EP2171106B1 - Method for ore enrichment by means of hydrophobic, solid surfaces - Google Patents
Method for ore enrichment by means of hydrophobic, solid surfaces Download PDFInfo
- Publication number
- EP2171106B1 EP2171106B1 EP08785971A EP08785971A EP2171106B1 EP 2171106 B1 EP2171106 B1 EP 2171106B1 EP 08785971 A EP08785971 A EP 08785971A EP 08785971 A EP08785971 A EP 08785971A EP 2171106 B1 EP2171106 B1 EP 2171106B1
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- EP
- European Patent Office
- Prior art keywords
- hydrophobic
- solid
- process according
- dispersion
- mixture
- 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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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000007787 solid Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 230000005661 hydrophobic surface Effects 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims description 69
- 230000008569 process Effects 0.000 claims description 31
- 150000002736 metal compounds Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- 229910052948 bornite Inorganic materials 0.000 claims description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052947 chalcocite Inorganic materials 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims 2
- 239000003245 coal Substances 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000006249 magnetic particle Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 aeration indicated Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005021 gait Effects 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 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
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/08—Subsequent treatment of concentrated product
- B03D1/10—Removing adhering liquid from separated materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0008—Preliminary treatment without modification of the copper constituent by wet processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C2201/00—Details of magnetic or electrostatic separation
- B03C2201/20—Magnetic separation whereby the particles to be separated are in solid form
Definitions
- the present invention relates to a process for separating at least one hydrophobic substance from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, and the use of a solid, hydrophobic surface for separating at least one hydrophobic substance from the above-mentioned mixture.
- the invention comprises the separation of hydrophobic metal compounds, for example metal sulfides from a mixture of these hydrophobic metal compounds and hydrophilic metal oxides for ore enrichment by means of a hydrophobic surface.
- Flotation is a separation process in which water-dispersed or suspended substances are transported by adhering gas bubbles to the water surface where they are removed with a clearing device.
- air is introduced into the flotation bath and finely distributed.
- the hydrophobic particles, such as sulfidic ores, are difficult to wet with water and therefore adhere to the air bubbles. So these particles are carried by the air bubbles to the surface of the pool and can be skimmed off with the foam.
- a disadvantage of this process is that the air bubbles often lose their ballast on the way up. So that a sufficient yield can be obtained at all, chemical additives, for example xanthates, are added, which are intended to subsequently hydrophobicize the ore particles more strongly.
- the constant import in air is also associated with a high risk potential.
- the above-mentioned disadvantage could be circumvented in the so-called magnetic flotation.
- the sulfidic ore constituents are specifically coupled or coupled to magnetic particles in this method.
- a magnetic field is applied and the magnetic constituents containing the desired ore constituents are thus separated from the non-magnetic constituents.
- US 4,657,666 a method for the enrichment of ores, in which the hydrophobic magnetic particle adheres specifically to the hydrophobic, sulfidic ore.
- the magnetic particle is selected from magnetite or other magnetic iron oxides previously hydrophobized by attachment to silanes.
- the sulphidic ore is rendered hydrophobic with a mixture of flotation agents / collector agents in the presence of the oxidic gangue.
- the magnetic particle is separated from the ore by treatment with 50 vol .-% H 2 O 2 -Lösu.
- US 4,906,382 discloses a process for the enrichment of sulfidic ores in which they are stirred with magnetic pigments modified with bifunctional molecules.
- One of the two functional groups adheres to the magnetic core.
- the magnetic particles can be reversibly agglomerated by varying the pH.
- the magnetic particles can be used to concentrate sulfide ores.
- DE 195 14 515 discloses a method to concentrate recyclables with magnetite or hematite particles.
- the magnetite or hematite particles are modified with carboxylic acids or functionalized alkanols.
- SU-A-544464 discloses a method for separating magnetic and non-magnetic portions by passing this mixture past a rotating induction roller from which the magnetic portions are attracted.
- a disadvantage of the methods for ore enrichment described in the prior art is that high magnetic fields are required to efficiently separate the magnetized particles from the original mixture. For this complex, expensive devices are necessary. Furthermore, it must be ensured that the magnetic particle coupled to the ore remains stably connected during the flotation process and can be effectively separated again after the separation.
- the method according to the invention serves to separate at least one hydrophobic substance from a mixture comprising this at least one hydrophobic substance and at least one hydrophilic substance.
- hydrophobic means that the corresponding surface can be hydrophobic on its own or can subsequently be rendered hydrophobic. It is also possible that a per se hydrophobic surface is additionally hydrophobicized.
- the at least one hydrophobic substance is at least one hydrophobic metal compound or carbon
- the at least one hydrophilic substance is preferably at least one hydrophilic metal compound.
- the process is used in particular for separating sulfidic ores from a mixture comprising these sulfidic ores and at least one hydrophilic metal compound selected from the group consisting of oxidic metal compounds.
- the at least one hydrophobic metal compound is preferably selected from the group consisting of sulfidic ores.
- the at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic metal compounds.
- sulfidic ores which can be used according to the invention are selected, for example, from the group of copper ores consisting of chalcopyrite (copper pyrites) CuFeS 2 , bornite Co 5 FeS 4 , chalcocite (copper gloss) 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 , preferably hexagonal modifications, feldspars, for example albite Ma (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH, F) 2 AlSi 3 O 10 ], and mixtures thereof.
- untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
- an ore mixture to be used according to the invention to be separated before the process according to the invention is ground to a particle size ⁇ 100 ⁇ m, more preferably ⁇ 60 ⁇ m.
- Preferably usable ore mixtures have a content of sulfidic minerals of at least 0.4 wt .-%, particularly preferably at least 10 wt .-%, on.
- sulphidic minerals which are present in the ore mixtures which can be used according to the invention are those mentioned above.
- sulfides of metals other than copper may also be present in the ore mixtures, for example sulfides of lead, zinc, molybdenum, PbS, ZnS and / 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 carbonates, may be present in the ore mixtures to be treated according to the invention.
- 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 process of the invention comprises preparing a slurry or dispersion of the mixture to be treated in at least one suitable solvent.
- Suitable dispersants are all dispersants suitable in which the mixtures to be treated are not completely soluble.
- Suitable dispersants for the preparation of the slurry or dispersion according to step (A) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds and mixtures thereof.
- the dispersant in step (A) is water.
- the amount of dispersant can be chosen according to the invention so that a slurry or dispersion is obtained which is readily stirrable and / or conveyable.
- the amount of mixture to be treated based on the total slurry or dispersion, is up to 100% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight.
- the slurry or dispersion can be prepared according to the invention by all methods known to those skilled in the art.
- the mixture to be treated and the corresponding amount of dispersant or dispersant mixture are combined in a suitable reactor, for example a glass reactor, and devices known to those skilled in the art stirred, for example in a glass pan with a mechanically stirred paddle stirrer.
- At least one adhesion-improving substance may be added in addition to the mixture to be treated and the dispersing agent or dispersing agent mixture.
- adhesion-enhancing substances are long and short-chain amines, ammonia, long-chain alkanes and long-chain, unbranched alcohols.
- the slurry or dispersion dodecylamine is added, the amount, based on the dry ore and magnetic particle amount, preferably 0.1 to 0.5 wt .-%, particularly preferably 0.3 wt .-% is.
- the optionally added adhesion-improving substance is generally added in an amount which is sufficient to ensure the adhesion-improving effect of this substance.
- the at least one adhesion-improving substance is added to 0.01 to 10 wt .-%, particularly preferably 0.05 to 0.5 wt .-%, each based on the total slurry or dispersion.
- the at least one hydrophobic substance present in the mixture is hydrophobicized with at least one substance before step (B) of the process according to the invention.
- the hydrophobing of the at least one hydrophobic substance can be carried out before step (A), i. before preparing the slurry or dispersion of the mixture to be treated.
- step (A) i. before preparing the slurry or dispersion of the mixture to be treated.
- the hydrophobic substance it is also possible for the hydrophobic substance to be separated to be hydrophobized after preparing the slurry or dispersion according to step (A).
- the mixture to be treated is rendered hydrophobic before step (A) with a suitable substance.
- hydrophobizing substance all substances which are capable of further hydrophobicizing the hydrophobic metal compound to be separated off at the surface thereof.
- the hydrophobizing reagent is generally composed of a radical and an anchor group, wherein the anchor group preferably has at least 1, more preferably 3 reactive groups, which interacts with the hydrophobic substance to be separated, preferably the hydrophobic metal compound to be separated.
- Suitable anchor groups are phosphonic acid groups or thiol groups.
- hydrophobicizing compounds are added individually or in admixture with each other in an amount of 0.01 to 50 wt .-%, particularly preferably 0.1 to 50 wt .-%, based on the mixture to be treated.
