EP0201815B1 - Use of surfactant mixtures as flotation agents for non-sulfide ores - Google Patents
Use of surfactant mixtures as flotation agents for non-sulfide ores Download PDFInfo
- Publication number
- EP0201815B1 EP0201815B1 EP86106023A EP86106023A EP0201815B1 EP 0201815 B1 EP0201815 B1 EP 0201815B1 EP 86106023 A EP86106023 A EP 86106023A EP 86106023 A EP86106023 A EP 86106023A EP 0201815 B1 EP0201815 B1 EP 0201815B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flotation
- component
- collector
- alkyl
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 title description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title 1
- 239000008396 flotation agent Substances 0.000 title 1
- 238000005188 flotation Methods 0.000 claims abstract description 61
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 42
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 28
- 239000011707 mineral Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 15
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 239000002563 ionic surfactant Substances 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 37
- -1 alkyl sulfosuccinates Chemical class 0.000 claims description 29
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 8
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000003139 primary aliphatic amines Chemical group 0.000 claims description 4
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 34
- 229910052799 carbon Inorganic materials 0.000 description 32
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003925 fat Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 229910052586 apatite Inorganic materials 0.000 description 7
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- WZEMZTZDHLCBTC-UHFFFAOYSA-N 1-o-octadecyl 4-o-sulfo butanedioate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC(=O)OS(O)(=O)=O WZEMZTZDHLCBTC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- MBDHLQKZIVIDEY-UHFFFAOYSA-N Olivin Natural products COc1cc(C=C(C)/C(=O)c2c(O)cc(O)cc2O)ccc1O MBDHLQKZIVIDEY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- SHVBTTRUEDMJTK-UHFFFAOYSA-N hexadec-1-en-1-amine Chemical compound CCCCCCCCCCCCCCC=CN SHVBTTRUEDMJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000009282 microflotation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- WGNKXCMZCXHUHX-UHFFFAOYSA-N octadec-1-en-1-amine Chemical compound CCCCCCCCCCCCCCCCC=CN WGNKXCMZCXHUHX-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- PIHTXGRVQBTVRE-KFYAXVMHSA-N olivin Chemical compound OC1=CC(O)=C2C(O)=C(C(=O)[C@H]([C@H]([C@H](OC)C(=O)[C@@H](O)[C@@H](C)O)C3)O)C3=CC2=C1 PIHTXGRVQBTVRE-KFYAXVMHSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- TYLSDQJYPYQCRK-UHFFFAOYSA-N sulfo 4-amino-4-oxobutanoate Chemical compound NC(=O)CCC(=O)OS(O)(=O)=O TYLSDQJYPYQCRK-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- 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
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- 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
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
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- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- 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
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
Definitions
- the invention relates to the use of mixtures of nonionic ethylene oxide / propylene oxide addition products and anionic or cationic surfactants known per se as collectors for flotation processes as auxiliaries for the flotation of non-sulfidic ores.
- Flotation is a generally used sorting process for the processing of mineral raw materials, in which the valuable minerals are separated from the worthless ones.
- Non-sulfidic minerals are, for example, apatite, fluorite, scheelite and other salt-like minerals, cassiterite and other metal oxides, e.g. Oxides of titanium and zirconium, as well as certain silicates and aluminosilicates.
- the ore is pre-shredded and dry, but preferably wet ground, and suspended in the water.
- Collectors are usually added to the non-sulfidic ores, often in conjunction with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), in order to support the separation of the valuable minerals from the undesirable gangue components in the ore during the subsequent flotation .
- auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators)
- these reagents are allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) in order to produce a foam on their surface.
- the collector ensures that the surface of the minerals is rendered hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration.
- the mineral components are made hydrophobic selectively in such a way that the components of the ore which are undesirable do not adhere to the gas bubbles.
- the mineral-containing foam is stripped off and processed.
- the aim of flotation is to extract the mineral of value from the ores in the highest possible yield, while at the same time maintaining the best possible enrichment.
- anionic and cationic surfactants are used as collectors.
- Known anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids and oleic acid, alkyl sulfates, in particular alkyl sulfates derived from fatty alcohols or fatty alcohol mixtures, alkylarylsulfonates, alkylsulfosuccinates, alkylsulfosuccinamates and acyllactylates.
- Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats and oils, as well as certain alkyl-substituted and hydroxyalkyl-substituted alkylenediamines and the water-soluble acid addition salts of these amines.
- Typical collectors for non-sulfidic minerals develop a foam that is suitable for flotation because of their surfactant character. However, it may also be necessary to develop the foam using special foamers or to modify it in a suitable manner.
- foamers for flotation are alcohols with 4 to 10 carbon atoms, polypropylene glycols, polyethylene glycol or polypropylene glycol ethers, terpene alcohols (pine oils) and cresylic acids.
- modifying reagents are added to the suspensions (turbidity) to be floated, for example regulators for the pH value, activators for the mineral to be obtained in the foam or deactivators for the minerals undesirable in the foam, and optionally also dispersants.
- nonionic surfactants are hardly used as collectors in flotation.
- combinations of ionic and nonionic surfactants are also occasionally described as collectors.
- Cationic, anionic and ampholytic collectors are used for the flotation of non-sulfidic ores, which in many cases do not lead to a satisfactory application of valuable minerals with economically justifiable collector quantities.
- the object of the present invention was therefore to improve known collectors (primary collectors) for the flotation of non-sulfidic ores by suitable additives (co-collectors) in such a way that, with practically the same selectivity of the collectors, the application of valuable minerals in the flotation pro zess significantly increased, which effect can also be used so that (compared to the collector amounts of the prior art) reduced amounts of collectors and co-collectors constant yields of valuable minerals are obtained.
- ethylene oxide-ipropylene oxide addition products are known substances which can be synthesized by known processes. As a rule, they are obtained by adding the intended amounts of ethylene oxide and propylene oxide to the fatty alcohols used as the starting material using known alkaline alkoxylation catalysts.
- alkylene oxides can be carried out either by reacting an appropriate mixture of ethylene oxide and propylene oxide with the fatty alcohol starting material or by adding one alkylene oxide first and then the other.
- the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) can consist of straight-chain and branched, saturated and unsaturated compounds of this category with 8 to 22 carbon atoms, for example n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n- Hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-hexadecanol, isotridecanol and isooctadecanol.
- the fatty alcohols mentioned can individually form the basis of the ethylene oxide / propylene oxide addition products.
- fatty alcohol mixtures being derived from the fatty acid component of fats and oils of animal or vegetable origin.
- fatty alcohol mixtures can be known from the native fats and oils, u. a. win over the transesterification of the triglycerides with methanol and subsequent catalytic hydrogenation of the fatty acid methyl ester.
- Both the fatty alcohol mixtures obtained in the production process and suitable fractions with a limited chain length spectrum can serve as the basis for the addition of ethylene oxide and propylene oxide.
- fatty alcohol mixtures obtained from natural fats and oils synthetically obtained fatty alcohol mixtures, for example the known Ziegler and oxo fatty alcohols, are also suitable as starting materials for the production of the ethylene oxide / propylene oxide addition products defined under a). Addition products of ethylene oxide and propylene oxide onto fatty alcohols having 12 to 18 carbon atoms are preferably used as component a).
- the polyalkylene glycol part of the addition products mentioned contains, on average, 1 to 10 moles of ethylene glycol units and 1 to 15 moles of propylene glycol units per mole of fatty alcohol.
- the molar amounts are coordinated so that 2 to 25 moles of alkylene glycol units are present per mole of fatty alcohol and that the molar ratio between ethylene glycol and propylene glycol units is in the range from 1: 5 to 2: 1.
- Products which contain 2 to 6 ethylene glycol units and 4 to 12 propylene glycol units per mole of fatty alcohol and in which the molar ratio between ethylene glycol units and propylene glycol units is in the range from 1: 1 to 1: 2 are preferred.
- Component b) includes anionic, cationic and ampholytic surfactants, which are known per se as collectors for the flotation of non-sulfidic ores.
- anionic surfactants are to be used according to the invention as component b), they are selected in particular from the group consisting of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates and acyl lactylates.
- Suitable fatty acids are in particular the straight-chain fatty acids with 12 to 18 carbon atoms, in particular those with 16 to 18 carbon atoms, obtained from vegetable or animal fats and oils, for example by fat splitting and optionally fractionation and / or separation by the crosslinking process. Oleic acid and tall oil fatty acid are of particular importance here.
- Suitable as alkyl sulfates are the sulfuric acid semiesters of fatty alcohols with 8 to 22 carbon atoms Men, preferably of fatty alcohols with 12 to 18 carbon atoms, which can be straight-chain or branched.
- the fatty alcohol component of the sulfuric acid half-esters the previous information applies analogously to the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a).
- Suitable alkyl sulfosuccinates are sulfosuccinic acid semiesters of fatty alcohols having 8 to 22 carbon atoms, preferably fatty alcohols having 12 to 18 carbon atoms. These alkyl sulfosuccinates can be obtained, for example, by reacting appropriate fatty alcohols or fatty alcohol mixtures with maleic anhydride and subsequent addition of alkali metal sulfite or alkali metal bisulfite.
- the fatty alcohol component of the sulfosuccinic acid esters the information on the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) applies analogously.
- the alkyl sulfosuccinamates considered as possible component b) correspond to the formula I, in which R is an alkyl or alkenyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, R 'is hydrogen or an alkyl radical having 1 to 3 carbon atoms and M is a hydrogen ion, an alkali metal cation, or an ammonium ion, preferably a sodium or ammonium ion represent.
- the alkylsulfosuccinamates of the formula 1 are known substances which are obtained, for example, by reacting corresponding primary or secondary amines with maleic anhydride, followed by addition of alkali metal sulfite or alkali metal bisulfite.
- Primary amines suitable for the preparation of the alkylsulfosuccinamates are, for example, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-hexadecenylamine and n-octadecenylamine.
- the amines mentioned can individually form the basis of the alkylsulfosuccinamates.
- amine mixtures are used to prepare the alkylsulfosuccinamates, the alkyl radicals of which come from the fatty acid content of fats and oils of animal or vegetable origin.
- such amine mixtures can be obtained from the fatty acids of native fats and oils obtained by fat cleavage via the associated nitriles by reduction with sodium and alcohols or by catalytic hydrogenation.
