EP0368061A1 - Surface-active derivatives of fatty-acid esters and/or fatty acids as collectors in the flotation of non-sulfidic ores - Google Patents
Surface-active derivatives of fatty-acid esters and/or fatty acids as collectors in the flotation of non-sulfidic ores Download PDFInfo
- Publication number
- EP0368061A1 EP0368061A1 EP89119493A EP89119493A EP0368061A1 EP 0368061 A1 EP0368061 A1 EP 0368061A1 EP 89119493 A EP89119493 A EP 89119493A EP 89119493 A EP89119493 A EP 89119493A EP 0368061 A1 EP0368061 A1 EP 0368061A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- flotation
- ester
- collectors
- acid esters
- 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.)
- Granted
Links
- -1 fatty-acid esters Chemical class 0.000 title claims abstract description 56
- 238000005188 flotation Methods 0.000 title claims abstract description 48
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 39
- 239000000194 fatty acid Substances 0.000 title claims abstract description 39
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 39
- 150000004665 fatty acids Chemical class 0.000 title claims description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 claims abstract description 15
- 239000012434 nucleophilic reagent Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 23
- 239000011707 mineral Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 15
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical group O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052586 apatite Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 4
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000010428 baryte Substances 0.000 claims description 3
- 229910052601 baryte Inorganic materials 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000004707 phenolate Chemical class 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 239000000126 substance Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003945 anionic surfactant Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JUUBMADBGZQVFT-KHPPLWFESA-N (z)-2-methyloctadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCC(C)C(O)=O JUUBMADBGZQVFT-KHPPLWFESA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SRIJLARXVRHZKD-UHFFFAOYSA-N OP(O)=O.C=CC1=CC=CC=C1 Chemical compound OP(O)=O.C=CC1=CC=CC=C1 SRIJLARXVRHZKD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ROAYSRAUMPWBQX-UHFFFAOYSA-N ethanol;sulfuric acid Chemical group CCO.OS(O)(=O)=O ROAYSRAUMPWBQX-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000011835 investigation Methods 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003139 primary aliphatic amines Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003626 triacylglycerols Chemical class 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- 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 surface-active fatty acid ester and / or fatty acid derivatives, which can be obtained via the reaction of epoxidized fatty acid esters with sulfur trioxide, subsequent reaction with nucleophilic reagents and optionally saponification of the ester bond, as a collector in the flotation of non-sulfidic ores.
- Non-sulfidic minerals in the sense of the present invention are, for example, apatite, fluorite, scheelite, barite, iron oxides and other metal oxides, e.g. B. the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates.
- the ore is first crushed and dry, but preferably wet-ground and suspended in water.
- collectors are usually added, often in connection with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), which support the separation of the valuable minerals from the gangue minerals of the ore during the subsequent flotation.
- these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning).
- 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 undesirable components of the ore 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 and at the same time to obtain the best possible enrichment of the mineral.
- anionic surfactants as collectors in the flotation of non-sulfidic ores is in itself state of the art.
- Known anionic collectors are, for example, saturated and unsaturated fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates, acylatylates, alkyl phosphates and alkyl ether phosphates.
- the invention therefore relates to the use of surface-active fatty acid ester and / or fatty acid derivatives which can be obtained by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C, the reaction product (A) with nucleophilic reagents reacting and optionally saponifying the ester bond; as a collector in the flotation of non-sulfidic ores.
- the substances proposed here as collectors are known from DE-A-36 12 481.
- the epoxy fatty acid esters used as starting materials in their production can in turn be obtained by epoxidation of esters of unsaturated fatty acids, for example according to the method described in J. Am. Chem. Soc. 67 (1945), pp. 412-414 can be obtained by reacting unsaturated fatty acid esters with peracetic acid.
- Suitable fatty acid esters are those of unsaturated fatty acids with 14 to 22 carbon atoms and mono- or polyhydric alcohols with 1 to 6 carbon atoms, for example methyl esters, ethyl esters, isopropyl esters, ethylene glycol esters, triglycerides, trimethylol propane esters, pentaerythritol esters and sorbitan esters.
- Preferred epoxy fatty acid esters are epoxidized C1-C4 alkyl esters of monounsaturated fatty acids with 16 to 22 carbon atoms or such Fatty acid mixtures consisting predominantly of monounsaturated fatty acids with 16 to 22 carbon atoms are used.