- These hydrophobicizing substances can be applied to the hydrophobic substance to be separated off, preferably the at least one metal compound to be separated off, by all methods known to the person skilled in the art.
- the mixture to be treated is ground and / or stirred with the appropriate amount of hydrophobing substance, for example in a planetary ball mill. Suitable devices are known in the art.
- Step (B) of the process according to the invention comprises contacting the slurry or dispersion from step (A) with at least one solid, hydrophobic surface for attachment of the at least one hydrophobic substance to be separated, preferably the at least one metal compound to be separated to the solid, hydrophobic surface
- Solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
- the binding of the hydrophobic substance to the solid, hydrophobic surface is effected by hydrophobic interactions.
- the solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill, for example solid or mobile, or the inner wall of a reactor. More preferably, the solid, hydrophobic surface is the inner wall of a reactor or the solid or mobile hydrophobic surface of a treadmill having fibrous micro 3D structures on the surface.
- a solid, hydrophobic surface is used, which is hydrophobic per se by the material which forms the solid, hydrophobic surface.
- hydrophobic surfaces which are not hydrophobic by themselves are applied by applying at least one hydrophobic layer.
- a solid surface made of metal, plastic, glass, wood or metal alloys is rendered hydrophobic by applying a hydrophobic compound, which is optionally surface-coated with suitable substances.
- this surface consisting of hydrophobic compounds is inherently hydrophobic enough to be used in the process according to the invention.
- the application of the hydrophobic layer can be done, for example, by vapor deposition.
- all the hydrophobic materials known to those skilled in the art, which are suitable for forming a corresponding hydrophobic layer can be used to form this hydrophobic layer.
- a hydrophobic layer is a layer that has no polar groups and therefore has a water-repellent character.
- Examples of suitable compounds are bifunctional compounds which adhere to one functional group on the solid surface by a covalent or coordinative bond and to the other hydrophobic functional group on the ore by a covalent or coordinative bond.
- groups with which the binding to the inorganic compound takes place are the carboxyl group -COOH, the phosphonic acid group -PO 3 H 2 , the trihalosilyl group -SiHal 3 with Hal equal to one another independently of one another F, Cl, Br, I, trialkoxysilyl group -Si ( OR 5 ) 3 with R 5 are each, independently of one another, C 1 -C 12 -alkyl and / or C 2 -C 12 -alkenyl.
- the solid, hydrophobic surface is the surface of a continuous treadmill which is agitated by the slurry or dispersion containing the mixture to be treated.
- the surface of the treadmill can be increased in a preferred embodiment by methods known in the art, for example by applying a three-dimensional structure on the treadmill.
- An example of such a three-dimensional structure are fibers attached to the surface of the treadmill.
- the treadmill can be made of any materials known and suitable to those skilled in the art, for example polymers such as polyethylene terephthalate, metallic materials such as aluminum, multi-component materials such as aluminum alloys.
- the fibers may also be of any suitable and suitable materials known to those skilled in the art.
- Step (C) of the method according to the invention comprises removing the at least one solid, hydrophobic surface to which the at least one hydrophobic substance, preferably the at least one hydrophobic metal compound is attached from step (B), from the slurry or dispersion in which the at least one a hydrophilic substance is included.
- the hydrophobic metal to be separated preferably the hydrophobic metal compound to be separated, is at least partially attached to the hydrophobic solid surface.
- the hydrophilic substance present in the mixture to be treated remains in the slurry or dispersion because it does not bind to the hydrophobic surface.
- Removal of the loaded, hydrophobic, solid surface may be accomplished by any method known to those skilled in the art. For example, a plate having the hydrophobic solid surface may be lifted out of a bath containing the slurry or dispersion. Furthermore, it is possible according to the invention that the hydrophobic, solid surface is mounted on a treadmill which moves through the slurry or dispersion. When the hydrophobic solid surface is attached to the inside of a pipe or reactor, in a preferred embodiment, the slurry or dispersion is passed through the reactor or through the pipe. Removal of the solid, hydrophobic surface thus occurs by passing the slurry or dispersion past this surface. It is also possible according to the invention that, when the hydrophobic solid surface is the inner wall of a reactor, the removal of this hydrophobic solid surface occurs by draining the slurry or dispersion to be treated from the reactor.
- Step (D) comprises separating the at least one hydrophobic material, preferably the at least one hydrophobic metal compound, from the solid, hydrophobic surface.
- step (C) the hydrophobic, solid surface with the hydrophobic substance to be separated from the reaction mixture to be treated, at least partially laden.
- This separation can be carried out by any of the methods known to those skilled in the art, which are suitable for separating the hydrophobic substance from said surface without impairing either the hydrophobic substance and / or the surface.
- the separation in step (D) of the process according to the invention is carried out by treating the solid, hydrophobic surface with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, surface-active compounds and mixtures thereof.
- organic solvents examples include 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 and mixtures thereof.
- Examples of basic compounds which can be used according to the invention are aqueous solutions of basic compounds, for example aqueous solutions of alkali metal and / or alkaline earth metal hydroxides, for example KOH, NaOH, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 7 3 N, where R 7 is selected from Group consisting of C 1 -C 8 -alkyl, optionally substituted with further functional groups.
- 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.
- H 2 O 2 can be used as the oxidizing agent, for example as a 30% strength by weight aqueous solution (perhydrol).
- Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
- the hydrophobic solid surface, to which the hydrophobic material to be separated is attached is washed with an organic solvent, more preferably with acetone, to form the hydrophobic substance separated from the hydrophobic, solid surface.
- an organic solvent more preferably with acetone
- This process can also be supported mechanically.
- the organic solvent or other separation reagent mentioned above is applied with pressure on the hydrophobic surface loaded with the hydrophobic ore.
- ultrasound may be used to assist the separation process, if appropriate in addition.
- the organic solvent is used in an amount sufficient to dissolve as much as possible of the entire adhering to the hydrophobic surface amount of the hydrophobic metal compounds thereof.
- 20 to 100 ml of the organic solvent is used per gram of hydrophobic and hydrophilic fabric to be purified. It is preferred according to the invention that the hydrophobic solid surface is treated with several smaller portions, for example two portions of the organic solvent, which together give said total amount.
- the hydrophobic substance to be separated is present as a slurry or dispersion in said organic solvent.
- the hydrophobic material can be separated from the organic solvent by any method known to those skilled in the art, for example, decanting, filtering, distilling off the organic solvent, or settling the solids at the bottom of the container, after which the ore can be skimmed off at the bottom.
- the hydrophobic substance to be separated off preferably the hydrophobic metal compound to be separated, is separated from the organic solvent by filtration.
- the hydrophobic 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.
- the hydrophobic solid surface from which the hydrophobic substance has been separated in step (D) is dried.
- This drying may be carried out by any method known to those skilled in the art, for example by treatment in an oven at a temperature of for example 30 to 100 ° C.
- the hydrophobic, solid surface which has optionally been dried, is returned to the process according to the invention, ie used again in step (B) of the process according to the invention.
- the method according to the invention can be carried out so that the treadmill is continuously passed through the slurry or dispersion to be treated, treated with a solvent to separate the hydrophobic particles, dried, and returned to the bath to be treated.
- the hydrophobic solid surface It is according to the invention required that this is completely freed from the separation reagent used.
- the present invention also relates to the use of a solid hydrophobic surface for separating at least one hydrophobic substance, preferably a hydrophobic metal compound or carbon, from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, preferably at least one hydrophilic metal compound hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
- the recovered amount of Cu 2 S corresponds to a relative amount of 76%.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Abtrennen wenigstens eines hydrophoben Stoffes aus einer Mischung umfassend diesen wenigstens einen hydrophoben Stoff und wenigstens einen hydrophilen Stoff, sowie die Verwendung einer festen, hydrophoben Oberfläche zum Abtrennen wenigstens eines hydrophoben Stoffes aus der oben genannten Mischung.The present invention relates to a process for separating at least one hydrophobic substance from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, and the use of a solid, hydrophobic surface for separating at least one hydrophobic substance from the above-mentioned mixture.
Insbesondere umfasst die Erfindung die Abtrennung von hydrophoben Metallverbindungen, beispielsweise Metallsulfiden aus einer Mischung von diesen hydrophoben Metallverbindungen und hydrophilen Metalloxiden zur Erzanreicherung mittels einer hydrophoben Oberfläche.In particular, the invention comprises the separation of hydrophobic metal compounds, for example metal sulfides from a mixture of these hydrophobic metal compounds and hydrophilic metal oxides for ore enrichment by means of a hydrophobic surface.