- Particularly suitable secondary amines for the preparation of the alkylsulfosuccinamates of the formula are the N-methyl and N-ethyl derivatives of the above-mentioned primary amines.
- Alkylbenzenesulfonates suitable for use as component b) correspond to formula II, in which R is a straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and M is an alkali metal cation or an ammonium ion, preferably a sodium ion.
- Alkyl sulfonates which are suitable for use as component b) correspond to the formula III, in which R represents a straight-chain or branched alkyl radical, in particular having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M represents an alkali metal cation or an ammonium ion, preferably a sodium ion.
- the petroleum sulfonates suitable for use as component b) were obtained from lubricating oil fractions, generally by sulfonation with sulfur trioxide or oleum.
- Compounds in which the hydrocarbon radicals predominantly have chain lengths in the range from 8 to 22 carbon atoms are particularly suitable here.
- the acyl lactylates also considered as possible component b) correspond to the formula IV, in which R is an aliphatic, cycloaliphatic or alicyclic radical having 7 to 23 carbon atoms and X is a salt-forming cation.
- R is preferably an aliphatic, linear or branched hydrocarbon radical which can be saturated, mono- or polyunsaturated and optionally substituted by hydroxyl groups.
- cationic surfactants are to be used as component b), primary aliphatic amines and alkylene diamines substituted with a-branched alkyl radicals or hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines are particularly suitable.
- Particularly suitable primary aliphatic amines are the fatty amines with 8 to 22 carbon atoms derived from the fatty acids of the native fats and oils, which have already been described above in connection with the alkylsulfosuccinamates which are also suitable as component b).
- mixtures of fatty amines are generally used, for example tallow amines or hydrotalgamines, as are obtainable from the tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their hydrogenation.
- the preparation of these compounds and their use in flotation is described in the DDR-PS 64 275.
- the preparation of the compounds of formula V and their use in flotation is described in DE-A-25 47 987.
- the aforementioned amine compounds can be used as such or in the form of their water-soluble salts. If appropriate, the salts are obtained by neutralization, which can be carried out both with equimolar amounts and with an excess or an excess of acid. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
- ampholytic surfactants which are used according to the invention as component b) are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active groups preferably consisting of sulfonic acid or carboxyl groups and the cation-active groups consisting of amino groups, preferably on secondary or tertiary amino groups, consist.
- Particularly suitable ampholytic surfactants are sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates.
- the sarcosides suitable for use as component b) correspond to formula VII, in which R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms.
- R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms.
- These sarcosides are known compounds which can be prepared by known processes. With regard to their use in flotation, reference is made to H. Schubert, Auf Struktur solid mineral raw materials, 2nd edition, Leipzig 1977, pp. 310-311, and the references cited therein.
- the taurides suitable for use as component b) correspond to formula VIII, in which R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms. These taurides are known compounds that can be obtained by known methods. The use of taurids in flotation is known, see H. Schubert, loc. cit.
- N-substituted aminopropionic acids which are suitable for use as component b) correspond to the formula IX, in which n can be zero or a number from 1 to 4, while R denotes an alkyl or acyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the N-substituted aminopropionic acids mentioned are likewise known compounds which can be prepared in a known manner. With regard to their use as collectors in flotation, reference is made to H. Schubart, loc. cit. and on int. J. Min. Proc. 9 (1982), pp. 353-384, in particular p. 380.
- N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates suitable for use as component b) in the collector mixtures according to the invention correspond to the formula (X), in which R is an alkyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M is a hydrogen ion, an alkali metal cation or an ammonium ion, preferably a sodium ion.
- the N- (1,2-dicarboxyethyl) -N-alkylsulfosucinamates mentioned are known compounds which can be prepared by known methods. The use of these compounds as collectors in flotation is also known, see H. Schubert, loc. cit.
- the weight ratio of components a): b) is in the range from 1:19 to 3: 1, preferably in the range from 1: 4 to 1: 1.
- collector mixtures to be used according to the invention depend in each case on the type of ores to be floated and on their content of valuable minerals. As a result, the amounts required can vary within wide limits. In general, the collector mixtures according to the invention are used in amounts of 20 to 2000 g per ton of raw ore.
- the effectiveness of the collectors of the surfactant mixtures to be used according to the invention is practically not impaired by the hardness formers of the water used to produce the slurries.
- the mixtures of primary collectors and co-collectors to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of the known anionic, cationic and / or ampholytic collectors.
- the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous slurries of the ground ores.
- the flotation is carried out under the conditions of the methods of the prior art.
- the collector mixtures to be used according to the invention can be used, for example, in the flotation of apatite-Scheelite and tungsten ores, in the separation of fluorite from quartz, in the separation of quartz or alkali silicates from hematite, magnetite and chromite by inverse flotation, in the separation of cassiterite of quartz and silicates, and in the separation of oxides of iron and titanium from quartz for cleaning glass sands.
- the flotation tests were carried out in a laboratory flotation cell (model D-1 from Denver Equipment with a capacity of 1.2 liters) at approx. 20 ° C. Tap water with a hardness of 18 ° dH was used in Examples 1 to 6 to produce the slurries.
- the slurries for Examples 4 and 6 were prepared using hard water (945 ppm Ca 2+ and 1700 ppm Mg 2+ ). After the ore had been slurried in the flotation cell, the magnetite was removed with a hand magnet, washed and the wash water returned to the cell.
- the cloud density was 500 g / l. Water glass in quantities of 1000 and 2000 g / t was used as the pusher.
- the pH of the turbidity was adjusted to 11 in each case. Flotation was carried out at a rotation speed of the mixing device of 1500 per minute. The flotation time was 6 minutes. After the preliminary flotation (rougher flotation), the preconcentrate was cleaned twice, in Examples 3, 4 and 7, collectors were metered in for the first cleaning flotation.
- Column 2 of Table I below shows the collectors used and their quantities.
- Column 3 shows the amount of water glass used as a handle.
- Column 4 says “Magn.” for magnetite separation, "V.-F” for pre-flotation, "RF” for cleaning flotation and "conc.” for concentrate.
- Column 5 shows the total yield of the respective flotation stage, based on the total amount of ore, in column 6 the P 2 O 5 content of the mountains in the respective process stage and in column 7 the proportion of P 2 0 s applied in each process stage - Amount of the total amount of P 2 O 5 produced in the ore.
- the flotation tests were carried out under the conditions described for Examples 1 to 8 with the following deviations: Starch was used as the pusher. The pH of the turbidity was 10.5 in each case. The slurries were prepared using tap water with a hardness of 18 ° dH. The iron oxides had been removed by magnetic separation before the apatite flotation.
- the comparative composition used in Example 22 contained as component a) an adduct of 5 moles of ethylene oxide with one mole of nonylphenol (co-collector D ").
- the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Sci. 259 (1981), pp. 775-776 at 23 ° C. The individual tests were carried out with 2 g ore each. Distilled water was used to prepare the slurry. Sufficient collectors and co-collectors were added to the turbidities so that a total collector quantity of 500 g / t was available. The conditioning time was 15 minutes each. During the flotation, a flow of air was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 2 minutes in all experiments.
- the flotation experiments were carried out using a Humbold-Wedag laboratory flotation machine from KHD Industrieanlagen AG, Humbold-Wedag, Cologne (see Seifen-Fette-Wachsen 105 (1979), p. 248) using a 1 1 flotation cell. Tap water with a hardness of 18 ° dH was used to produce the cloudiness. The cloud density was 250 g / l. Aluminum sulfate was used as the activator, in each case in an amount of 500 g / t. The pH was adjusted to 3 using sulfuric acid. The conditioning time was 10 minutes. The flotation was carried out for 15 minutes at 23 ° C. and with a rotor speed of 1200 revolutions per minute. The collector was added to the slurries in 3 or 4 aliquots in the manner shown in Table IV below.
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Abstract
Description
Die Erfindung betrifft die Verwendung von Gemischen aus nichtionischen Ethylenoxid- /Propylenoxidanlagerungsprodukten und an sich als Sammler für Flotationsprozesse bekannten anionischen oder kationischen Tensiden als Hilfsmittel für die Flotation von nichtsulfidischen Erzen.The invention relates to the use of mixtures of nonionic ethylene oxide / propylene oxide addition products and anionic or cationic surfactants known per se as collectors for flotation processes as auxiliaries for the flotation of non-sulfidic ores.
Die Flotation ist ein allgemein angewandtes Sortierverfahren für die Aufbereitung von mineralischen Rohstoffen, bei dem die wertvollen Mineralien von den wertlosen getrennt werden. Nichtsulfidische Mineralien sind beispielsweise Apatit, Fluorit, Scheelit und andere salzartige Mineralien, Cassiterit und andere Metalloxide, z.B. Oxide des Titans und Zirkons, sowie bestimmte Silikate und Alumosilikate. Zur Flotation wird das Erz vorzerkleinert und trocken, vorzugsweise aber naß vermahlen, und im Wasser suspendiert. Den nichtsulfidischen Erzen werden normalerweise Sammler, häufig in Verbindung mit Schäumern und gegebenenfalls weiteren Hilfsreagenzien wie Reglern, Drückern (Desaktivatoren) und/oder Belebern (Aktivatoren), zugesetzt, um die Abtrennung der Wertmineralien von den unerwünschten Gangartbestandteilen des Erzes bei der anschließenden Flotation zu unterstützen. Üblicherweise laßt man diese Reagenzien eine gewisse Zeit auf das feingemahlene Erz einwirken (Konditionieren), bevor in die Suspension Luft eingeblasen wird (Flotieren), um an ihrer Oberfläche einen Schaum zu erzeugen. Dabei sorgt der Sammler für eine Hydrophobierung der Oberfläche der Mineralien, so daß ein Anhaften dieser Mineralien an den während der Belüftung gebildeten Gasblasen bewirkt wird. Die Hydrophobierung der Mineralbestandteile erfolgt selektiv in der Weise, daß die Bestandteile des Erzes, die unerwünscht sind, sich nicht an die Gasblasen heften. Der mineralhaltige Schaum wird abgestreift und weiterverarbeitet. Es ist das Ziel der Flotation, das Wertmineral der Erze in möglicht hoher Ausbeute zu gewinnen, dabei aber gleichzeitig eine möglichst gute Anreicherung zu erhalten.Flotation is a generally used sorting process for the processing of mineral raw materials, in which the valuable minerals are separated from the worthless ones. Non-sulfidic minerals are, for example, apatite, fluorite, scheelite and other salt-like minerals, cassiterite and other metal oxides, e.g. Oxides of titanium and zirconium, as well as certain silicates and aluminosilicates. For the flotation, the ore is pre-shredded and dry, but preferably wet ground, and suspended in the water. Collectors are usually added to the non-sulfidic ores, often in conjunction with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), in order to support the separation of the valuable minerals from the undesirable gangue components in the ore during the subsequent flotation . Usually these reagents are allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) in order to produce a foam on their surface. The collector ensures that the surface of the minerals is rendered hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration. The mineral components are made hydrophobic selectively in such a way that the components of the ore which are undesirable do not adhere to the gas bubbles. The mineral-containing foam is stripped off and processed. The aim of flotation is to extract the mineral of value from the ores in the highest possible yield, while at the same time maintaining the best possible enrichment.
