 2 S are found again.
Es werden 0,5 g Pd-gecoatetes ZnO in 10 mL VE-Wasser dispergiert, wobei sich die Lösung grau färbt. Anschließend werden 0.5 g Thiol-modifiziertes Fe3O4 zugeben und kräftig gerührt. Nach 1 h wird ein Co/Sm-Magnet an die Gefäß-Außenwand gehalten, wobei sich die Lösung weitestgehend aufklärt. Die überstehende Lösung wird von den magnetischen Bestandteilen abdekantiert und die flüchtigen Bestandteile im Vakuum entfernt. Es werden 0,1 g g Pd-gecoatetes ZnO wieder gefunden, d.h. der Rest des ZnO wird magnetisch aus dem Gemisch abgetrennt.0.5 g of Pd-coated ZnO are dispersed in 10 ml of demineralized water, whereupon the solution turns gray. Subsequently, 0.5 g of thiol-modified Fe 3 O 4 are added and stirred vigorously. After 1 h, a Co / Sm magnet is held to the outer wall of the vessel, whereby the solution is largely clarified. The supernatant solution is decanted off from the magnetic components and the volatiles are removed in vacuo. There are found again 0.1 gg Pd-coated ZnO, ie the rest of the ZnO is magnetically separated from the mixture.
1,00 g Palladiumpulver werden mit 1,7 Gew.-% Octanthiol in der Kugelmühle vermengt und in 50 mL VE-Wasser gegeben. Anschließend werden 4,00 g hydrophobiertes Fe3O4 zugegeben und das System 3 mal 15 min geschüttelt. Anschließend wird ein Co/Sm-Magnet an die eine Seite des Reaktionsgefäßes gehalten. Das Wasser wird abdekantiert, wobei der Magnet die festen Bestandteile an der Glaswand hält. Aus der überstehenden Lösung werden 0,11 g Palladium isoliert. Der Rest (0,89 g, entsprechend 89%) sind entsprechend magnetisch aus der Lösung abgetrennt und am Magneten gesammelt worden.1.00 g of palladium powder are mixed with 1.7 wt .-% octanethiol in the ball mill and placed in 50 mL of deionized water. Subsequently, 4.00 g of hydrophobized Fe 3 O 4 are added and the system is shaken for 3 times 15 min. Subsequently, a Co / Sm magnet is held to one side of the reaction vessel. The water is decanted off, with the magnet holding the solid components on the glass wall. From the supernatant solution, 0.11 g of palladium are isolated. The remainder (0.89 g, corresponding to 89%) are correspondingly magnetically separated from the solution and collected on the magnet.
Es wird 1 g Cu2S (-325 mesh, Fa. Aldrich) mit 0,065 g Kaliumoctylxanthat in 50 mL Wasser für 30 min. verrührt. Anschließend werden 3 g mit Octylphosphonsäure modifizierter Magnetit (Magnetic Black 345) und weitere 100 mL Wasser zugegeben. Nach 1 h wird das Wasser abgelassen, und es wird für 1 min. Druckluft über den Rückstand geleitet. Dann werden 500 mL Diesel ("Super Diesel-Kraftstoff") zugegeben und das Reaktionsgemisch für 20 min. kräftig gemischt und anschließend noch für 10 min. im Ultraschallbad behandelt. Es wird anschließend die Dieselphase über einen Magneten so abdekantiert, dass die magnetischen Bestandteile zurückgehalten werden. Die Dieselphase mit den unmagnetischen Bestandteilen wird einer Filtration unterworfen, und anschließend wird der feste Rückstand getrocknet. Es werden 0,98 g Feststoff zurückgewonnen, der zu 98% aus Cu2S besteht. Der Anteil an Fe3O4 ist kleiner 0.01 g.It is 1 g of Cu 2 S (-325 mesh, Fa. Aldrich) with 0.065 g of potassium octylxanthate in 50 ml of water for 30 min. stirred. Subsequently, 3 g of magnetitol modified with octylphosphonic acid (Magnetic Black 345) and another 100 mL of water are added. After 1 h, the water is drained off, and it is for 1 min. Compressed air passed over the residue. Then 500 mL of diesel ("super diesel fuel") are added and the reaction mixture for 20 min. vigorously mixed and then for 10 min. treated in an ultrasonic bath. Subsequently, the diesel phase is decanted off via a magnet in such a way that the magnetic components are retained. The diesel phase with the non-magnetic constituents is subjected to filtration, and then the solid residue is dried. There are recovered 0.98 g of solid which consists of 98% Cu 2 S. The content of Fe 3 O 4 is less than 0.01 g.