Zurzeit werden 90% aller Blei-, Zink- und Kupfererze durch die so genannte Flotation aufkonzentriert. Die Flotation ist ein Trennverfahren, bei dem in Wasser dispergierte oder suspendierte Stoffe durch anhaftende Gasblasen an die Wasseroberfläche transportiert und dort mit einer Räumeinrichtung entfernt werden. Hierbei wird in das Flotationsbad Luft eingetragen und fein verteilt. Die hydrophoben Partikel, beispielsweise sulfidische Erze, lassen sich schlecht mit Wasser benetzen und haften daher an den Luftblasen. So werden diese Partikel von den Luftbläschen an die Oberfläche des Schwimmbeckens getragen und können mit dem Schaum abgeschöpft werden. Ein Nachteil bei diesem Prozess ist, dass die Luftbläschen auf dem Weg nach oben öfters ihren Ballast verlieren. Damit überhaupt eine ausreichende Ausbeute erhalten werden kann, werden chemische Zusätze, beispielsweise Xanthate, zugegeben, die die Erzpartikel nachträglich stärker hydrophobisieren sollen. Die konstante Einfuhr an Luft ist zudem mit einem hohen Gefahrenpotential verbunden.Currently, 90% of all lead, zinc and copper ores are concentrated by so-called flotation. Flotation is a separation process in which water-dispersed or suspended substances are transported by adhering gas bubbles to the water surface where they are removed with a clearing device. Here, air is introduced into the flotation bath and finely distributed. The hydrophobic particles, such as sulfidic ores, are difficult to wet with water and therefore adhere to the air bubbles. So these particles are carried by the air bubbles to the surface of the pool and can be skimmed off with the foam. A disadvantage of this process is that the air bubbles often lose their ballast on the way up. So that a sufficient yield can be obtained at all, chemical additives, for example xanthates, are added, which are intended to subsequently hydrophobicize the ore particles more strongly. The constant import in air is also associated with a high risk potential.
Der oben genannte Nachteil könnte bei der so genannten magnetischen Flotation umgangen werden. Prinzipiell werden bei dieser Methode die sulfidischen Erzbestandteile gezielt an magnetische Teilchen gekoppelt bzw. an diese gekoppelt. In einem zweiten Schritt wird ein Magnetfeld angelegt und die magnetischen Bestandteile enthaltend die gewünschten Erzbestandteile, so von den unmagnetischen Bestandteilen abgetrennt.The above-mentioned disadvantage could be circumvented in the so-called magnetic flotation. In principle, the sulfidic ore constituents are specifically coupled or coupled to magnetic particles in this method. In a second step, a magnetic field is applied and the magnetic constituents containing the desired ore constituents are thus separated from the non-magnetic constituents.
Beispielsweise beschreibt
Nachteilig an den im Stand der Technik beschriebenen Verfahren zur Erzanreicherung ist, dass hohe Magnetfelder benötigt werden, um die magnetisierten Partikel effizient aus der ursprünglichen Mischung abzutrennen. Dazu sind aufwendige, kostenintensive Vorrichtungen notwendig. Des Weiteren muss gewährleistet sein, dass das an das Werterz angekoppelte magnetische Teilchen während des Flotationsvorganges stabil angebunden bleibt und sich nach der Trennung wieder effektiv abtrennen lässt.A disadvantage of the methods for ore enrichment described in the prior art is that high magnetic fields are required to efficiently separate the magnetized particles from the original mixture. For this complex, expensive devices are necessary. Furthermore, it must be ensured that the magnetic particle coupled to the ore remains stably connected during the flotation process and can be effectively separated again after the separation.
Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren bereitzustellen, um hydrophobe Stoffe effizient und mit hoher Reinheit aus einer Mischung umfassend diese hydrophoben Stoffe und hydrophile Stoffe, abzutrennen. Des Weiteren ist es eine Aufgabe der vorliegenden Erfindung, ein solches Verfahren bereitzustellen, welches das Ankoppeln von magnetisierbaren Teilchen an die abzutrennenden hydrophoben Bestandteile und die Verwendung eines Luftstromes vermeidet.It is therefore an object of the present invention to provide a process for separating hydrophobic substances efficiently and with high purity from a mixture comprising these hydrophobic substances and hydrophilic substances. Furthermore, it is an object of the present invention to provide such a method which avoids the coupling of magnetizable particles to the hydrophobic constituents to be separated and the use of an air stream.
Diese Aufgaben werden gelöst durch ein Verfahren zum Abtrennen wenigstens eines hydrophoben Stoffes aus einer Mischung umfassend diesen wenigstens einen hydrophobe Stoff und wenigstens einen hydrophilen Stoff, umfassend die Schritte:
- (A)
- Herstellen einer Aufschlämmung oder Dispersion der zu behandelnden Mischung in wenigstens einem geeigneten Dispersionsmittel,
- (B)
- Inkontaktbringen der Aufschlämmung oder Dispersion aus Schritt (A) mit wenigs- tens einer festen, hydrophoben Oberfläche zur Anbindung des abzutrennenden wenigsten einen hydrophoben Stoffes an diese, wobei die feste hydrophobe Oberfläche die Innenwand eines Rohres, die Oberfläche einer Platte, die Oberflä- che eines Laufbandes oder die Innenwand eines Reaktors ist,
- (C)
- Entfernen der wenigstens einen festen, hydrophoben Oberfläche, an der der we- nigstens eine hydrophobe Stoff angebunden ist aus Schritt (B), aus der Auf- schlämmung oder Dispersion, in der der wenigstens eine hydrophile Stoff enthal- ten ist und
- (D)
- Abtrennen des wenigstens einen hydrophoben Stoffes von der festen, hydropho- ben Oberfläche.
- (A)
- Preparing a slurry or dispersion of the mixture to be treated in at least one suitable dispersing agent,
- (B)
- Contacting the slurry or dispersion of step (A) with at least one solid, hydrophobic surface for attachment of the at least one hydrophobic substance to be separated thereon, the solid hydrophobic material being attached to the slurry Surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor,
- (C)
- Removing the at least one solid, hydrophobic surface to which the at least one hydrophobic substance is attached from step (B), from the slurry or dispersion in which the at least one hydrophilic substance is contained, and
- (D)
- Separating the at least one hydrophobic substance from the solid, hydrophobic surface.
Das erfindungsgemäße Verfahren dient zum Abtrennen wenigstens eines hydrophoben Stoffes aus einer Mischung umfassend diesen wenigstens einen hydrophoben Stoff und wenigstens einen hydrophilen Stoff.The method according to the invention serves to separate at least one hydrophobic substance from a mixture comprising this at least one hydrophobic substance and at least one hydrophilic substance.
Im Rahmen der vorliegenden Erfindung bedeutet "hydrophob", dass die entsprechende Oberfläche von sich aus hydrophob sein kann, oder nachträglich hydrophobiert sein kann. Es ist auch möglich, dass eine an sich hydrophobe Oberfläche zusätzlich hydrophobiert wird.In the context of the present invention, "hydrophobic" means that the corresponding surface can be hydrophobic on its own or can subsequently be rendered hydrophobic. It is also possible that a per se hydrophobic surface is additionally hydrophobicized.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der wenigstens eine hydrophobe Stoff wenigstens eine hydrophobe Metallverbindung oder Kohle, und der wenigstens eine hydrophile Stoff ist bevorzugt wenigstens eine hydrophile Metallverbindung.In a preferred embodiment of the method according to the invention, the at least one hydrophobic substance is at least one hydrophobic metal compound or carbon, and the at least one hydrophilic substance is preferably at least one hydrophilic metal compound.
Erfindungsgemäß dient das Verfahren insbesondere zur Abtrennung von sulfidischen Erzen aus einer Mischung umfassend diese sulfidischen Erze und wenigstens eine hydrophile Metallverbindung ausgewählt aus der Gruppe bestehend aus oxidischen Metallverbindungen.According to the invention, the process is used in particular for separating sulfidic ores from a mixture comprising these sulfidic ores and at least one hydrophilic metal compound selected from the group consisting of oxidic metal compounds.
Somit ist die wenigstens eine hydrophobe Metallverbindung bevorzugt ausgewählt aus der Gruppe bestehend aus sulfidischen Erzen. Die wenigstens eine hydrophile Metallverbindung ist bevorzugt ausgewählt aus der Gruppe bestehend aus oxidischen Metallverbindungen.Thus, the at least one hydrophobic metal compound is preferably selected from the group consisting of sulfidic ores. The at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic metal compounds.