Bei den bekannten Flotationsprozessen für nichtsulfidische Erze werden anionische und kationische Tenside als Sammler eingesetzt. Bekannte anionische Sammler sind beispielsweise gesättigte und ungesättigte Fettsäuren, insbesondere Tallölfettsäuren und Ölsäure, Alkylsulfate, insbesondere von Fettalkoholen oder Fettalkoholgemischen abgeleitete Alkylsulfate, Alkylarylsulfonate, Alkylsulfosuccinate, Alkylsulfosuccinamate und Acyllactylate. Bekannte kationische Sammler sind beispielsweise primäre aliphatische Amine, insbesondere die von den Fettsäuren der pflanzlichen und tierischen Fette und Öle abstammenden Fettamine, sowie bestimmte alkylsubstituierte und hydroxyalkylsubstituierte Alkylendiamine und die wasserlöslichen Säureadditionssalze dieser Amine.In the known flotation processes for non-sulfidic ores, anionic and cationic surfactants are used as collectors. Known anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids and oleic acid, alkyl sulfates, in particular alkyl sulfates derived from fatty alcohols or fatty alcohol mixtures, alkylarylsulfonates, alkylsulfosuccinates, alkylsulfosuccinamates and acyllactylates. Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats and oils, as well as certain alkyl-substituted and hydroxyalkyl-substituted alkylenediamines and the water-soluble acid addition salts of these amines.
Viele Sammler für nichtsulfidische Mineralien entwickeln wegen ihres Tensidcharakters selbst einen für die Flotation geeigneten Schaum. Es kann jedoch auch notwendig sein, durch spezielle Schäumer den Schaum zu entwickeln oder in geeigneter Weise zu modifizieren. Bekannte Schäumer für die Flotation sind Alkohole mit 4 bis 10 Kohlenstoffatomen, Polypropylenglykole, Polyethylenglykol- oder Polypropylenglykolether, Terpenalkohole (Pine Oils) und Kresylsäuren. Soweit erforderlich, werden den zu flotierenden Suspensionen (Trüben) modifizierende Reagenzien zugegeben, beispielsweise Regler für den pH-Wert, Aktivatoren für das im Schaum zu gewinnende Mineral oder Desaktivatoren für die im Schaum unerwünschten Mineralien, und gegebenenfalls auch Dispergatoren.Many collectors for non-sulfidic minerals develop a foam that is suitable for flotation because of their surfactant character. However, it may also be necessary to develop the foam using special foamers or to modify it in a suitable manner. Known foamers for flotation are alcohols with 4 to 10 carbon atoms, polypropylene glycols, polyethylene glycol or polypropylene glycol ethers, terpene alcohols (pine oils) and cresylic acids. If necessary, modifying reagents are added to the suspensions (turbidity) to be floated, for example regulators for the pH value, activators for the mineral to be obtained in the foam or deactivators for the minerals undesirable in the foam, and optionally also dispersants.
Im Unterschied zu anionischen und kationischen Tensiden werden nichtionische Tenside in der Flotation kaum als Sammler eingesetzt. A. Doren, D. Vargas und J. Goldfarb berichten in Trans. Inst. Met. Min. Sect. C., 84 (1975), S. 34-39 über Flotationsversuche an Quarz, Cassiterit und Chrysocolla, die mit einem Anlagerungsprodukt von 9 bis 10 Mol Ethylenoxid an Octylphenol als Sammler durchgeführt wurden. In der einschlägigen Literatur werden auch vereinzelt Kombinationen aus ionischen und nichtionischen Tensiden als Sammler beschrieben. So berichtet A. Doren, A. van Lierde und J.A. de Cuyper in Dev. Min. Proc. 2 (1979), S. 86-109 über Flotationsversuche, die an Cassiterit mit einer Kombination aus einem Anlagerungsprodukt von 9 bis 10 Mol Ethylenoxid an Octylphenol und einem Octadecylsulfosuccinat durchgeführt wurden. V. M. Lovell beschreibt in A.M. Gaudin Memorial Volume, herausgegeben von M.C. Fuerstenau, AIME, New York 1976, Vol. I. S. 597-620 Flotationsversuche, die an Apatit mit einer Kombination aus Tallölfettsäure und Nonylphenyltetraglykolether durchgeführt wurden.In contrast to anionic and cationic surfactants, nonionic surfactants are hardly used as collectors in flotation. A. Doren, D. Vargas and J. Goldfarb report in Trans. Inst. Met. Min. Sect. C., 84 (1975), pp. 34-39 on flotation tests on quartz, cassiterite and chrysocolla, which were carried out with an adduct of 9 to 10 moles of ethylene oxide with octylphenol as a collector. In the relevant literature, combinations of ionic and nonionic surfactants are also occasionally described as collectors. A. Doren, A. van Lierde and J.A. de Cuyper in Dev. Min. Proc. 2 (1979), pp. 86-109 on flotation tests which were carried out on cassiterite with a combination of an adduct of 9 to 10 mol of ethylene oxide with octylphenol and an octadecylsulfosuccinate. V. M. Lovell describes in A.M. Gaudin Memorial Volume, edited by M.C. Fuerstenau, AIME, New York 1976, Vol. I. pp. 597-620 flotation experiments which were carried out on apatite using a combination of tall oil fatty acid and nonylphenyltetraglycol ether.
Für die Flotation von nichtsulfidischen Erzen werden kationische, anionische und ampholytische Sammler eingesetzt, die in vielen Fällen bei ökonomisch vertretbaren Sammlermengen nicht zu einer befriedigenden Ausbringung der Wertmineralien führen. Im Sinne einer wirtschaftlicheren Gestaltung der Flotationsprozesse ist es erstrebenswert, verbesserte Sammler aufzufinden, mit denen entweder bei gleichbleibenden Sammlermengen größere Ausbeuten an Wertmineralien, oder bei verminderten Sammlermengen gleichbleibende Wertmineralausbeuten erzielt werden.Cationic, anionic and ampholytic collectors are used for the flotation of non-sulfidic ores, which in many cases do not lead to a satisfactory application of valuable minerals with economically justifiable collector quantities. In the sense of a more economical design of the flotation processes, it is worthwhile to find improved collectors with which greater yields of valuable minerals can be achieved either with the same amount of collectors or constant mineral yields with reduced amounts of collectors.
Der vorliegenden Erfindung lag deshalb die Aufgabe zugrunde, für die Flotation von nichtsulfidischen Erzen bekannte Sammler (Primärsammler) durch geeignete Zusätze (Co-Sammler) so zu verbessern, daß bei praktisch gleichbleibender Selektivität der Sammler das Ausbringen an Wertmineralien im Flotationsprozess signifikant erhöht wird, wobei dieser Effekt auch so genutzt werden kann, daß bei (im Vergleich zu den Sammlermengen des Standes der Technik) verminderten Mengen an Sammler und Co-Sammler gleichbleibende Ausbeuten an Wertmineralien erhalten werden.The object of the present invention was therefore to improve known collectors (primary collectors) for the flotation of non-sulfidic ores by suitable additives (co-collectors) in such a way that, with practically the same selectivity of the collectors, the application of valuable minerals in the flotation pro zess significantly increased, which effect can also be used so that (compared to the collector amounts of the prior art) reduced amounts of collectors and co-collectors constant yields of valuable minerals are obtained.
Es wurde gefunden, daß Anlagerungsprodukte von Ethylenoxid und Propylenoxid an Fettalkohole mit 8 bis 22 Kohlenstoffatomen sehr wirkungsvolle Zusätze zu anionischen, kationischen oder ampholytischen Tensiden, die als Sammler für die Flotation von nichtsulfidischen Erzen bekannt sind, im Sinne von Co-Sammlern darstellen.It has been found that addition products of ethylene oxide and propylene oxide onto fatty alcohols having 8 to 22 carbon atoms are very effective additives to anionic, cationic or ampholytic surfactants, which are known as collectors for the flotation of non-sulfidic ores, in the sense of co-collectors.
Gegenstand der Erfindung ist die Verwendung von Gemischen aus
- a) mindestens einem Anlagerungsprodukt von Ethylenoxid und Propylenoxid an einen Fettalkohol mit 8 bis 22 Kohlenstoffatomen und
- b) mindestens einem anionischen, kationischen oder ampholytischen Tensid
als Sammler bei der Flotation von nichtsulfidischen Erzen.
- a) at least one adduct of ethylene oxide and propylene oxide with a fatty alcohol having 8 to 22 carbon atoms and
- b) at least one anionic, cationic or ampholytic surfactant
as a collector in the flotation of non-sulfidic ores.