Dieser Versuch wird 3 Mal entsprechend wiederholt, wobei lediglich der Magnetit aus dem ersten Trennzyklus eingesetzt wird. Die Auswagen an Cu2S entsprechen 0,87 g (Gehalt an Cu2S 88%), 0,99 g (Gehalt an Cu2S 87%), 0,93 g (Gehalt an Cu2S 95%). In keinem Fall wird ein Gehalt an Fe3O4 von mehr als 0,01 g detektiert.This experiment is repeated 3 times, using only the magnetite from the first separation cycle. The weighings of Cu 2 S correspond to 0.87 g (content of Cu 2 S 88%), 0.99 g (content of Cu 2 S 87%), 0.93 g (content of Cu 2 S 95%). In no case is a content of Fe 3 O 4 of more than 0.01 g detected.
Anfangsgehalte des zu trennenden Erzes: Cu 0,54 Gew.-%, Mo 0,029 Gew.-%Initial contents of the ore to be separated: Cu 0.54% by weight, Mo 0.029% by weight
Vor den Trennexperimenten wird das Erzgestein in einer Hammermühle trocken zerkleinert, bis 90 Gew.-% des Erzes in der Fraktion in einer Größe von weniger als 125 µm vorliegen.Before the separation experiments, the ore rock is comminuted dry in a hammer mill until 90% by weight of the ore in the fraction is less than 125 μm in size.
Magnetpigment 345 (BASF SE) wird mit 0,5 Gew.-% Octylphosphonsäure in wässriger Lösung über 30 min bei Raumtemperatur (RT) behandelt. Der Feststoff wird abfiltriert, bis zur Leitfähigkeit von ca. 50 µS mit heißem Wasser (50 °C) gewaschen und bei 80 °C im Vakuum getrocknet.Magnetic Pigment 345 (BASF SE) is treated with 0.5% by weight of octylphosphonic acid in aqueous solution for 30 minutes at room temperature (RT). The solid is filtered off, washed until the conductivity of about 50 .mu.S with hot water (50 ° C) and dried at 80 ° C in a vacuum.
1 L Trenngut wird über eine Reihe von stationären Permanentmagneten geleitet. Der Auslauf wird als Fraktion A1 gesammelt. Der an den Magneten festgehaltene Anteil wird unter Bewegung der Magnete mit 1 L Wasser gewaschen, wobei der ausgetragene Feststoff als Fraktion A2 gesammelt wird. Die an den Magneten weiterhin zurückgehaltene Fraktion R sowie die Fraktionen A1 und A2 werden auf Cu-, Fe- und Mo-Gehalt untersucht.1 L separating material is passed through a series of stationary permanent magnets. The spout is collected as fraction A1. The portion held on the magnet is washed by moving the magnets with 1 L of water, collecting the discharged solid as fraction A2. The fraction R retained on the magnet and fractions A1 and A2 are analyzed for Cu, Fe and Mo content.
100 g Erz werden in einer Schwingmühle (160 mL ZrO2 Kugeln, Ø 1,7-2,7 mm) mit 60 mL Wasser, 0,065 g Kalium-n-Octylxanthat und 0,04 g Shellsol D40 über 5 min konditioniert. Anschließend wird eine Suspension von 3 g hydrophobiertem Magnetit in 3 g Isopropanol in das Mahlgefäß zugegeben und noch einmal 5 min konditioniert. Die Mahlsuspension wird von den Mahlkörpern abgetrennt, auf 1 L verdünnt und der Trennprozedur (s. o.) unterworfen. Die Fraktion R (6,4 g) enthält das gesamte eingesetzte Magnetit sowie 92,4 % des Kupfers und 86,1 % des Molybdäns.100 g of ore are conditioned in a vibrating mill (160 mL ZrO2 spheres, Ø 1.7-2.7 mm) with 60 mL water, 0.065 g potassium n-octyl xanthate and 0.04 g Shellsol D40 for 5 min. Subsequently, a suspension of 3 g of hydrophobized magnetite in 3 g of isopropanol is added to the grinding vessel and conditioned again for 5 min. The grinding suspension is separated from the grinding media, diluted to 1 L and subjected to the separation procedure (see above). The fraction R (6.4 g) contains all the magnetite used and 92.4% of the copper and 86.1% of the molybdenum.