Beispiele für erfindungsgemäß einsetzbare sulfidische Erze sind z.B. ausgewählt aus der Gruppe der Kupfererze bestehend aus Chalkopyrit (Kupferkies) CuFeS2, Bornit Co5FeS4, 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 chalcopyrite (copper pyrites) CuFeS 2 , bornite Co 5 FeS 4 , chalcocite (copper gloss) Cu 2 S and mixtures thereof.
Geeignete erfindungsgemäß einsetzbare oxidische Metallverbindungen sind bevorzugt ausgewählt aus der Gruppe bestehend aus Siliziumdioxid SiO2, bevorzugt hexagonale Modifikationen, Feldspate, beispielsweise Albit Ma(Si3Al)O8, Glimmer, beispielsweise Muskovit KAl2[(OH,F)2AlSi3O10], 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 , preferably hexagonal modifications, feldspars, for example albite Ma (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH, F) 2 AlSi 3 O 10 ], and mixtures thereof.
In das erfindungsgemäße 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 wird eine erfindungsgemäß einsetzbare zu trennende Erzmischung vor dem erfindungsgemäßen Verfahren auf eine Teilchengröße ≤ 100 µm, besonders bevorzugt ≤ 60 µm vermahlen. Bevorzugt einsetzbare Erzmischungen weisen einen Gehalt an sulfidischen Mineralien von mindestens 0,4 Gew.-%, besonders bevorzugt mindestens 10 Gew.-%, auf.In a preferred embodiment, an ore mixture to be used according to the invention to be separated before the process according to the invention is ground to a particle size ≦ 100 μm, more preferably ≦ 60 μm. Preferably usable ore mixtures have a content of sulfidic minerals of at least 0.4 wt .-%, particularly preferably at least 10 wt .-%, on.
Beispiele für sulfidische Mineralien, die in den erfindungsgemäß einsetzbaren Erzmischungen vorliegen, sind die oben genannten. Zusätzlich können in den Erzmischungen auch Sulfide anderer Metalle als Kupfer vorliegen, beispielsweise Sulfide von Blei, Zink, Molybdän, PbS, ZnS und/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 Carbonate, vorliegen.Examples of sulphidic minerals which are present in the ore mixtures which can be used according to the invention are those mentioned above. In addition, sulfides of metals other than copper may also be present in the ore mixtures, for example sulfides of lead, zinc, molybdenum, PbS, ZnS and / or MoS 2 . Furthermore, oxidic compounds of metals and semimetals, for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or carbonates, may be present in the ore mixtures to be treated according to the invention.
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 Herstellen einer Aufschlämmung oder Dispersion der zu behandelnden Mischung in wenigstens einem geeigneten Lösungsmittel.Step (A) of the process of the invention comprises preparing a slurry or dispersion of the mixture to be treated in at least one suitable solvent.
Als geeignete Dispersionsmittel sind alle Dispersionsmittel geeignet, in denen die zu behandelnden Mischungen nicht vollständig löslich sind. Geeignete Dispersionsmittel zur Herstellung der Aufschlämmung oder Dispersion gemäß Schritt (A) des erfindungsgemäßen Verfahrens sind ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Verbindungen und Mischungen davon.Suitable dispersants are all dispersants suitable in which the mixtures to be treated are not completely soluble. Suitable dispersants for the preparation of the slurry or dispersion according to step (A) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds 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.
Im Allgemeinen kann die Menge an Dispersionsmittel 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 100 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%, ganz besonders bevorzugt 1 bis 5 Gew.-%.In general, the amount of dispersant can be chosen according to the invention so that a slurry or dispersion is obtained which is readily stirrable and / or conveyable. In a preferred embodiment, the amount of mixture to be treated, based on the total slurry or dispersion, is up to 100% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight.
Die Aufschlämmung oder Dispersion kann erfindungsgemäß nach allen dem Fachmann bekannten Verfahren hergestellt werden. In einer bevorzugten Ausführungsform werden die zu behandelnde Mischung 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 gerührten Flügelrührer.The slurry or dispersion can be prepared according to the invention by all methods known to those skilled in the art. In a preferred embodiment, the mixture to be treated and the corresponding amount of dispersant or dispersant mixture are combined in a suitable reactor, for example a glass reactor, and devices known to those skilled in the art stirred, for example in a glass pan with a mechanically stirred paddle stirrer.
In einer weiteren bevorzugten Ausführungsform des vorliegenden Verfahrens kann zusätzlich zu der zu behandelnden Mischung und dem Dispersionsmittel bzw. Dispersionsmittelgemisch wenigstens eine haftverbessernde Substanz zugesetzt werden.In a further preferred embodiment of the present process, at least one adhesion-improving substance may be added in addition to the mixture to be treated and the dispersing agent or dispersing agent mixture.
Beispiele für geeignete haftverbesserende Substanzen sind lang- und kurzkettige Amine, Ammoniak, langkettige Alkane und langkettige, unverzweigte Alkohole. In einer besonders bevorzugten Ausführungsform wird der Aufschlämmung oder Dispersion Dodecylamin zugegeben, wobei die Menge, bezogen auf die trockene Erz- und Magnetteilchenmenge, bevorzugt 0,1 bis 0,5 Gew.-%, besonders bevorzugt 0,3 Gew.-% beträgt.Examples of suitable adhesion-enhancing substances are long and short-chain amines, ammonia, long-chain alkanes and long-chain, unbranched alcohols. In a particularly preferred embodiment, the slurry or dispersion dodecylamine is added, the amount, based on the dry ore and magnetic particle amount, preferably 0.1 to 0.5 wt .-%, particularly preferably 0.3 wt .-% is.
Die gegebenenfalls zuzusetzende haftverbessernde Substanz wird im Allgemeinen in einer Menge zugesetzt, die ausreicht, um die haftverbessernde Wirkung dieser Substanz zu gewährleisten. In einer bevorzugten Ausführungsform wird die wenigstens eine haftverbessernde Substanz zu 0,01 bis 10 Gew.-%, besonders bevorzugt 0,05 bis 0,5 Gew.-%, jeweils bezogen auf die gesamte Aufschlämmung oder die Dispersion, hinzugefügt.The optionally added adhesion-improving substance is generally added in an amount which is sufficient to ensure the adhesion-improving effect of this substance. In a preferred embodiment, the at least one adhesion-improving substance is added to 0.01 to 10 wt .-%, particularly preferably 0.05 to 0.5 wt .-%, each based on the total slurry or dispersion.
In einer besonders bevorzugten Ausführungsform wird der in der Mischung vorliegende, wenigstens eine hydrophobe Stoff vor Schritt (B) des erfindungsgemäßen Verfahrens mit wenigstens einer Substanz hydrophobiert.In a particularly preferred embodiment, the at least one hydrophobic substance present in the mixture is hydrophobicized with at least one substance before step (B) of the process according to the invention.
Das Hydrophobieren des wenigstens einen hydrophoben Stoffes, bevorzugt der wenigstens einen hydrophoben Metallverbindung, kann vor Schritt (A), d.h. vor Herstellung der Aufschlämmung oder Dispersion der zu behandelnden Mischung, erfolgen. Erfindungsgemäß ist es jedoch auch möglich, dass der abzutrennende hydrophobe Stoff nach Herstellen der Aufschlämmung oder Dispersion gemäß Schritt (A) hydrophobiert wird. In einer bevorzugten Ausführungsform wird die zu behandelnde Mischung vor Schritt (A) mit einer geeigneten Substanz hydrophobiert.The hydrophobing of the at least one hydrophobic substance, preferably the at least one hydrophobic metal compound, can be carried out before step (A), i. before preparing the slurry or dispersion of the mixture to be treated. According to the invention, however, it is also possible for the hydrophobic substance to be separated to be hydrophobized after preparing the slurry or dispersion according to step (A). In a preferred embodiment, the mixture to be treated is rendered hydrophobic before step (A) with a suitable substance.
Erfindungsgemäß können als hydrophobierende Substanz alle Substanzen eingesetzt werden, die dazu befähigt sind, die abzutrennende hydrophobe Metallverbindung an deren Oberfläche noch weiter zu hydrophobieren. Das Hydrophobierungsreagenz ist im Allgemeinen aus einem Rest und einer Ankergruppe aufgebaut, wobei die Ankergruppe bevorzugt mindestens 1, besonders bevorzugt 3 reaktive Gruppen aufweist, die mit dem abzutrennenden hydrophoben Stoff, bevorzugt der abzutrennenden hydrophoben Metallverbindung, wechselwirkt. Geeignete Ankergruppen sind Phosphonsäuregruppen oder Thiolgruppen.According to the invention, it is possible to use as hydrophobizing substance all substances which are capable of further hydrophobicizing the hydrophobic metal compound to be separated off at the surface thereof. The hydrophobizing reagent is generally composed of a radical and an anchor group, wherein the anchor group preferably has at least 1, more preferably 3 reactive groups, which interacts with the hydrophobic substance to be separated, preferably the hydrophobic metal compound to be separated. Suitable anchor groups are phosphonic acid groups or thiol groups.