Als Komponente a) werden insbesondere Anlagerungsprodukte von m Mol Ethylenoxid und n Mol Propylenoxid an Fettalkohole mit 8 bis 22 Kohlenstoffatomen eingesetzt, wobei m und n jeweils Zahlen von 1 bis 15 darstellen, die Summe von m und n 2 bis 25 beträgt und das Verhältnis m : n im Bereich von 1 : 5 bis 2 : 1 liegt. Diese Ethylenoxid-iPropylenoxid-Anlagerungsprodukte stellen bekannte Substanzen dar, die nach bekannten Verfahren synthetisiert werden können. In der Regel werden sie dadurch erhalten, daß man unter Verwendung von bekannten alkalischen Alkoxylierungskatalysatoren die vorgesehene Mengen Ethylenoxid Propylenoxid an die als Ausgangsmaterial verwendeten Fettalkohole anlagert. Die Anlagerung der Alkylenoxide kann dabei sowohl so vorgenommen werden, daß man ein entsprechendes Gemisch aus Ethylenoxid und Propylenoxid mit dem Fettalkoholausgangsmaterial zur Reaktion bringt, als auch in der Weise, daß man zuerst das eine Alkylenoxid und danach das andere anlagert. Vorzugsweise setzt man in den erfindungsgemäß zu verwendenden Mischungen solche Produkte als Komponente a) ein, die durch Anlagerung von Ethylenoxid und anschließende Umsetzung mit Propylenoxid erhalten wurden.As component a), in particular adducts of m moles of ethylene oxide and n moles of propylene oxide with fatty alcohols having 8 to 22 carbon atoms are used, where m and n each represent numbers from 1 to 15, the sum of m and n is 2 to 25 and the ratio m : n is in the range of 1: 5 to 2: 1. These ethylene oxide-ipropylene oxide addition products are known substances which can be synthesized by known processes. As a rule, they are obtained by adding the intended amounts of ethylene oxide and propylene oxide to the fatty alcohols used as the starting material using known alkaline alkoxylation catalysts. The addition of the alkylene oxides can be carried out either by reacting an appropriate mixture of ethylene oxide and propylene oxide with the fatty alcohol starting material or by adding one alkylene oxide first and then the other. In the mixtures to be used according to the invention, preference is given to using, as component a), those products which have been obtained by addition of ethylene oxide and subsequent reaction with propylene oxide.
Die Fettalkoholkomponente der unter a) definierten Ethylenoxid-/Propylenoxidanlagerungsprodukte kann aus geradkettigen und verzweigten, gesättigten und ungesättigten Verbindungen dieser Kategorie mit 8 bis 22 Kohlenstoffatomen bestehen, beispielsweise aus n-Octanol, n-Decanol, n-Dodecanol, n-Tetradecanol, n-Hexadecanol, n-Octadecanol, n-Eicosanol, n-Docosanol, n-Hexadecanol, Isotridecanol und Isooctadecanol. Die genannten Fettalkohole können einzeln die Basis der Ethylenoxid-/Propylenoxidanlagerungsprodukte bilden. In der Regel werden als Komponente a) jedoch Produkte auf Basis von Fettalkoholgemischen eingesetzt, wobei diese Fettalkoholgemische aus dem Fettsäureanteil von Fetten und Ölen tierischen oder pflanzlichen Ursprungs herstammen. Solche Fettalkoholgemische lassen sich bekanntlich aus den nativen Fetten und Ölen, u. a. über die Umesterung der Triglyceride mit Methanol und nachfolgende katalytische Hydrierung der Fettsäuremethylester, gewinnen. Hier können sowohl die herstellungsmäßig anfallenden Fettalkoholgemische als auch geeignete Fraktionen mit einem begrenzten Kettenlängenspektrum als Basis für die Anlagerung von Ethylenoxid und Propylenoxid dienen. Neben den aus natürlichen Fetten und Ölen gewonnenen Fettalkoholgemischen sind auch synthetisch gewonnene Fettalkoholgemische, beispielsweise die bekannten Ziegler- und Oxofettalkohole als Ausgangsmaterial für die Herstellung der unter a) definierten Ethylenoxid-/Propylenoxidanlagerungsprodukte geeignet. Als Komponente a) werden bevorzugt Anlagerungsprodukte von Ethylenoxid und Propylenoxid an Fettalkohole mit 12 bis 18 Kohlenstoffatomen eingesetzt.The fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) can consist of straight-chain and branched, saturated and unsaturated compounds of this category with 8 to 22 carbon atoms, for example n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n- Hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-hexadecanol, isotridecanol and isooctadecanol. The fatty alcohols mentioned can individually form the basis of the ethylene oxide / propylene oxide addition products. As a rule, however, products based on fatty alcohol mixtures are used as component a), these fatty alcohol mixtures being derived from the fatty acid component of fats and oils of animal or vegetable origin. Such fatty alcohol mixtures can be known from the native fats and oils, u. a. win over the transesterification of the triglycerides with methanol and subsequent catalytic hydrogenation of the fatty acid methyl ester. Both the fatty alcohol mixtures obtained in the production process and suitable fractions with a limited chain length spectrum can serve as the basis for the addition of ethylene oxide and propylene oxide. In addition to the fatty alcohol mixtures obtained from natural fats and oils, synthetically obtained fatty alcohol mixtures, for example the known Ziegler and oxo fatty alcohols, are also suitable as starting materials for the production of the ethylene oxide / propylene oxide addition products defined under a). Addition products of ethylene oxide and propylene oxide onto fatty alcohols having 12 to 18 carbon atoms are preferably used as component a).
Der Polyalkylenglykolteil der genannten Anlagerungsprodukte enthält im statistischen Mittel pro Mol Fettalkohol 1 bis 10 Mol Ethylenglykoleinheiten und 1 bis 15 Mol Propylenglykoleinheiten. Die molaren Mengen sind dabei so aufeinander abgestimmt, daß 2 bis 25 Mol Alkylenglykoleinheiten pro Mol-Fettalkohol vorhanden sind, und daß das Molverhältnis zwischen Ethylenglykol- und Propylenglykoleinheiten im Bereich von 1 : 5 bis 2 : 1 liegt. Bevorzugt sind hier Produkte, die 2 bis 6 Ethylenglykoleinheiten und 4 bis 12 Propylenglykoleinheiten pro Mol Fettalkohol vorhanden sind, und in denen das Molverhältnis zwischen Ethylenglykoleinheiten und Propylenglykoleinheiten im Bereich von 1 : 1 bis 1 : 2 liegt.The polyalkylene glycol part of the addition products mentioned contains, on average, 1 to 10 moles of ethylene glycol units and 1 to 15 moles of propylene glycol units per mole of fatty alcohol. The molar amounts are coordinated so that 2 to 25 moles of alkylene glycol units are present per mole of fatty alcohol and that the molar ratio between ethylene glycol and propylene glycol units is in the range from 1: 5 to 2: 1. Products which contain 2 to 6 ethylene glycol units and 4 to 12 propylene glycol units per mole of fatty alcohol and in which the molar ratio between ethylene glycol units and propylene glycol units is in the range from 1: 1 to 1: 2 are preferred.
Als Komponente b) kommen anionische, kationische und ampholytische Tenside in Betracht, die an sich als Sammler für die Flotation von nichtsulfidischen Erzen bekannt sind.Component b) includes anionic, cationic and ampholytic surfactants, which are known per se as collectors for the flotation of non-sulfidic ores.
Sollen anionische Tenside erfindungsgemäß als Komponente b) eingesetzt werden, so werden sie insbesondere aus der aus Fettsäuren, Alkylsulfaten, Alkylsulfosuccinaten, Alkylsulfosuccinamaten, Alkylbenzolsulfonaten Alkylsulfonaten, Petroleumsulfonaten und Acyllactylaten bestehenden Gruppe ausgewählt.If anionic surfactants are to be used according to the invention as component b), they are selected in particular from the group consisting of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates and acyl lactylates.
Als Fettsäuren kommen hier vor allem die aus pflanzlichen oder tierischen Fetten und Ölen, beispielsweise durch Fettspaltung und gegebenenfalls Fraktionierung und/oder Trennung nach dem Umnetzverfahren, gewonnenen geradkettigen Fettsäuren mit 12 bis 18 Kohlenstoffatomen, insbesondere solche mit 16 bis 18 Kohlenstoffatomen, in Betracht. Ölsäure und Tallölfettsäure kommt hier eine besondere Bedeutung zu.Suitable fatty acids here are in particular the straight-chain fatty acids with 12 to 18 carbon atoms, in particular those with 16 to 18 carbon atoms, obtained from vegetable or animal fats and oils, for example by fat splitting and optionally fractionation and / or separation by the crosslinking process. Oleic acid and tall oil fatty acid are of particular importance here.
Als Alkylsulfate eignen sich die Schwefelsäurehalbester von Fettalkoholen mit 8 bis 22 Kohlenstoffatomen, vorzugsweise von Fettalkoholen mit 12 bis 18 Kohlenstoffatomen, die geradkettig oder verzweigt sein können. Für die Fettalkoholkomponente der Schwefelsäurehalbester gelten die vorhergehenden Angaben über die Fettalkoholkomponente der unter a) definierten Ethylenoxid-/Propylenoxidanlagerungsprodukte sinngemäß.Suitable as alkyl sulfates are the sulfuric acid semiesters of fatty alcohols with 8 to 22 carbon atoms Men, preferably of fatty alcohols with 12 to 18 carbon atoms, which can be straight-chain or branched. For the fatty alcohol component of the sulfuric acid half-esters, the previous information applies analogously to the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a).
Als Alkylsulfosuccinate kommen Sulfobernsteinsäurehalbester von Fettalkoholen mit 8 bis 22 Kohlenstoffatomen, vorzugsweise von Fettalkoholen mit 12 bis 18 Kohlenstoffatomen in Betracht. Diese Alkylsulfosuccinate können beispielsweise durch Umsetzung entsprechender Fettalkohole oder Fettalkoholgemische mit Maleinsäureanhydrid und nachfolgende Anlagerung von Alkalimetallsulfit oder Alkalimetallhydrogensulfit erhalten werden. Für die Fettalkoholkomponente der Sulfobernsteinsäureester gelten wiederum die Angaben über die Fettalkoholkomponente der unter a) definierten Ethylenoxid-/Propylenoxidanlagerungsprodukte sinngemäß.Suitable alkyl sulfosuccinates are sulfosuccinic acid semiesters of fatty alcohols having 8 to 22 carbon atoms, preferably fatty alcohols having 12 to 18 carbon atoms. These alkyl sulfosuccinates can be obtained, for example, by reacting appropriate fatty alcohols or fatty alcohol mixtures with maleic anhydride and subsequent addition of alkali metal sulfite or alkali metal bisulfite. For the fatty alcohol component of the sulfosuccinic acid esters, the information on the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) applies analogously.