100 g Erz werden in einem Rührbehälter, ausgestattet mit einem Propellerrührer, in 900 mL Wasser suspendiert. Eine Lösung von 0,065 g Kalium-di-n-octyldithiophosphinat in 100 mL Wasser sowie 0,04 mL Shellsol werden unter Rühren zugegeben und das Erz 1 h durch Rühren konditioniert. Anschließend wird eine Suspension von 3 g hydrophobiertem Magnetit in 3 g Isopropanol zugegeben und weitere 30 min gerührt. Anschließend wird sie der oben beschriebenen Trennprozedur unterworfen. Die Fraktion R (8,97 g) enthält das gesamte eingesetzte Magnetit sowie 85,8 % des Kupfers und 82,3 % des Molybdäns.100 g of ore are suspended in 900 ml of water in a stirred tank equipped with a propeller stirrer. A solution of 0.065 g of potassium di-n-octyl dithiophosphinate in 100 mL water and 0.04 mL Shellsol are added with stirring and the ore is conditioned by stirring for 1 h. Subsequently, a suspension of 3 g of hydrophobized magnetite in 3 g of isopropanol is added and stirred for a further 30 min. Subsequently, it is subjected to the separation procedure described above. The fraction R (8.97 g) contains all the magnetite used and 85.8% of the copper and 82.3% of the molybdenum.
100 g Erz werden in einer Schwingmühle (160 mL ZrO2 Kugeln, Ø 1,7-2,7 mm) mit 60 mL Wasser, 0,065 g Kalium-di-n-Octyldithiophosphinat und 0,04 g Shellsol D40 über 5 min konditioniert. Anschließend wird eine Suspension von 3 g hydrophobiertem Magnetit in 3 g Isopropanol in das Mahlgefäß zugegeben und noch einmal 5 min konditioniert. Die Mahlsuspension wird von den Mahlkörpern abgetrennt, auf 1 L verdünnt und der Trennprozedur (s. o.) unterworfen. Die Fraktion R (6,9 g) enthält das gesamte eingesetzte Magnetit sowie 94,7 % des Kupfers und 83,2 % des Molybdäns. Die Fraktion besteht zu 35% aus Chalcopyrit (aus XRD Daten).100 g of ore are conditioned in a vibrating mill (160 mL ZrO 2 spheres, Ø 1.7-2.7 mm) with 60 mL water, 0.065 g potassium di-n-octyl dithiophosphinate and 0.04 g Shellsol D40 for 5 min. Subsequently, a suspension of 3 g of hydrophobized magnetite in 3 g of isopropanol is added to the grinding vessel and conditioned again for 5 min. The millbase is separated from the media, diluted to 1 L and subjected to the separation procedure (see above). The fraction R (6.9 g) contains all the magnetite used and 94.7% of the copper and 83.2% of the molybdenum. The fraction consists of 35% chalcopyrite (from XRD data).
Claims (8)
- 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, which comprises the following steps:(A) contacting of the mixture comprising at least one first material and at least one second material with at least one surface-active substance, optionally in the presence of at least one dispersant, resulting in the surface-active substance becoming attached to the at least one first material,(B) optionally addition of at least one dispersant to the mixture obtained in step (A) to give a dispersion,(C) treatment of the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle so that the at least one first material to which the at least one surface-active substance is bound and the at least one magnetic particle become attached to one another,(D) separation of the addition product from step (C) from the mixture by application of a magnetic field,(E) 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, where the surface-active substance is a substance of the general formula (I)
A-Z (I)
whereA is selected from among linear or branched C3-C30-alkyl, C3-C30-heteroalkyl, optionally substituted C6-C30-aryl, optionally substituted C6-C30-heteroalkyl, C6-C30-aralkyl, andZ is a group by means of which the compound of the general formula (I) binds to the at least one first material. - The process according to claim 1, wherein the first material is a hydrophobic metal compound or coal and the second material is a hydrophilic metal compound.
- The process according to claim 1 or 2, wherein Z is selected from the group consisting of anionic groups (X)n-PO3 2-, -(X)n-PO2S2-, -(X)n-POS2 2-, -(X)n-PS3 2-, -(X)n-PS2 -, -(X)n-POS-, -(X)n-PO2 -, -(X)n-PO3 2--(X)n-CO2 -, -(X)n-CS2 -, -(X)n-COS-, -(X)n-C(S)NHOH, - (X)n-S- where X is selected from the group consisting of 0, S, NH, CH2 and n = 0, 1 or 2, with, if appropriate, cations selected from the group consisting of hydrogen, NR4 + where the radicals R are each, independently of one another, hydrogen or C1-C8-alkyl, an alkali metal or an alkaline earth metal.