In einer besonders bevorzugten Ausführungsform sind die hydrophobierenden Substanzen ausgewählt aus der Gruppe bestehend aus Phosphor-enthaltenden Verbindungen der allgemeinen Formel (I)
- R1
- Wasserstoff oder verzweigter oder unverzweigter C1-C20-Alkylrest, C2-C20- Alkenylrest, C5-C20-Aryl- oder Heteroarylrest, bevorzugt C2-C20-Alkylrest, und
- R2
- Wasserstoff, OH oder verzweigter oder unverzweigter C1-C20-Alkylrest, C2- C20-Alkenylrest, C5-C20-Aryl- oder Heteroarylrest, bevorzugt OH, bedeutet,
- R3
- verzweigter oder unverzweigter C1-C20-Alkylrest, C2-C20-Alkenylrest, C5-C20- Aryl- oder Heteroarylrest, bevorzugt C2-C20-Alkyrest, und
- R2
- Wasserstoff, oder verzweigter oder unverzweigter C1-C20-Alkylrest, C2-C20- Alkenylrest, C5-C20-Aryl- oder Heteroarylrest, bevorzugt Wasserstoff, be- deutet,
In einer ganz besonders bevorzugten Ausführungsform wird Octylphosphonsäure eingesetzt, d.h. in der allgemeinen Fromel (I) bedeuten R1 C8-Alkylrest und R2 bedeutet OH.In a particularly preferred embodiment, the hydrophobizing substances are selected from the group consisting of phosphorus-containing compounds of the general formula (I)
- R 1
- Is hydrogen or branched or unbranched C 1 -C 20 alkyl, C 2 -C 20 - alkenyl, C 5 -C 20 aryl or heteroaryl, preferably C 2 -C 20 alkyl radical, and
- R 2
- Hydrogen, OH or a branched or unbranched C 1 -C 20 alkyl, C 2 - C 20 alkenyl, C 5 -C 20 aryl or heteroaryl radical, preferably OH, means
- R 3
- branched or unbranched C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 5 -C 20 - aryl or heteroaryl, preferably C 2 -C 20 -alkyl radical, and
- R 2
- Is hydrogen, or branched or unbranched C 1 -C 20 alkyl, C 2 -C 20 - alkenyl, C 5 -C 20 aryl or heteroaryl, preferably hydrogen, aeration indicated,
In a very particularly preferred embodiment, octylphosphonic acid is used, ie in the general formula (I) R 1 is C 8 -alkyl and R 2 is OH.
Diese hydrophobierend wirkenden Verbindungen werden einzeln oder im Gemisch mit einander in einer Menge von 0,01 bis 50 Gew.-%, besonders bevorzugt 0,1 bis 50 Gew.-%, bezogen auf die zu behandelnde Mischung, zugegeben. Diese hydrophobierend wirkenden Substanzen können durch alle dem Fachmann bekannte Verfahren auf den abzutrennenden hydrophoben Stoff, bevorzugt die abzutrennende wenigstens eine Metallverbindung aufgebracht werden. In einer bevorzugten Ausführungsform wird das zu behandelnde Gemisch mit der entsprechenden Menge an hydrophobierender Substanz, beispielsweise in einer Planetenkugelmühle, vermahlen und/oder verrührt. Geeignete Vorrichtungen sind dem Fachmann bekannt.These hydrophobicizing compounds are added individually or in admixture with each other in an amount of 0.01 to 50 wt .-%, particularly preferably 0.1 to 50 wt .-%, based on the mixture to be treated. These hydrophobicizing substances can be applied to the hydrophobic substance to be separated off, preferably the at least one metal compound to be separated off, by all methods known to the person skilled in the art. In a preferred embodiment, the mixture to be treated is ground and / or stirred with the appropriate amount of hydrophobing substance, for example in a planetary ball mill. Suitable devices are known in the art.
Schritt (B) des erfindungsgemäßen Verfahrens umfasst das Inkontaktbringen der Aufschlämmung oder Dispersion aus Schritt (A) mit wenigstens einer festen, hydrophoben Oberfläche zur Anbindung des abzutrennenden wenigstens einen hydrophoben Stoffes, bevorzugt der abzutrennenden wenigstens einen Metallverbindung an die feste, hydrophobe Oberfläche, wobei die feste hydrophobe Oberfläche die Innenwand eines Rohres, die Oberfläche einer Platte, die Oberfläche eines Laufbandes oder die Innenwand eines Reaktors ist.Step (B) of the process according to the invention comprises contacting the slurry or dispersion from step (A) with at least one solid, hydrophobic surface for attachment of the at least one hydrophobic substance to be separated, preferably the at least one metal compound to be separated to the solid, hydrophobic surface Solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
Die Bindung des hydrophoben Stoffes an die feste, hydrophobe Oberfläche erfolgt durch hydro-phobe Wechselwirkungen.The binding of the hydrophobic substance to the solid, hydrophobic surface is effected by hydrophobic interactions.
Die feste, hydrophobe Oberfläche ist die Innenwand eines Rohres, die Oberfläche einer Platte, die, beispielsweise feste oder bewegliche, Oberfläche eines Laufbandes oder die Innenwand eines Reaktors. Besonders bevorzugt ist die feste, hydrophobe Oberfläche die Innenwand eines Reaktors oder die feste oder bewegliche hydrophobe Oberfläche eines Laufbandes mit faserigen, micro-3D-Strukturen auf der Oberfläche.The solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill, for example solid or mobile, or the inner wall of a reactor. More preferably, the solid, hydrophobic surface is the inner wall of a reactor or the solid or mobile hydrophobic surface of a treadmill having fibrous micro 3D structures on the surface.
Es ist erfindungsgemäß möglich, dass eine feste, hydrophobe Oberfläche verwendet wird, die durch das Material, das die feste, hydrophobe Oberfläche bildet, an sich hydrophob ist. Es ist jedoch erfindungsgemäß auch möglich, dass an sich nicht hydrophobe Oberflächen durch Aufbringen wenigstens einer hydrophoben Schicht hydrophobiert werden.It is possible according to the invention that a solid, hydrophobic surface is used, which is hydrophobic per se by the material which forms the solid, hydrophobic surface. However, it is also possible according to the invention that hydrophobic surfaces which are not hydrophobic by themselves are applied by applying at least one hydrophobic layer.
In einer bevorzugten Ausführungsform wird eine feste Oberfläche aus Metall, Kunststoff, Glas, Holz oder Metalllegierungen durch Aufbringen einer hydrophoben Verbindung, welche gegebenenfalls mit geeigneten Substanzen oberflächenbeschichtet ist, hydrophobiert. Diese aus hydrophoben Verbindungen bestehende Oberfläche ist in einer Ausführungsform des erfindungsgemäßen Verfahrens an sich hydrophob genug, um in dem erfindungsgemäßen Verfahren verwendet zu werden. Das Aufbringen der hydrophoben Schicht kann beispielsweise durch Aufdampfen erfolgen. Erfindungsgemäß können zur Ausbildung dieser hydrophoben Schicht alle dem Fachmann bekannten hydrophoben Materialien verwendet werden, die dazu geeignet sind, eine entsprechende hydrophobe Schicht auszubilden. Eine hydrophobe Schicht ist eine Schicht, die keine polaren Gruppen hat und daher wasserabstoßenden Charakter aufweist.In a preferred embodiment, a solid surface made of metal, plastic, glass, wood or metal alloys is rendered hydrophobic by applying a hydrophobic compound, which is optionally surface-coated with suitable substances. In one embodiment of the process according to the invention, this surface consisting of hydrophobic compounds is inherently hydrophobic enough to be used in the process according to the invention. The application of the hydrophobic layer can be done, for example, by vapor deposition. According to the invention, all the hydrophobic materials known to those skilled in the art, which are suitable for forming a corresponding hydrophobic layer, can be used to form this hydrophobic layer. A hydrophobic layer is a layer that has no polar groups and therefore has a water-repellent character.