Die als mögliche Komponente b) in Betracht gezogenen Alkylsulfosuccinamate entsprechen der Formel I,
Für die Verwendung als Komponente b) geeignete Alkylbenzolsulfonate entsprechen der Formel II,
Alkylsulfonate, die für die Verwendung als Komponente b) in Betracht kommen, entsprechen der Formel 111,
Die für die Verwendung als Komponente b) geeigneten Petroleumsulfonate wurden aus Schmierölfraktionen, in der Regel durch Sulfonierung mit Schwefeltrioxid oder Oleum erhalten. Hier kommen insbesondere solche Verbindungen in Betracht, in denen die Kohlenwasserstoffreste überwiegend Kettenlängen im Bereich von 8 bis 22 Kohlenstoffatomen, besitzen.The petroleum sulfonates suitable for use as component b) were obtained from lubricating oil fractions, generally by sulfonation with sulfur trioxide or oleum. Compounds in which the hydrocarbon radicals predominantly have chain lengths in the range from 8 to 22 carbon atoms are particularly suitable here.
Die weiterhin als mögliche Komponente b) in Betracht gezogenen Acyllactylate entsprechen der Formel IV,
Wenn erfindungsgemäß kationische Tenside als Komponente b) eingesetzt werden sollen, so kommen insbesondere primäre aliphatische Amine sowie mit a-verzweigten Alkylresten substituierte Alkylendiamine oder hydroxyalkylsubstituierte Alkylendiamine und wasserlösliche Säureadditionssalze dieser Amine in Betracht.If, according to the invention, cationic surfactants are to be used as component b), primary aliphatic amines and alkylene diamines substituted with a-branched alkyl radicals or hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines are particularly suitable.
Als primäre aliphatische Amine eignen sich vor allem die von den Fettsäuren der nativen Fette und Öle abstammenden Fettamine mit 8 bis 22 Kohlenstoffatomen, die bereits weiter oben im Zusammenhang mit den ebenfalls als Komponente b) in Betracht kommenden Alkylsulfosuccinamaten beschrieben wurden. Auch hier werden in der Regel Gemische von Fettaminen eingesetzt, beispielsweise Talgamine oder Hydrotalgamine, wie sie aus den Talgfettsäuren bzw. den hydrierten Talgfettsäuren über die entsprechenden Nitrile und deren Hydrierung zugänglich sind.Particularly suitable primary aliphatic amines are the fatty amines with 8 to 22 carbon atoms derived from the fatty acids of the native fats and oils, which have already been described above in connection with the alkylsulfosuccinamates which are also suitable as component b). Here too, mixtures of fatty amines are generally used, for example tallow amines or hydrotalgamines, as are obtainable from the tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their hydrogenation.
Die für die Verwendung als Komponente b) geeigneten alkylsubstituierten Alkylendiamine entsprechen der Formel V,
Die für die Verwendung als Komponente b) geeigneten hydroxyalkylsubstituierten Alkylendiamine entsprechen der Formel VI,
Die vorgenannten Aminverbindungen können als solche oder in Form ihrer wasserlöslichen Salze verwendet werden. Die Salze werden im gegebenen Fall durch Neutralisation, die sowohl mit äquimolaren Mengen als auch mit einem Überschuß oder Unterschuß an Säure durchgeführt werden kann, erhalten. Geeignete Säuren sind beispielsweise Schwefelsäure, Phosphorsäure, Salzsäure, Essigsäure und Ameisensäure.The aforementioned amine compounds can be used as such or in the form of their water-soluble salts. If appropriate, the salts are obtained by neutralization, which can be carried out both with equimolar amounts and with an excess or an excess of acid. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
Bei den ampholytischen Tensiden, die erfindungsgemäß als Komponente b) eingesetzt werden, handelt es sich um Verbindungen, die im Molekül mindestens eine anionenaktive und eine kationenaktive Gruppe enthalten, wobei die anionenaktiven Gruppen vorzugsweise aus Sulfonsäure- oder Carboxylgruppen und die kationenaktiven Gruppen aus Aminogruppen, vorzugsweise auf sekundären oder tertiären Aminogruppen, bestehen. Als ampholytische Tenside kommen insbesondere Sarkoside, Tauride, N-substituierte Aminopropionsäuren und N-(1,2-Dicarboxyethyl)-N-alkylsulfosuccinamate in Betracht.The ampholytic surfactants which are used according to the invention as component b) are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active groups preferably consisting of sulfonic acid or carboxyl groups and the cation-active groups consisting of amino groups, preferably on secondary or tertiary amino groups, consist. Particularly suitable ampholytic surfactants are sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates.
Die für die Verwendung als Komponente b) geeigneten Sarkoside entsprechen der Formel VII,
Die für die Verwendung als Komponente b) geeigneten Tauride entsprechen der Formel VIII,
N-substituierte Aminopropionsäuren, die sich für die Verwendung als Komponente b) eignen, entsprechen der Formel IX,
Die für die Verwendung als Komponente b) in den erfindungsgemäßen Sammlergemischen geeigneten N-(1,2-Dicarboxyethyl)-N-alkylsulfosuccinamate entsprechen der Formel (X),
In den erfindungsgemäß zu verwendenden Gemischen aus nichtionogenen und ionogenen Tensiden liegt das Gewichtsverhältnis der Komponenten a) : b) im Bereich von 1 : 19 bis 3 : 1, vorzugsweise im Bereich von 1 : 4 bis 1 : 1.In the mixtures of nonionic and ionic surfactants to be used according to the invention, the weight ratio of components a): b) is in the range from 1:19 to 3: 1, preferably in the range from 1: 4 to 1: 1.
Die Mengen, in denen die erfindungsgemäß zu verwendenden Sammlergemische eingesetzt werden, hängen jeweils von der Art der zu flotierenden Erze und von deren Gehalt an Wertmineralien ab. Demzufolge können die jeweils notwendigen Einsatzmengen in weiten Grenzen schwanken. Im allgemeinen werden die erfindungsgemäßen Sammlergemische in Mengen von 20 bis 2000 g pro Tonne Roherz eingesetzt.The amounts in which the collector mixtures to be used according to the invention are used depend in each case on the type of ores to be floated and on their content of valuable minerals. As a result, the amounts required can vary within wide limits. In general, the collector mixtures according to the invention are used in amounts of 20 to 2000 g per ton of raw ore.
Die Sammlerwirksamkeit der erfindungsgemäß zu verwendenden Tensidgemische wird durch die Härtebildner des zur Herstellung der Trüben verwendeten Wassers praktisch nicht beeinträchtigt.The effectiveness of the collectors of the surfactant mixtures to be used according to the invention is practically not impaired by the hardness formers of the water used to produce the slurries.
In der Praxis werden die erfindungsgemäß zu verwendenden Gemische aus primären Sammlern und Co-Sammlern in den bekannten Flotationsverfahren für nichtsulfidische Erze anstelle der bekannten anionischen, kationischen und/oder ampholytischen Sammler eingesetzt. Dementsprechend werden auch hier neben den Sammlergemischen die jeweils gebräuchlichen Reagenzien wie Schäumer, Regler, Aktivatoren, Desaktivatoren usw. den wäßrigen Aufschlämmungen der vermahlenen Erze zugesetzt. Die Durchführung der Flotation erfolgt unter den Bedingungen der Verfahren des Standes der Technik. In diesem Zusammenhang sei auf die folgenden Literaturstellen zur Technologie der Erzaufbereitung verwiesen: H. Schubert, Aufbereitung fester mineralischer Rohstoffe, Leipzig 1967; B. Wills, Mineral Processing Technology Plant Design, New York, 1978; D. B. Purchas (ed.), Solid/Liquid Separation Equipment Scale-up, Croydon 1977; E.S. Perry, C.J. van Oss, E. Grushka (ed.), Separation and Purification Methods, New York 1973-1978.In practice, the mixtures of primary collectors and co-collectors to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of the known anionic, cationic and / or ampholytic collectors. Accordingly, in addition to the collector mixtures, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous slurries of the ground ores. The flotation is carried out under the conditions of the methods of the prior art. In this context, reference is made to the following references on ore processing technology: H. Schubert, Processing of Solid Mineral Raw Materials, Leipzig 1967; B. Wills, Mineral Processing Technology Plant Design, New York, 1978; D. B. Purchas (ed.), Solid / Liquid Separation Equipment Scale-up, Croydon 1977; IT. Perry, C.J. van Oss, E. Grushka (ed.), Separation and Purification Methods, New York 1973-1978.
Die erfindungsgemäß zu verwendenden Sammlergemische können beispielsweise eingesetzt werden bei der Flotation von Apatit- Scheelit- und Wolframiterzen, bei der Trennung von Fluorit von Quarz, bei der Trennung von Quarz oder Alkalisilikaten von Hämatit, Magnetit und Chromit durch inverse Flotation, bei der Trennung von Cassiterit von Quarz und Silikaten, und bei der Trennung von Oxiden des Eisens und Titans von Quarz zur Reinigung von Glassanden.The collector mixtures to be used according to the invention can be used, for example, in the flotation of apatite-Scheelite and tungsten ores, in the separation of fluorite from quartz, in the separation of quartz or alkali silicates from hematite, magnetite and chromite by inverse flotation, in the separation of cassiterite of quartz and silicates, and in the separation of oxides of iron and titanium from quartz for cleaning glass sands.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Abtrennung nichtsulfidischer Mineralien aus einem Erz durch Flotation, bei dem man gemahlenes Erz mit Wasser zu einer Erzsuspension vermischt, in die Suspension in Gegenwart eines als Sammler wirksamen anionischen, kationischen oder ampholytischen Tensids Luft einleitet und den entstandenen Schaum zusammen mit dem darin enthaltenen Mineral abtrennt. Dieses Verfahren ist dadurch gekennzeichnet, daß man als Sammler Gemische aus
- a) mindestens einem Anlagerungsprodukt von Ethylenoxid und Propylenoxid an einen Fettalkohol mit 8 bis 22 Kohlenstoffatomen und
- b) mindestens einem anionischen, kationischen oder ampholytischen Tensid
einsetzt.
- a) at least one adduct of ethylene oxide and propylene oxide with a fatty alcohol having 8 to 22 carbon atoms and
- b) at least one anionic, cationic or ampholytic surfactant
starts.