- the epoxidized esters of technical fatty acid fractions which contain up to about 20% by weight of saturated fatty acids with 14 to 22 carbon atoms and / or up to about 50% by weight of polyunsaturated fatty acids, for example linoleic acid, are also suitable.
- Portions of non-epoxidized, unsaturated fatty acid esters are also sulfonated on the double bond.
- the sulfonation on the double bond proceeds in the sense of the known sulfonation of olefins and leads to sulfoalkenecarboxylic esters with -SO3H groups in the alpha position to the double bond, and to 2- and 3-hydroxyalkanesulfonates.
- reaction products of the first stage of the process according to the invention are distinguished in that they now have a glycol sulfate group instead of the epoxy groups.
- This is reactive and can be implemented in the second stage with numerous nucleophilic reagents with the formation of new fatty acid ester derivatives.
- Suitable nucleophilic reagents are, for example, hydroxides, alcoholates, phenolates or carboxylates, ammonia, primary, secondary and tertiary amines.
- the glycol sulfate ring opens with the formation of beta-substituted ethyl sulfate groups according to the following formula: where, for example, R2 can be a hydrogen atom, a C1-C4 alkyl, phenyl, benzyl or C1-C4 acyl group and R3, R4 and R5 can each represent a hydrogen atom or a C1-C4 alkyl group.
- the fatty acid ester derivatives accessible in this way have surface-active properties due to the water-solubilizing sulfate ester groups -OSO3 ( ⁇ ) and optionally sulfonate groups -SO3 ( ⁇ ).
- metal hydroxides in particular alkali metal hydroxides
- hydrolytic splitting of the glycol sulfate group to give beta-hydroxyethane sulfate groups.
- the content of anionic surfactant in the aqueous surfactant solutions obtained can be determined by determining the content of sulfonate groups and sulfate groups by the so-called two-phase titration method (DGF unit method H-111-10). The breakdown of the glycol sulfate groups is complete when the anionic surfactant content no longer increases.
- sulfonate and sulfate groups can be made by two-phase titration after acid hydrolysis.
- the sulfate groups can be split off by acid hydrolysis, so that only the content of sulfonate groups is then determined.
- the surface-active derivatives of free fatty acids also contemplated for use in the context of the invention are obtained from the fatty acid ester derivatives described above by saponification of the ester bond with at least stoichiometric amounts of alkali metal hydroxide, preferably sodium hydroxide.
- alkali metal hydroxide preferably sodium hydroxide.
- the reaction can be accelerated by using a higher temperature and applying pressure.
- reaction product (A) In cases where the reaction product (A) is reacted with alkali metal hydroxide as a nucleophilic reagent, the reaction product (A) can be converted into the desired di-salt in one step if it is reacted with an amount of alkali metal hydroxide which both sufficient for the hydrolytic breakdown of the glycol sulfate groups and for the hydrolysis of the ester bonds.
- Mixtures can be selected by suitable selection of the working-up conditions for the reaction product (A) be prepared from surface-active fatty acid ester derivatives and fatty acid derivatives.
- surface-active fatty acid ester and / or fatty acid derivatives are used, which are obtainable by contacting the reaction product (A) in aqueous solution with 1 to 2 moles of alkali metal hydroxide per mole of sulfur trioxide added and until the glycol sulfate groups are split up or heated to the hydrolysis of the ester groups.
- the invention further relates to a process for the separation of non-sulfidic minerals from an ore by flotation, in which ground ore is mixed with water to form a suspension, air is passed into the suspension in the presence of a collector and the resulting foam is separated off together with the mineral contained therein , in which one uses fatty acid ester and / or fatty acid derivatives as collectors, which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C, the reaction product (A) with nucleophilic reagents for the reaction brings and optionally saponified the ester bond.
- the collectors In order to achieve economically useful results in the flotation of non-sulfidic ores, the collectors must be used in a certain minimum amount. However, a maximum amount of collectors must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.
- the amounts in which the collectors 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 the necessary quantities vary within wide limits.
- the collectors according to the invention are used in amounts of 50 to 2000, preferably 100 to 1500 g per metric ton of crude ore.
- Anionic collectors suitable for combination with the substances to be used according to the invention are, for example, fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, petroleum sulfonates, acyl lactates, alkyl phosphates, alkyl ether phosphates and styrene phosphonic acid.
- Suitable cationic collectors are e.g.