Beispiele für geeignete Verbindungen sind bifunktionelle Verbindungen, die mit der einen funktionellen Gruppe an der festen Oberfläche durch eine kovalente oder koordinative Bindung haften und mit der anderen hydrophoben funktionellen Gruppe an dem Werterz durch eine kovalente oder koordinative haften. Beispiele für Gruppen, mit denen die Bindung an die anorganische Verbindung erfolgt, sind die Carboxylgruppe - COOH, die Phosphonsäuregruppe -PO3H2, die Trihalogensilylgruppe -SiHal3 mit Hal gleich unabhängig voneinander F, Cl, Br, I, Trialkoxysiliylgruppe -Si(OR5)3 mit R5 gleich unabhängig voneinander C1-C12-Alkyl und/oder C2-C12-Alkenyl.Examples of suitable compounds are bifunctional compounds which adhere to one functional group on the solid surface by a covalent or coordinative bond and to the other hydrophobic functional group on the ore by a covalent or coordinative bond. Examples of groups with which the binding to the inorganic compound takes place are the carboxyl group -COOH, the phosphonic acid group -PO 3 H 2 , the trihalosilyl group -SiHal 3 with Hal equal to one another independently of one another F, Cl, Br, I, trialkoxysilyl group -Si ( OR 5 ) 3 with R 5 are each, independently of one another, C 1 -C 12 -alkyl and / or C 2 -C 12 -alkenyl.
Beispiele für Gruppen, mit denen die Bindung an das Werterz erfolgt, sind verzweigte oder unverzweigte C1-C20-Alkylgruppen, C5-C20-Aryl- und Heteroarylgruppen, Verbindungen der allgemeinen Formel (III)
- n
- 1 bis 25,
- X
- unabhängig voneinander S oder O, und
- R6
- verzweigter oder unverzweigter C1-C10-Alkylrest, Ammonium, einwertiges Metallkation, beispielsweise Alkalimetallkation bedeuten.
- n
- 1 to 25,
- X
- independently of one another S or O, and
- R 6
- branched or unbranched C 1 -C 10 -alkyl radical, ammonium, monovalent metal cation, for example alkali metal cation.
Im Fall, dass R6 Ammonium oder einwertiges Metallkation bedeutet, liegt eine ionische Verbindung (III) vor, in der der Rest -[CH2]n-X-C(=X)-X- am endständigen X einfach negativ geladen ist, wobei diese Ladung durch Ammonium oder das einwertige Metallkation ausgeglichen wird.In the case where R 6 is ammonium or monovalent metal cation is an ionic compound (III), in which the radical - [CH 2] n -X-C (= X) -X - is a single negative charge at the terminal X, which Charge is compensated by ammonium or the monovalent metal cation.
Bevorzugt erfolgt die Bindung an das Werterz über eine Gruppe der allgemeinen Formel (IIIa)
- n
- 2 bis 20 und
- R6
- verzweigter oder unverzweigter C1-C5-Alkylrest bedeuten.
- n
- 2 to 20 and
- R 6
- branched or unbranched C 1 -C 5 -alkyl radical.
In einer weiteren bevorzugten Ausführungsform ist die feste, hydrophobe Oberfläche die Oberfläche eines kontinuierlichen Laufbandes, welches durch die Aufschlämmung oder Dispersion enthaltend die zu behandelnde Mischung, bewegt wird. Die Oberfläche des Laufbandes kann in einer bevorzugten Ausführungsform durch dem Fachmann bekannte Verfahren vergrößert werden, beispielsweise durch Aufbringen einer dreidimensionalen Struktur auf dem Laufband. Ein Beispiel für eine solche dreidimensionale Struktur sind Fasern, die an der Oberfläche des Laufbandes angebracht sind. Das Laufband kann aus allen dem Fachmann bekannten und geeigneten Materialien sein, beispielsweise Polymere wie Polyethylenterephthalat, metallische Werkstoffe wie Aluminium, Mehrkomponentenwerkstoffe wie Aluminiumlegierungen. Die Fasern können ebenfalls aus allen dem Fachmann bekannten und geeigneten Werkstoffen sein.In another preferred embodiment, the solid, hydrophobic surface is the surface of a continuous treadmill which is agitated by the slurry or dispersion containing the mixture to be treated. The surface of the treadmill can be increased in a preferred embodiment by methods known in the art, for example by applying a three-dimensional structure on the treadmill. An example of such a three-dimensional structure are fibers attached to the surface of the treadmill. The treadmill can be made of any materials known and suitable to those skilled in the art, for example polymers such as polyethylene terephthalate, metallic materials such as aluminum, multi-component materials such as aluminum alloys. The fibers may also be of any suitable and suitable materials known to those skilled in the art.
Schritt (C) des erfindungsgemäßen Verfahrens umfasst das Entfernen der wenigstens einen festen, hydrophoben Oberfläche, an der der wenigstens eine hydrophobe Stoff, bevorzugt die wenigstens eine hydrophobe Metallverbindung angebunden ist aus Schritt (B), von der Aufschlämmung oder Dispersion, in der der wenigstens eine hydrophile Stoff enthalten ist.Step (C) of the method according to the invention comprises removing the at least one solid, hydrophobic surface to which the at least one hydrophobic substance, preferably the at least one hydrophobic metal compound is attached from step (B), from the slurry or dispersion in which the at least one a hydrophilic substance is included.
Nach Inkontaktbringen der Aufschlämmung oder Dispersion aus Schritt (A) mit wenigstens einer festen, hydrophoben Oberfläche (B) ist der abzutrennende hydrophobe Stoff, bevorzugt die abzutrennende hydrophobe Metallverbindung, zumindest teilweise, an die hydrophobe, feste Oberfläche angebunden. Der hydrophile Stoff, der in der zu behandelnden Mischung vorliegt, verbleibt jedoch in der Aufschlämmung oder Dispersion zurück, da dieser nicht an die hydrophobe Oberfläche anbindet. Somit gelingt es, die Konzentration an hydrophoben Stoffen in der zu behandelnden Mischung durch Entfernen dieser Verbindungen mit der hydrophoben Oberfläche zu senken.After contacting the slurry or dispersion of step (A) with at least one solid hydrophobic surface (B), the hydrophobic metal to be separated, preferably the hydrophobic metal compound to be separated, is at least partially attached to the hydrophobic solid surface. However, the hydrophilic substance present in the mixture to be treated remains in the slurry or dispersion because it does not bind to the hydrophobic surface. Thus, it is possible to reduce the concentration of hydrophobic substances in the mixture to be treated by removing these compounds with the hydrophobic surface.
Das Entfernen der beladenen, hydrophoben, festen Oberfläche kann durch alle dem Fachmann bekannte Verfahren erfolgen. Beispielsweise kann eine die hydrophobe, feste Oberfläche aufweisende Platte aus einem Bad enthaltend die Aufschlämmung oder Dispersion herausgehoben werden. Des Weiteren ist es erfindungsgemäß möglich, dass die hydrophobe, feste Oberfläche auf einem Laufband angebracht ist, welches sich durch die Aufschlämmung oder Dispersion bewegt. Ist die hydrophobe, feste Oberfläche an der Innenseite eines Rohrs bzw. eines Reaktors angebracht, so wird in einer bevorzugten Ausführungsform die Aufschlämmung oder Dispersion durch den Reaktor bzw. durch das Rohr geleitet. Das Entfernen der festen, hydrophoben Oberfläche geschieht somit dadurch, dass die Aufschlämmung oder Dispersion an dieser Oberfläche vorbeigeleitet wird. Es ist erfindungsgemäß auch möglich, dass, wenn die hydrophobe, feste Oberfläche die Innenwand eines Reaktors ist, das Entfernen dieser hydrophoben, festen Oberfläche dadurch geschieht, dass die zu behandelnde Aufschlämmung oder Dispersion aus dem Reaktor abgelassen wird.Removal of the loaded, hydrophobic, solid surface may be accomplished by any method known to those skilled in the art. For example, a plate having the hydrophobic solid surface may be lifted out of a bath containing the slurry or dispersion. Furthermore, it is possible according to the invention that the hydrophobic, solid surface is mounted on a treadmill which moves through the slurry or dispersion. When the hydrophobic solid surface is attached to the inside of a pipe or reactor, in a preferred embodiment, the slurry or dispersion is passed through the reactor or through the pipe. Removal of the solid, hydrophobic surface thus occurs by passing the slurry or dispersion past this surface. It is also possible according to the invention that, when the hydrophobic solid surface is the inner wall of a reactor, the removal of this hydrophobic solid surface occurs by draining the slurry or dispersion to be treated from the reactor.
Schritt (D) umfasst das Abtrennen des wenigstens einen hydrophoben Stoffes, bevorzugt der wenigstens einen hydrophoben Metallverbindung von der festen, hydrophoben Oberfläche.Step (D) comprises separating the at least one hydrophobic material, preferably the at least one hydrophobic metal compound, from the solid, hydrophobic surface.