Die nachfolgenden Beispiele sollen die Überlegenheit der erfindungsgemäß zu verwendenden Sammlergemische zeigen. Unter Laborbedingungen wurde teilweise mit erhöhten Sammlerkonzentrationen gearbeitet, die in der Praxis erheblich unterschritten werden können. Die Anwendungsmöglichkeiten und Anwendungsbedingungen sind daher nicht auf die in den Beispielen beschriebenen Trennaufgaben und Versuchsbedingungen beschränkt. Alle Prozentangaben sind, sofern nicht anders angegeben, in Gewichtsprozent. Die Mengenangaben für Reagenzien beziehen sich jeweils auf Aktivsubstanz.The following examples are intended to demonstrate the superiority of the collector mixtures to be used according to the invention. Under laboratory conditions, increased collector concentrations were sometimes used, which can be considerably undercut in practice. The possible uses and applications conditions are therefore not limited to the separation tasks and test conditions described in the examples. Unless otherwise stated, all percentages are in percent by weight. The amounts of reagents are based on the active substance.
Das zu flotierende Material bestand aus einem Apatiterz aus dem südafrikanischen Phalaborawa-Komplex, das folgende Mineralien als Hauptbestandteile enthält:
- 39% Magnetit
- 11 % Carbonate
- 9% Olivin
- 14% Phlogopid
- 18% Apatit
- 39% magnetite
- 11% carbonates
- 9% olivine
- 14% phlogopid
- 18% apatite
Der P2O5-Gehalt des Erzes beträgt 6,4%. Die Flotationsaufgabe hatte folgende Korngrößenverteilung:
- 18% <25 µm
- 34% 25-100 µm
- 43% 100-200 µm
- 5% >200 µm
- 18% <25 µm
- 34% 25-100 µm
- 43% 100-200 µm
- 5%> 200 µm
Als Sammler wurden folgende Substanzen oder Substanzgemische eingesetzt (GT = Gewichtsteile):The following substances or substance mixtures were used as collectors (GT = parts by weight):
- 2,00 GT technische Ölsäure (gesättigt: 1% C12; 3% C14; 0,5 C15; 5% C16; 1% C17; 2% C18; einfach ungesättigt: 6% C16; 70% C18; zweifach ungesättigt: 10% C18; dreifach ungesättigt 0,5% C12; Säurezahl 199-204; Verseifungszahl 200-205; Jodzahl 86-96)2.00 GT technical oleic acid (saturated: 1% C 12 ; 3% C 14 ; 0.5 C 15 ; 5% C 16 ; 1% C 17 ; 2% C 18 ; monounsaturated: 6% C 16 ; 70% C 18 ; double unsaturated: 10% C 18 ; triple unsaturated 0.5% C 12 ; acid number 199-204; saponification number 200-205; iodine number 86-96)
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (0-3% C10; 48-58% C12; 19-24% C14; 9-12% C16; 10-13% C18; Säurezahl 0; Hydroxylzahl 265-275; Verseifungszahl 1,2; Jodzahl 0,5)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (0-3% C 10 ; 48-58% C 12 ; 19-24% C 14 ; 9-12% C 16 ; 10-13 % C 18 ; acid number 0; hydroxyl number 265-275; saponification number 1.2; iodine number 0.5)
- 2,00 GT Natrium-/Ammoniumsalz (Molverhältnis Na+ : NH4 = 1 : 1) eines Monoalkylsulfosuccinates, dessen Alkylrest sich von einem technischen Oleyl-Cetylalkohol (2% C12; 3-8% C14; 27-36% C16; 58-68% C1s; 0-2% C20; Säurezahl 0,5; Hydroxylzahl 210-225; Verseifungszahl 2; Jodzahl 48-55) ableitet.2.00 GT sodium / ammonium salt (molar ratio Na + : NH4 = 1: 1) of a monoalkylsulfosuccinate, the alkyl radical of which is derived from an industrial oleyl cetyl alcohol (2% C 12 ; 3-8% C 14 ; 27-36% C 16 ; 58-68% C 1 s; 0-2% C 20 ; acid number 0.5; hydroxyl number 210-225; saponification number 2; iodine number 48-55).
- 1,0 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.0 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
- 2,00 GT Natrium-/Ammoniumsalz eines Monoalkylsulfosuccinates (siehe Sammler C)2.00 GT sodium / ammonium salt of a monoalkyl sulfosuccinate (see collector C)
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol Isotridecanol1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of isotridecanol
- 2,00 GT Natrium-/Ammoniumsalz eines Monoalkylsulfosuccinates (siehe Sammler C).2.00 pbw of sodium / ammonium salt of a monoalkyl sulfosuccinate (see collector C).
- 1,00 GT Anlagerungsprodukt von 5 Mol Propylenoxid an 1 Mol 2-Ethylhexanol.1.00 GT adduct of 5 moles of propylene oxide with 1 mole of 2-ethylhexanol.
- 2,00 GT Acetat eines N-(2-Hydroxy-C11-14-alkyl)-ethylendiamins, hergestellt durch Umsetzung eines 1,2-Epoxy-C11-14-alkans (Kettenlängenverteilung: 22% C11; 30% C12; 26% C13; 22% C14) mit Ethylendiamin und anschließende Neutralisation mit Eisessig.2.00 pbw of acetate of an N- (2-hydroxy-C 11-14 -alkyl) -ethylenediamine, prepared by reacting a 1,2-epoxy-C 11-14 -alkane (chain length distribution: 22% C 11 ; 30% C 12 ; 26% C 13 ; 22% C 14 ) with ethylenediamine and subsequent neutralization with glacial acetic acid.
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A).1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A).
- 2,00 GT Acetat eines N-(2-Hydroxy-C11-14-alkyl)-ethylendiamins (siehe Sammler G)2.00 pbw of acetate of an N- (2-hydroxy-C 11-14 alkyl) ethylenediamine (see collector G)
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol Isotridecanol1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of isotridecanol
Die Flotationsversuche wurden in einer Laboratoriumsflotationszelle (Modell D-1 der Firma Denver Equipment mit einem Fassungsvermögen von 1,2 Liter) bei ca. 20°C durchgeführt. Zur Herstellung der Trüben wurde in den Beispielen 1 bis 6 Leitungswasser mit einer Härte von 18 °dH verwendet. Die Trüben für die Beispiele 4 und 6 wurden unter Verwendung von hartem Wasser (945 ppm Ca2+ und 1700 ppm Mg2+) hergestellt. Nach dem Aufschlämmen des Erzes in der Flotationszelle wurde der Magnetit mit einem Handmagneten entfernt, gewaschen und das Waschwasser in die Zelle zurückgeführt. Die Trübedichte betrug 500 g/I. Als Drücker wurde Wasserglas in Mengen von 1000 und 2000 g/t eingesetzt. Der pH-Wert der Trüben wurde jeweils auf 11 eingestellt. Flotiert wurde bei einer Umdrehungszahl der Mischvorrichtung von 1500 pro Minute. Die Flotationszeit betrug 6 Minuten. Nach der Vorflotation (rougher-Flotation) wurde das Vorkonzentrat zweimal nachgereinigt, wobei in den Beispielen 3, 4 und 7 für die erste Reinigungsflotation Sammler nachdosiert wurde.The flotation tests were carried out in a laboratory flotation cell (model D-1 from Denver Equipment with a capacity of 1.2 liters) at approx. 20 ° C. Tap water with a hardness of 18 ° dH was used in Examples 1 to 6 to produce the slurries. The slurries for Examples 4 and 6 were prepared using hard water (945 ppm Ca 2+ and 1700 ppm Mg 2+ ). After the ore had been slurried in the flotation cell, the magnetite was removed with a hand magnet, washed and the wash water returned to the cell. The cloud density was 500 g / l. Water glass in quantities of 1000 and 2000 g / t was used as the pusher. The pH of the turbidity was adjusted to 11 in each case. Flotation was carried out at a rotation speed of the mixing device of 1500 per minute. The flotation time was 6 minutes. After the preliminary flotation (rougher flotation), the preconcentrate was cleaned twice, in Examples 3, 4 and 7, collectors were metered in for the first cleaning flotation.
In der nachfolgenden Tabelle I sind in Spalte 2 die jeweils eingesetzten Sammler und ihre Mengen angegeben. In Spalte 3 ist jeweils die Menge des als Drücker eingesetzten Wasserglases verzeichnet. In Spalte 4 steht "Magn." für Magnetitabtrennung, "V.-F" für Vorflotation, "R-F" für Reinigungsflotation und "Konz." für Konzentrat. In Spalte 5 ist das Gesamtausbringen der jeweiligen Flotationsstufe, bezogen auf die gesamte Erzmenge, angegeben, in Spalte 6 der P2O5-Gehalt der Berge in der jeweiligen Verfahrensstufe und in Spalte 7 der Anteil der in jeder verfahrensstufe ausgebrachten P20s-Menge an der im Erz entstandenen P2O5-Gesamtmenge.
Das zu flotierende Erz bestand aus einem Apatiterz aus Brasilien, das ca. 20% Apatit, ca. 35% Magnetit, Limonit und Hämatit sowie ca. 16 % Calcit enthält. Der P20s-Gehalt des Erzes beträgt ca. 22 %. Die Flotationsaufgabe besaß folgende Korngrößenverteilung:
- 21% <25 µm
- 38% 40 - 100 µm
- 35% 100 - 250 µm
- 6% >250 µm
- Folgende Sammler wurden eingesetzt:
- 21% <25 µm
- 38% 40-100 µm
- 35% 100-250 µm
- 6%> 250 µm
- The following collectors were used:
- 1,00 GT Natriumsalz eines von einem Talgamin abgeleiteten Sulfosuccinamates1.00 pbw of sodium salt of a sulfosuccinamate derived from a tallow amine
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
Die Flotationsversuche wurden unter den für die Beispiele 1 bis 8 beschriebenen Bedingungen mit den folgenden Abweichungen durchgeführt: Als Drücker wurde Stärke eingesetzt. Der pH-Wert der Trüben betrug jeweils 10,5. Die Trüben wurden unter Verwendung von Leitungswasser mit einer Härte von 18° dH hergestellt. Die Eisenoxide waren vor der Apatitflotation durch Magnetscheidung entfernt worden.The flotation tests were carried out under the conditions described for Examples 1 to 8 with the following deviations: Starch was used as the pusher. The pH of the turbidity was 10.5 in each case. The slurries were prepared using tap water with a hardness of 18 ° dH. The iron oxides had been removed by magnetic separation before the apatite flotation.