- The process according claim 2 or 3, wherein the at least one hydrophobic metal compound is selected from the group consisting of sulfidic ores, oxidic ores and carbonate-comprising ores.
- The process according to any of claims 2 to 4, wherein the at least one hydrophilic metal compound is selected from the group consisting of oxidic and hydroxidic metal compounds.
- The process according to any of claims 1 to 5, wherein the at least one magnetic particle is selected from the group consisting of magnetic metals and mixtures thereof, ferromagnetic alloys of magnetic metals and mixtures thereof, magnetic iron oxides, cubic ferrites of the general formula (II)
M2+ xFe2+ 1-xFe3+ 2O4 (II)
whereM is selected from among Co, Ni, Mn, Zn and mixtures thereof andx is ≤ 1,hexagonal ferrites and mixtures thereof. - The process according to any of claims 1 to 6, wherein the dispersion medium is water.
- The process according to any of claims 1 to 7, wherein the mixture comprising at least one first material and at least one second material is milled to particles having a size of from 100 nm to 100 µm before or during step (A).
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| EP08803482.2A EP2190584B1 (en) | 2007-09-03 | 2008-09-01 | Processing rich ores using magnetic particles |
| PL08803482T PL2190584T3 (en) | 2007-09-03 | 2008-09-01 | Processing rich ores using magnetic particles |
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| EP08803482.2A EP2190584B1 (en) | 2007-09-03 | 2008-09-01 | Processing rich ores using magnetic particles |
| PCT/EP2008/061503 WO2009030669A2 (en) | 2007-09-03 | 2008-09-01 | Processing rich ores using magnetic particles |
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| US (1) | US8318025B2 (en) |
| EP (1) | EP2190584B1 (en) |
| JP (1) | JP2010537818A (en) |
| CN (1) | CN101815581B (en) |
| AR (1) | AR068164A1 (en) |
| AU (1) | AU2008294826B2 (en) |
| BR (1) | BRPI0816189A2 (en) |
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| CN105873653B (en) | 2014-01-08 | 2018-08-10 | 巴斯夫欧洲公司 | The method for reducing the volume flow comprising magnetic agglomerate by elutriation |
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| CN111500879B (en) * | 2020-05-28 | 2021-07-27 | 清华大学 | Method for extracting rare earth elements based on magnetic Janus particles |
| CN112718231B (en) * | 2020-12-15 | 2023-04-21 | 中国地质科学院郑州矿产综合利用研究所 | Mineral separation method of molybdenite of magnesium-rich mineral |
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| US8033398B2 (en) | 2005-07-06 | 2011-10-11 | Cytec Technology Corp. | Process and magnetic reagent for the removal of impurities from minerals |
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| EA201000407A1 (en) | 2010-10-29 |
| ZA201002330B (en) | 2011-06-29 |
| PE20090869A1 (en) | 2009-08-08 |
| BRPI0816189A2 (en) | 2015-04-14 |
| PT2190584E (en) | 2013-08-28 |
| WO2009030669A3 (en) | 2009-04-23 |
| CN101815581B (en) | 2015-01-21 |
| US20100300941A1 (en) | 2010-12-02 |
| AR068164A1 (en) | 2009-11-04 |
| CA2698216C (en) | 2017-01-10 |
| AU2008294826A1 (en) | 2009-03-12 |
| ES2426614T3 (en) | 2013-10-24 |
| AU2008294826B2 (en) | 2013-02-07 |
| WO2009030669A2 (en) | 2009-03-12 |
| CA2698216A1 (en) | 2009-03-12 |
| MX2010002462A (en) | 2010-03-26 |
| EP2190584A2 (en) | 2010-06-02 |
| PL2190584T3 (en) | 2013-11-29 |
| CN101815581A (en) | 2010-08-25 |
| UA97543C2 (en) | 2012-02-27 |
| EA017511B1 (en) | 2013-01-30 |
| JP2010537818A (en) | 2010-12-09 |
| CL2008002609A1 (en) | 2009-10-23 |
| US8318025B2 (en) | 2012-11-27 |
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