Nach Schritt (C) ist die hydrophobe, feste Oberfläche mit dem abzutrennenden hydrophoben Stoff aus der zu behandelnden Reaktionsmischung, zumindest teilweise, beladen. Um den abzutrennenden hydrophilen Stoff zu erhalten, ist es erfindungsgemäß notwendig, diesen hydrophoben Stoff von der hydrophoben, festen Oberfläche abzutrennen.After step (C), the hydrophobic, solid surface with the hydrophobic substance to be separated from the reaction mixture to be treated, at least partially laden. In order to obtain the hydrophilic substance to be separated, it is necessary according to the invention to separate this hydrophobic substance from the hydrophobic, solid surface.
Dieses Abtrennen kann nach allen dem Fachmann bekannten Verfahren erfolgen, die dazu geeignet sind, den hydrophoben Stoff von der genannten Oberfläche abzutrennen, ohne entweder den hydrophoben Stoff und/oder die Oberfläche zu beeinträchtigen.This separation can be carried out by any of the methods known to those skilled in the art, which are suitable for separating the hydrophobic substance from said surface without impairing either the hydrophobic substance and / or the surface.
In einer bevorzugten Ausführungsform erfolgt das Abtrennen in Schritt (D) des erfindungsgemäßen Verfahrens durch Behandlung der festen, hydrophoben Oberfläche mit einer Substanz ausgewählt aus der Gruppe bestehend aus organischen Lösungsmitteln, basischen Verbindungen, sauren Verbindungen, Oxidationsmitteln, oberflächenaktiven Verbindungen und Mischungen davon.In a preferred embodiment, the separation in step (D) of the process according to the invention is carried out by treating the solid, hydrophobic surface with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing 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 und Mischungen davon. Beispiele für erfindungsgemäß einsetzbare basische Verbindungen sind wässrige Lösungen basischer Verbindungen, beispielsweise wässrige Lösungen von Alkali- und/oder Erdalkalihydroxiden, beispielsweise KOH, NaOH, wässrige Ammoniaklösungen, wässrige Lösungen organischer Amine der allgemeinen Formel R7 3N, wobei R7 ausgewählt ist aus der Gruppe bestehend aus C1-C8-Alkyl, gegebenenfalls substituiert mit weiteren funktionellen Gruppen. 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).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 and mixtures thereof. Examples of basic compounds which can be used according to the invention are aqueous solutions of basic compounds, for example aqueous solutions of alkali metal and / or alkaline earth metal hydroxides, for example KOH, NaOH, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 7 3 N, where R 7 is selected from Group consisting of C 1 -C 8 -alkyl, optionally substituted with further functional groups. 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. For example, H 2 O 2 can be used as the oxidizing agent, for example as a 30% strength by weight aqueous solution (perhydrol).
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 die hydrophobe, feste Oberfläche, an die der abzutrennende hydrophobe Stoff angebunden ist, mit einem organischen Lösungsmittel, besonders bevorzugt mit Aceton, gewaschen, um den hydrophoben Stoff von der hydrophoben, festen Oberfläche abzutrennen. Dieser Vorgang kann auch mechanisch unterstützt werden. In einer bevorzugten Ausführungsform wird das organische Lösungsmittel oder ein anderes oben genanntes Trennungsreagenz mit Druck auf die hydrophobe Oberfläche, die mit dem hydrophoben Werterz beladen ist, aufgebracht. In einer weiteren bevorzugten Ausführungsform kann, gegebenenfalls zusätzlich, Ultraschall zur Unterstützung des Trennungsvorgangs eingesetzt werden.In a preferred embodiment, the hydrophobic solid surface, to which the hydrophobic material to be separated is attached, is washed with an organic solvent, more preferably with acetone, to form the hydrophobic substance separated from the hydrophobic, solid surface. This process can also be supported mechanically. In a preferred embodiment, the organic solvent or other separation reagent mentioned above is applied with pressure on the hydrophobic surface loaded with the hydrophobic ore. In a further preferred embodiment, ultrasound may be used to assist the separation process, if appropriate in addition.
Im Allgemeinen wird das organische Lösungsmittel in einer Menge verwendet, die ausreicht, um möglichst die gesamte, an der hydrophoben Oberfläche anhaftende Menge der hydrophoben Metallverbindungen von dieser zu lösen. In einer bevorzugten Ausführungsform werden 20 bis 100 ml des organischen Lösungsmittels pro Gramm aufzureinigendem Gemisch aus hydrophobem und hydrophilem Stoff verwendet. Es ist erfindungsgemäß bevorzugt, dass die hydrophobe, feste Oberfläche mit mehreren kleineren Portionen, beispielsweise zwei Portionen des organischen Lösungsmittels, die zusammen die genannte Gesamtmenge ergeben, behandelt wird.In general, the organic solvent is used in an amount sufficient to dissolve as much as possible of the entire adhering to the hydrophobic surface amount of the hydrophobic metal compounds thereof. In a preferred embodiment, 20 to 100 ml of the organic solvent is used per gram of hydrophobic and hydrophilic fabric to be purified. It is preferred according to the invention that the hydrophobic solid surface is treated with several smaller portions, for example two portions of the organic solvent, which together give said total amount.
Erfindungsgemäß liegt der abzutrennende hydrophobe Stoff als Aufschlämmung oder Dispersion in dem genannten organischen Lösungsmittel vor. Der hydrophobe Stoff kann durch alle dem Fachmann bekannten Verfahren von dem organischen Lösungsmittel abgetrennt werden, beispielsweise Dekantieren, Filtrieren, Abdestillation des organischen Lösungsmittels oder Absetzen der festen Bestandteile am Boden des Behältnisses, wonach das Erz am Bodengrund abgeschöpft werden kann. Bevorzugt wird der abzutrennende hydrophobe Stoff, bevorzugt die abzutrennende hydrophobe Metallverbindung, von dem organischen Lösungsmittel durch Filtration getrennt. Der so erhältliche hydrophobe Stoff kann durch weitere, dem Fachmann bekannte Verfahren gereinigt werden. Das Lösungsmittel kann, gegebenenfalls nach Aufreinigung, wieder in das erfindungsgemäße Verfahren zurückgeführt werden.According to the invention, the hydrophobic substance to be separated is present as a slurry or dispersion in said organic solvent. The hydrophobic material can be separated from the organic solvent by any method known to those skilled in the art, for example, decanting, filtering, distilling off the organic solvent, or settling the solids at the bottom of the container, after which the ore can be skimmed off at the bottom. Preferably, the hydrophobic substance to be separated off, preferably the hydrophobic metal compound to be separated, is separated from the organic solvent by filtration. The hydrophobic 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.
In einer weiteren bevorzugten Ausführungsform wird die hydrophobe, feste Oberfläche, von der in Schritt (D) der hydrophobe Stoff abgetrennt worden ist, getrocknet. Dieses Trocknen kann durch alle dem Fachmann bekannte Verfahren geschehen, beispielsweise durch Behandlung in einem Ofen, bei einer Temperatur von beispielsweise 30 bis 100°C.In another preferred embodiment, the hydrophobic solid surface from which the hydrophobic substance has been separated in step (D) is dried. This drying may be carried out by any method known to those skilled in the art, for example by treatment in an oven at a temperature of for example 30 to 100 ° C.
In einer weiteren bevorzugten Ausführungsform wird die hydrophobe, feste Oberfläche, welche gegebenenfalls getrocknet worden ist, wieder in das erfindungsgemäße Verfahren zurückgeführt, d. h. wieder in Schritt (B) des erfindungsgemäßen Verfahrens, eingesetzt. Beispielsweise kann bei Verwendung eines Laufbandes das erfindungsgemäße Verfahren so durchgeführt werden, dass das Laufband kontinuierlich durch die zu behandelnde Aufschlämmung oder Dispersion geführt, mit einem Lösungsmittel zur Abtrennung der hydrophoben Teilchen behandelt, getrocknet, und wieder in das zu behandelnde Bad geführt wird. Beim Rückführen der hydrophoben, festen Oberfläche ist es erfindungsgemäß erforderlich, dass diese vollständig von dem verwendeten Trennungsreagenz befreit ist.In a further preferred embodiment, the hydrophobic, solid surface, which has optionally been dried, is returned to the process according to the invention, ie used again in step (B) of the process according to the invention. For example, when using a treadmill, the method according to the invention can be carried out so that the treadmill is continuously passed through the slurry or dispersion to be treated, treated with a solvent to separate the hydrophobic particles, dried, and returned to the bath to be treated. When recycling the hydrophobic solid surface It is according to the invention required that this is completely freed from the separation reagent used.