Die gefundenen Ergebnisse sind in der nachstehenden Tabelle II wiedergegeben, in der die Ergebnisse der 1. und 2. Reinigungsflotation zusammengefaßt sind, für die aber im übrigen die Erläuterungen zur Tabelle I sinngemäß gelten.
Als zu flotierendes Material wurde ein Scheeliterz aus Österreich mit der nachstehenden chemischen Zusammensetzung bezogen auf die Hauptbestandteile eingesetzt:
- W03 0,4%
- CaO 6,8%
- Si02 59,5%
- Fe203 7.0%
- A1203 12,1%
- MgO 5,7%
- W0 3 0.4%
- CaO 6.8%
- Si0 2 59.5%
- Fe 2 0 3 7.0%
- A1 2 0 3 12.1%
- MgO 5.7%
Die Flotationsaufgabe hatte die folgende Korngrößenverteilung:
- 28% <25 µm
- 43% 25-100 µm
- 29% 100-200 µm
- 28% <25 µm
- 43% 25-100 µm
- 29% 100-200 µm
Alle eingesetzten Sammlermischungen enthielten als erfindungsgemäß zu verwendenden Komponente b) ein Natrium-/Ammoniumsalz (Molverhältnis Na : NH4 = 1 : 1) eines Monoalkylsulfosuccinates, dessen Alkylrest sich von einem technischen Oleyl-Cetylalkohol (2% C12; 3-8% C14; 27-36% C18; 0-2% C20; Säurezahl 0,5; Hydroxylzahl 210-225; Verseifungszahl 2; Jodzahl 48-55) ableitet (in der nachstehenden Tabelle als Sammler A' bezeichnet).All of the collector mixtures used contained, as component b) to be used according to the invention, a sodium / ammonium salt (molar ratio Na: NH4 = 1: 1) of a monoalkylsulfosuccinate, the alkyl radical of which is derived from technical oleyl cetyl alcohol (2% C 12 ; 3-8% C 14 ; 27-36% C 18 ; 0-2% C 20 ; acid number 0.5; hydroxyl number 210-225; saponification number 2; iodine number 48-55) (referred to as collector A 'in the table below).
Als erfindungsgemäß zu verwendenden Komponente a) wurden die nachstehend genannten Anlagerungsprodukte von Ethylenoxid und Propylenoxid an einen technischen Laurylalkohol (0-3% C10; 48-58% C12; 19-24% C14; 9-12% C16; 10-13% C18; Säurezahl 0; Hydroxylzahl 265-275; Verseifungszahl 1,2; Jodzahl 0,5) eingesetzt:
- - ein Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol Fettalkohol (in der nachstehenden Tabelle III als Co-Sammler A" bezeichnet)
- - ein Anlagerungsprodukt von 2,5 Mol Ethylenoxid und 6 Mol Propylenoxid an 1 Mol Fettalkohol (Co-Sammler B")
- - ein Anlagerungsprodukt von 4 Mol Ethylenoxid und 5 Mol Propylenoxid an 1 Mol Fettalkohol (Co-Sammler C").
- an adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of fatty alcohol (referred to as Co-Collector A "in Table III below)
- an adduct of 2.5 moles of ethylene oxide and 6 moles of propylene oxide with 1 mole of fatty alcohol (co-collector B ")
- - An adduct of 4 moles of ethylene oxide and 5 moles of propylene oxide with 1 mole of fatty alcohol (co-collector C ").
Die im Beispiel 22 eingesetzte Vergleichszusammensetzung enthielt als Komponente a) ein Anlagerungsprodukt von 5 Mol Ethylenoxid an ein Mol Nonylphenol (Co-Sammler D").The comparative composition used in Example 22 contained as component a) an adduct of 5 moles of ethylene oxide with one mole of nonylphenol (co-collector D ").
Die Flotationsversuche wurden in einer modifizierten Hallimond-Röhre (Mikroflotationszelle) nach B. Dobias, Colloid & Polymer Sci. 259 (1981), S. 775-776 bei 23°C durchgeführt. Die einzelnen Versuche wurden mit jeweils 2 g Erz durchgeführt. Zur Herstellung der Trübe wurde destilliertes Wasser verwendet. Den Trüben wurde jeweils so viel Sammler und Co-Sammler zugegeben, daß eine Sammlergesamtmenge von 500 g/t vorhanden war. Die Konditionierungszeit betrug jeweils 15 Minuten. Während der Flotation wurde ein Luftstrom mit einem Durchfluß von 4 ml/min durch die Trübe geleitet. Die Flotationsdauer war in allen Versuchen 2 Minuten.The flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Sci. 259 (1981), pp. 775-776 at 23 ° C. The individual tests were carried out with 2 g ore each. Distilled water was used to prepare the slurry. Sufficient collectors and co-collectors were added to the turbidities so that a total collector quantity of 500 g / t was available. The conditioning time was 15 minutes each. During the flotation, a flow of air was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 2 minutes in all experiments.
Die gefundenen Ergebnisse sind in der nachfolgenden Tabelle III wiedergegeben. Dabei sind in den Spalten 2 und 3 die jeweils verwendeten Sammler und Co-Sammler, in Spalte 4 deren Gewichtsverhältnis angegeben. In Spalte 5 ist das Gesamtausbringen, bezogen auf die gesamte Erzmenge, und in Spalte 6 das Metallausbringen, bezogen auf die im Erz vorhandene W03-Gesamtmenge, verzeichnet. In den Spalten 7, 8 und 9 sind die W03-, CaO- und Si02-Gehalte der jeweiligen Konzentrate wiedergegeben.
Das zu flotierende Material bestand aus einem Kaoliniterz aus der Oberpfalz, das 55,1% Tonsubstanz und 44,9% Feldspat enthielt. Die Flotationsaufgabe hatte die folgende Korngrößenverteilung:
- 64% <25 µm
- 22% 25-40 µm
- 14% >40 µm
- 64% <25 µm
- 22% 25-40 µm
- 14%> 40 µm
Als Sammler wurden folgende Substanzen oder Substanzgemische eingesetzt:The following substances or mixtures of substances were used as collectors:
- 3,00 GT handelsübliches Natriumalkylbenzolsulfonat, dessen Alkylreste 12 bis 16 Kohlenstoffatome, überwiegend 12 Kohlenstoffatome, aufweisen3.00 pbw of commercially available sodium alkylbenzenesulfonate, the alkyl radicals of which have 12 to 16 carbon atoms, predominantly 12 carbon atoms
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
- 2,00 GT handelsübliches Alkylbenzolsulfonat (siehe Sammler I)2.00 pbw of commercially available alkylbenzenesulfonate (see collector I)
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
- 1,00 GT handelsübliches Alkylbenzolsulfonat (siehe Sammler I)1.00 GT commercial alkylbenzenesulfonate (see collector I)
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
- 2,00 GT N-ß-Hydroxy-C12-14.-alkylethylendiaminformiat, hergestellt durch Umsetzung eines linearen α-C12-14-Epoxyalkans mit Ethylendiamin und anschließende Neutralisation mit Ameisensäure2.00 GT N-ß-hydroxy-C 12-14. Alkylethylendiaminformiat-produced by the reaction of a linear α-C 12-14 -Epoxyalkans with ethylene diamine and subsequent neutralization with formic acid
- 1,00 GT Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol technischen Laurylalkohol (siehe Sammler A)1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of technical lauryl alcohol (see collector A)
Die Flotationsversuche wurden mit einer Humbold-Wedag-Labor-Flotationsmaschine der Fa. KHD Industrieanlagen AG, Humbold-Wedag, Köln (siehe Seifen-Fette-Wachse 105 (1979), S. 248) unter Verwendung einer 1 1-Flotationszelle durchgeführt. Zur Herstellung der Trüben wurde Leitungswasser mit einer Härte von 18° dH verwendet. Die Trübedichte betrug 250 g/l. Als Aktivator wurde Aluminiumsulfat und zwar jeweils in einer Menge von 500 g/t eingesetzt. Der pH-Wert wurde mit Hilfe von Schwefelsäure auf 3 eingestellt. Die Konditionierzeit betrug 10 Minuten. Flotiert wurde 15 Minuten lang bei 23°C und mit einer Umdrehungszahl des Rotors von 1200 Umdrehungen pro Minute. Der Sammler wurde in der aus der nachstehenden Tabelle IV ersichtlichen Weise in 3 oder 4 Teilmengen den Trüben zugesetzt.The flotation experiments were carried out using a Humbold-Wedag laboratory flotation machine from KHD Industrieanlagen AG, Humbold-Wedag, Cologne (see Seifen-Fette-Wachsen 105 (1979), p. 248) using a 1 1 flotation cell. Tap water with a hardness of 18 ° dH was used to produce the cloudiness. The cloud density was 250 g / l. Aluminum sulfate was used as the activator, in each case in an amount of 500 g / t. The pH was adjusted to 3 using sulfuric acid. The conditioning time was 10 minutes. The flotation was carried out for 15 minutes at 23 ° C. and with a rotor speed of 1200 revolutions per minute. The collector was added to the slurries in 3 or 4 aliquots in the manner shown in Table IV below.
Die gefundenen Ergebnisse sind in der Tabelle IV verzeichnet, für die die Erläuterungen zur Tabelle I sinngemäß gelten.