Die vorliegenden Erfindung betrifft auch die Verwendung einer festen, hydrophoben Oberfläche zum Abtrennen wenigstens eines hydrophoben Stoffes, bevorzugt einer hydrophoben Metallverbindung oder Kohle, aus einer Mischung umfassend diesen wenigstens einen hydrophoben Stoff und wenigstens einen hydrophilen Stoff, bevorzugt wenigstens eine hydrophile Metallverbindung, wobei die feste hydrophobe Oberfläche die Innenwand eines Rohres, die Oberfläche einer Platte, die Oberfläche eines Laufbandes oder die Innenwand eines Reaktors ist.The present invention also relates to the use of a solid hydrophobic surface for separating at least one hydrophobic substance, preferably a hydrophobic metal compound or carbon, from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, preferably at least one hydrophilic metal compound hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
Bezüglich der festen, hydrophoben Oberfläche, der hydrophoben Stoffe, der hydrophilen Stoffe und der Mischung umfassend diesen wenigstens eine hydrophoben Stoff und wenigstens einen hydrophilen Stoff gilt das bezüglich des erfindungsgemäßen Verfahrens Gesagte.With regard to the solid, hydrophobic surface, the hydrophobic substances, the hydrophilic substances and the mixture comprising these at least one hydrophobic substance and at least one hydrophilic substance, what has been said with regard to the method according to the invention applies.
-
Figur 1 zeigt eine besonders bevorzugte Ausführungsform des erfindunsgemäßen Verfahrens, in der ein kontinuierliches Laufband als hydrophobe feste Fläche eingesetzt wird. Die Bezugszeichen haben die folgenden Bedeutungen:- 1
- Zu trennende Mischung aus wenigstens einem hydrophoben Stoff und wenigs- tens einem hydrophilem Stoff
- 2
- hydrophobes Laufband mit strukturierter Oberfläche
- 3
- hydrophobes Laufband mit anhaftendem hydrophobem Stoff
- 4
- Trennungsmittel, beispielsweise organisches Lösungsmittel
FIG. 1 shows a particularly preferred embodiment of the erfindunsgemäßen method in which a continuous treadmill is used as a hydrophobic solid surface. The numerals have the following meanings:- 1
- Separating mixture of at least one hydrophobic substance and at least one hydrophilic substance
- 2
- hydrophobic treadmill with structured surface
- 3
- hydrophobic treadmill with hydrophobic material attached
- 4
- Separating agent, for example organic solvent
-
Figur 2 zeigt eine Ausschnittsvergrößerung des Laufbandes in der Mischung aus wenigstens einem hydrophoben Stoff und wenigstens einem hydrophilem Stoff mit folgender Bedeutung- 5
- Strukturen an der Bandoberfläche
FIG. 2 shows an enlarged detail of the treadmill in the mixture of at least one hydrophobic substance and at least one hydrophilic substance with the following meaning- 5
- Structures on the strip surface
Ein 100 mL Becherglas wird so mit hydrophobiertem Magnetit (oberflächenbeschichtet mit 1-Dodecyltriclosilan, wobei 1 nm2 Magnetitoberfläche mit ca. 10 bis 50 Molekülen Trichlorsilan beladen ist; Durchmesser der Magnetitteilchen = 10 nm) beschichtet, dass eine Fläche an den Wänden von ca. 40 cm2 hydrophobiert ist. Es werden 50 mL Wasser, 0,05 g Dodecylamin (98%-ig; Alfa Aesar), 0,50 g Cu2S, verrührt mit 1,7 Gew.-% Octylphosphonsäure, und 0,50 g Meersand, der zu 100 % aus SiO2 besteht, mit Salzsäure gereinigt und verrührt mit 1,7 Gew.-% Octylphosphonsäure, in das so beschichtete Becherglas gegeben. Es wird 2 h bei 400 U/min. gerührt, anschließend wird das Wasser vorsichtig abgesaugt und der Inhalt des Becherglases vorsichtig getrocknet.A 100 mL beaker is so coated with hydrophobized magnetite (surface-coated with 1-dodecyltriclosilan, wherein 1 nm 2 magnetite surface is loaded with about 10 to 50 molecules of trichlorosilane, diameter of the magnetite particles = 10 nm) such that an area on the walls of approx. 40 cm 2 is hydrophobic. 50 ml of water, 0.05 g of dodecylamine (98% strength, Alfa Aesar), 0.50 g of Cu 2 S, stirred with 1.7% by weight of octylphosphonic acid, and 0.50 g of sea sand, which is 100 % of SiO 2 , cleaned with hydrochloric acid and stirred with 1.7 wt .-% octylphosphonic acid, placed in the thus coated beaker. It is 2 h at 400 rpm. stirred, then the water is carefully filtered by suction and the contents of the beaker are carefully dried.
Der am Boden liegende Sand wird entnommen und zurück gewonnen (0,46 g). Anschließend wird in das Becherglas 30 mL Aceton gegeben und 5 min. kräftig gerührt. Die Aceton-Phase wird anschließend abdekantiert und in ein zweites Becherglas überführt. Dieser Vorgang wird ein zweites Mal wiederholt. Nach Filtration werden 0,38 g Cu2S erhalten.The ground sand is removed and recovered (0.46 g). Subsequently, 30 ml of acetone are added to the beaker and 5 min. stirred vigorously. The acetone phase is then decanted off and transferred to a second beaker. This process is repeated a second time. After filtration, 0.38 g of Cu 2 S are obtained.
Die zurückgewonnene Menge an Cu2S entspricht einer relativen Menge von 76%.The recovered amount of Cu 2 S corresponds to a relative amount of 76%.
Claims (11)
- A process for separating at least one hydrophobic material from a mixture comprising this at least one hydrophobic material and at least one hydrophilic material, which comprises the steps:(A) preparation of a slurry or dispersion of the mixture to be treated in at least one suitable dispersion medium,(B) contacting of the slurry or dispersion from step (A) with at least one solid, hydrophobic surface to bind the at least one hydrophobic material to be separated off to this, where the solid hydrophobic surface is the interior wall of a tube, the surface of a plate, the surface of a conveyor belt or the interior wall of a reactor,(C) removal of the at least one solid, hydrophobic surface to which the at least one hydrophobic material is bound from step (B) from the slurry or dispersion in which the at least one hydrophilic material is comprised and(D) separation of the at least one hydrophobic material from the solid, hydrophobic surface.
- The process according to claim 1, wherein the at least one hydrophobic material is at least one hydrophobic metal compound or coal and the at least one hydrophilic material is at least one hydrophilic metal compound.
- The process according to claim 1 or 2, wherein the at least one hydrophobic material present in the mixture is hydrophobicized by means of at least one substance before step (B).
- The process according to claim 2 or 3, wherein the at least one hydrophobic metal compound is selected from the group consisting of sulfidic 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 metal compounds.
- The process according to claim 4, wherein the sulfidic ores are selected from the group of copper ores consisting of chalcopyrite CuFeS2, bornite Cu5FeS4, chalcocite Cu2S and mixtures thereof.
- The process according to claim 5, wherein the oxidic metal compounds are selected from the group consisting of silicon dioxide SiO2, feldspars, mica and mixtures thereof.
- The process according to any of claims 1 to 7, wherein the dispersion medium in step (A) is water.
- The process according to any of claims 1 to 8, wherein the separation in step (D) is effected by treating the solid hydrophobic surface with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidants, surface-active compounds and mixtures thereof.
- The process according to any of claims 1 to 9, wherein the solid, hydrophobic surface is, after step (D), recirculated to step (B).
- The use of a solid, hydrophobic surface for separating at least one hydrophobic material from a mixture comprising this at least one hydrophobic material and at least one hydrophilic material, where the solid hydrophobic surface is the interior wall of a tube, the surface of a plate, the surface of a conveyor belt or the interior wall of a reactor.
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PL08785971T PL2171106T3 (en) | 2007-07-17 | 2008-07-08 | Method for ore enrichment by means of hydrophobic, solid surfaces |
EP08785971A EP2171106B1 (en) | 2007-07-17 | 2008-07-08 | Method for ore enrichment by means of hydrophobic, solid surfaces |
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EP08785971A EP2171106B1 (en) | 2007-07-17 | 2008-07-08 | Method for ore enrichment by means of hydrophobic, solid surfaces |
PCT/EP2008/058854 WO2009010422A1 (en) | 2007-07-17 | 2008-07-08 | Method for ore enrichment by means of hydrophobic, solid surfaces |
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AU2008277789A1 (en) | 2009-01-22 |
CN101778957A (en) | 2010-07-14 |
PT2171106E (en) | 2011-10-06 |
UA99623C2 (en) | 2012-09-10 |
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JP5496091B2 (en) | 2014-05-21 |
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CA2693902C (en) | 2016-06-28 |
PL2171106T3 (en) | 2012-02-29 |
AR067567A1 (en) | 2009-10-14 |
EP2171106A1 (en) | 2010-04-07 |
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