Claims (9)
as collectors in the flotation of non-sulfidic ores.
are used as collector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86106023T ATE65945T1 (en) | 1985-05-11 | 1986-05-02 | USE OF SURFACTANT MIXTURES AS AID FOR THE FLOTATION OF NON-SULPHIDE ORES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3517154 | 1985-05-11 | ||
| DE19853517154 DE3517154A1 (en) | 1985-05-11 | 1985-05-11 | USE OF SURFACTANT MIXTURES AS AUXILIARIES FOR THE FLOTATION OF NON-SULFIDIC ORES |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0201815A2 EP0201815A2 (en) | 1986-11-20 |
| EP0201815A3 EP0201815A3 (en) | 1989-10-18 |
| EP0201815B1 true EP0201815B1 (en) | 1991-08-07 |
| EP0201815B2 EP0201815B2 (en) | 1994-08-03 |
Family
ID=6270591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86106023A Expired - Lifetime EP0201815B2 (en) | 1985-05-11 | 1986-05-02 | Use of surfactant mixtures as flotation agents for non-sulfide ores |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4789466A (en) |
| EP (1) | EP0201815B2 (en) |
| AT (1) | ATE65945T1 (en) |
| AU (1) | AU581512B2 (en) |
| BR (1) | BR8602081A (en) |
| DE (2) | DE3517154A1 (en) |
| ES (1) | ES8900152A1 (en) |
| FI (1) | FI79952C (en) |
| MX (1) | MX170350B (en) |
| PT (1) | PT82561B (en) |
| TR (1) | TR24023A (en) |
| ZA (1) | ZA863466B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015000931A2 (en) | 2013-07-05 | 2015-01-08 | Akzo Nobel Chemicals International B.V. | The synthesis of new anionic surfactants and their use as collectors in froth flotation of non-sulphidic ores |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732667A (en) * | 1985-02-20 | 1988-03-22 | Berol Kemi Ab | Process and composition for the froth flotation beneficiation of iron minerals from iron ores |
| US4725358A (en) * | 1986-09-30 | 1988-02-16 | Union Carbide Corporation | Process for the separation of solid particulate matter |
| DE3641447A1 (en) * | 1986-12-04 | 1988-06-09 | Henkel Kgaa | TENSIDE MIXTURES AS COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES |
| DE3707034A1 (en) * | 1987-03-05 | 1988-09-15 | Henkel Kgaa | USE OF DERIVATIVES OF TRICYCLO- (5.3.1.0 (UP ARROW) 2 (UP ARROW) (UP ARROW), (UP ARROW) (UP ARROW) 6 (UP ARROW)) - DECENS-3 AS FOAMER IN COAL AND ORE FLOTATION |
| EP0298392A3 (en) * | 1987-07-07 | 1991-01-09 | Henkel Kommanditgesellschaft auf Aktien | Method and agents for obtaining minerals from sulphate ores by flotation |
| DE3818482A1 (en) * | 1988-05-31 | 1989-12-07 | Henkel Kgaa | TENSIDE MIXTURES AS COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES |
| US5147528A (en) * | 1990-04-12 | 1992-09-15 | Falconbridge Limited | Phosphate beneficiation process |
| CA2014882C (en) * | 1990-04-19 | 1996-02-20 | Richard R. Klimpel | Depression of the flotation of silica or siliceous gangue in mineral flotation |
| US5173208A (en) * | 1991-06-17 | 1992-12-22 | Nalco Canada Inc. | Liquid suspension of polyethylene oxide for use in treating paper and pulp wastewater |
| US5230808A (en) * | 1991-06-17 | 1993-07-27 | Nalco Canada Inc. | Liquid suspension of polyethylene oxide for use in treating paper and pulp wastewater |
| US6799682B1 (en) | 2000-05-16 | 2004-10-05 | Roe-Hoan Yoon | Method of increasing flotation rate |
| WO2006084170A2 (en) | 2005-02-04 | 2006-08-10 | Mineral And Coal Technologies, Inc. | Improving the separation of diamond from gangue minerals |
| EP2017009B1 (en) * | 2007-07-20 | 2013-07-03 | Clariant (Brazil) S.A. | Reverse iron ore flotation by collectors in aqueous nanoemulsion |
| ES2568777T3 (en) * | 2010-01-08 | 2016-05-04 | Université De Lorraine | Flotation process to recover feldspar from a feldspar mineral |
| EP2768618A2 (en) | 2011-10-18 | 2014-08-27 | Cytec Technology Corp. | Froth flotation processes |
| CA2852679A1 (en) | 2011-10-18 | 2013-04-25 | Cytec Technology Corp. | Collector compositions and method of using the same to collect value minerals in a froth flotation process |
| US9302273B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
| EP2708282A1 (en) * | 2012-09-13 | 2014-03-19 | Clariant International Ltd. | Composition for dressing phosphate ore |
| US10376901B2 (en) | 2014-09-18 | 2019-08-13 | Akzo Nobel Chemicals International B.V. | Use of branched alcohols and alkoxylates thereof as secondary collectors |
| CN104689924B (en) * | 2015-02-28 | 2017-02-22 | 东北大学 | Amphoteric combined collector for reverse flotation of hematite iron ore |
| CN105642448B (en) * | 2015-12-30 | 2018-07-27 | 中南大学 | A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore |
| RU2702044C2 (en) | 2016-03-22 | 2019-10-03 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Use of an emulsifier in a flotation agent composition |
| CN112638540B (en) * | 2018-08-30 | 2023-11-14 | 巴斯夫欧洲公司 | Enrichment of phosphate from phosphate-containing ores |
| WO2020083793A1 (en) | 2018-10-23 | 2020-04-30 | Basf Se | Collector composition and flotation process for beneficiation of phosphate |
| CN113262876A (en) * | 2021-04-09 | 2021-08-17 | 江西理工大学 | Beneficiation method for recovering wolframite from tailings |
| EP4129486A1 (en) * | 2021-08-04 | 2023-02-08 | Kao Corporation S.A.U | Collector for the flotation of carbonates in phosphate rock |
| EP4342587A1 (en) | 2022-09-22 | 2024-03-27 | ArrMaz Products Inc. | Collector composition for beneficiating carbonaceous phosphate ores |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2302338A (en) * | 1938-05-18 | 1942-11-17 | Moeller August | Froth flotation |
| US2611485A (en) * | 1949-04-21 | 1952-09-23 | Dow Chemical Co | Frothing agents for flotation of ores |
| US3595390A (en) * | 1968-06-18 | 1971-07-27 | American Cyanamid Co | Ore flotation process with poly(ethylene-propylene)glycol frothers |
| DE2547987C2 (en) * | 1975-10-27 | 1983-05-26 | Henkel KGaA, 4000 Düsseldorf | Flotation collector for Sylvin |
| US4090972A (en) * | 1976-09-16 | 1978-05-23 | American Cyanamid Company | Effective promoter extender for conventional fatty acids in non-sulfide mineral flotation |
| ZA767089B (en) * | 1976-11-26 | 1978-05-30 | Tekplex Ltd | Froth flotation process and collector composition |
| SU668710A1 (en) * | 1977-11-09 | 1979-06-25 | Белорусский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Галургии Мхп Ссср | Collector for flotation recovery of clay slime from potassium-containing ores |
| US4309282A (en) * | 1980-04-14 | 1982-01-05 | American Cyanamid Company | Process of phosphate ore beneficiation in the presence of residual organic polymeric flocculants |
| OA06199A (en) * | 1981-05-13 | 1981-06-30 | Berol Kemi Ab | Process for the flotation of phosphate minerals and a compound intended for this process. |
| SU986504A1 (en) * | 1981-07-10 | 1983-01-07 | Предприятие П/Я Р-6767 | Phosphate ore flotation method |
| FR2534492A1 (en) * | 1982-10-13 | 1984-04-20 | Elf Aquitaine | IMPROVEMENT IN MINERAL FLOTATION |
| DE3238060A1 (en) * | 1982-10-14 | 1984-04-19 | Henkel KGaA, 4000 Düsseldorf | FLOTATION AGENTS AND METHOD FOR FLOTATION OF NON-SULFIDIC MINERALS |
| SU1138189A1 (en) * | 1983-07-08 | 1985-02-07 | Белорусский Ордена Трудового Красного Знамени Технологический Институт Им.С.М.Кирова | Method of flotation clayish-carbonate slime from potassium ores |
| CA1265265A (en) * | 1984-08-29 | 1990-01-30 | Robert D. Hansen | Frother composition and a froth flotation process for the recovery of mineral |
| US4852596A (en) * | 1987-05-08 | 1989-08-01 | The University Of Virginia Alumni Patents Foundation | Micro slide irrigating unit |
-
1985
- 1985-05-11 DE DE19853517154 patent/DE3517154A1/en not_active Withdrawn
-
1986
- 1986-04-30 TR TR86/0224A patent/TR24023A/en unknown
- 1986-05-02 AT AT86106023T patent/ATE65945T1/en not_active IP Right Cessation
- 1986-05-02 EP EP86106023A patent/EP0201815B2/en not_active Expired - Lifetime
- 1986-05-02 DE DE8686106023T patent/DE3680709D1/en not_active Expired - Fee Related
- 1986-05-09 PT PT82561A patent/PT82561B/en not_active IP Right Cessation
- 1986-05-09 AU AU57312/86A patent/AU581512B2/en not_active Ceased
- 1986-05-09 US US06/861,672 patent/US4789466A/en not_active Expired - Fee Related
- 1986-05-09 BR BR8602081A patent/BR8602081A/en not_active IP Right Cessation
- 1986-05-09 FI FI861953A patent/FI79952C/en not_active IP Right Cessation
- 1986-05-09 ZA ZA863466A patent/ZA863466B/en unknown
- 1986-05-09 ES ES554819A patent/ES8900152A1/en not_active Expired
- 1986-05-09 MX MX002444A patent/MX170350B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015000931A2 (en) | 2013-07-05 | 2015-01-08 | Akzo Nobel Chemicals International B.V. | The synthesis of new anionic surfactants and their use as collectors in froth flotation of non-sulphidic ores |
Also Published As
| Publication number | Publication date |
|---|---|
| ES8900152A1 (en) | 1989-02-16 |
| PT82561A (en) | 1986-06-01 |
| PT82561B (en) | 1988-03-03 |
| MX170350B (en) | 1993-08-18 |
| FI79952C (en) | 1990-04-10 |
| ATE65945T1 (en) | 1991-08-15 |
| AU581512B2 (en) | 1989-02-23 |
| AU5731286A (en) | 1986-11-13 |
| US4789466A (en) | 1988-12-06 |
| DE3517154A1 (en) | 1986-11-13 |
| BR8602081A (en) | 1987-01-06 |
| EP0201815B2 (en) | 1994-08-03 |
| ZA863466B (en) | 1986-12-30 |
| FI79952B (en) | 1989-12-29 |
| EP0201815A3 (en) | 1989-10-18 |
| ES554819A0 (en) | 1989-02-16 |
| DE3680709D1 (en) | 1991-09-12 |
| EP0201815A2 (en) | 1986-11-20 |
| FI861953A (en) | 1986-11-12 |
| FI861953A0 (en) | 1986-05-09 |
| TR24023A (en) | 1991-02-01 |
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