- ampholytic collectors are, for example, sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates.
- nonionic collectors examples include adducts of ethylene oxide with alkylphenols or fatty alcohols, adducts of ethylene oxide and propylene oxide with fatty alcohols, fatty alcohol / ethylene oxide adducts end-capped with short-chain alkyl radicals and alkylglucosides.
- the surface-active fatty acid ester and / or fatty acid derivatives to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of known collectors used. Accordingly, in addition to the collectors described, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous sponges 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 the technological background of ore processing: H. Schubert, Processing of Solid Mineral Substances, Leipzig 1967; B.
- a preferred area of use for the collector mixtures to be used according to the invention is the processing of ores such as Scheelite, Barite or Apatite.
- the grain size of the flotation task was less than 200 ⁇ m.
- the products C, D, E and F described in the production examples were used as collectors.
- Products C and E were added to the flotation slurries in a dosage of 300 g / t and products D and F in a dosage of 200 g / t.
- Sodium oleate (product X) in a dosage of 500 g / t was used as a reference collector. (All information on the collector concentration relates to active substance).
- the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Science, 259 (1981) pages 775-776, each with 2 g of ore at 23 ° C. and the naturally occurring pH value. Distilled water was used to prepare the flotation slurry. The conditioning time was 15 minutes each. During the flotation, an air stream was passed through the slurry at a flow rate of 4 ml / min. The flotation lasted 2 minutes in all experiments.
- the substances to be used according to the invention Compared to sodium oleate, the substances to be used according to the invention, at low doses, lead to higher values for the WO3 output.
- the WO3 content in the flotation concentrate is not significantly lower despite the higher output. Since the highest possible yield must be achieved for an economical processing of ores in the first flotation stage with sufficient selectivity with a low collector dosage, the products to be used according to the invention offer clear advantages.
- a baryter ore from Mexico was used as the flotation task, which had the following chemical composition with regard to the main components: 69% by weight BaSO4 24% by weight SiO2 3 wt .-% AL2O3
- the flotation task had the following grain size distribution: 39% by weight ⁇ 25 ⁇ m 45% by weight 25-100 ⁇ m 16% by weight> 100 ⁇ m
- Products A and B described in the examples were used as collectors in doses of 230 and 170 g / t, respectively.
- Sodium dodecylbenzenesulfonate (product Y) in a dosage of 500 g / t, was used as a reference collector.
- the flotation experiments were carried out in a laboratory flotation machine (type D 2 from Denver Equipment with a 1 l flotation cell). Water with a Ca2+ ion content of 144 mg / l was used to produce the flotation turbidity. The cloud density was 500 g / l. Soda water glass with a dosage of 1000 g / t was used as the pusher in all experiments. The flotation took place at pH 9.5. The pusher, like the collector used, was conditioned at 1100 rpm for 5 minutes. The preconcentrate was cleaned twice in the 1 l cell without further reagent addition. For the The preconcentrate and the cleaning stages were each floated at 1000 rpm for 6 minutes.
- Table III Flotation from Barvt Collector Dosage (g / t) concentrate BaSO4 content (%) BaSO4 output (%) Product A 230 95.0 93 Product B 170 96.1 94 Product Y 500 98.8 93
- the flotation task had the following grain size distribution: 42.9% by weight ⁇ 25 ⁇ m 48.7% by weight 25-200 ⁇ m 8.4% by weight> 200 ⁇ m
- Products A and B described in the examples were used as collectors in a dosage of 200 g / t.
- Sodium oleate (product X) in a dosage of 700 g / t was used as the comparison collector.
- the flotation experiments were carried out in the laboratory flotation machine type D 2 mentioned in Example 2.
- the preflotation took place in 2 l cells, the cleaning flotation in 1 l cells.
- the cloud density was 36% by weight of solids in water with a total hardness of 27 ° dH.
- Sodium water glass with a dosage of 400 g / t was used as the pusher.
- Flotation was carried out at a pH of approx. 8, as established by the addition of water glass.
- Pushers and collectors were conditioned at 1400 rpm for 5 minutes each.
- the flotation was carried out at 1200 rpm for 6 minutes.
- the substances to be used according to the invention result in a substantially higher value mineral yield with a considerably reduced dosage.
- the very high P2O5 output also explains the somewhat lower mineral value in the concentrate. Because for an economical processing of ores, the extraction of valuable mineral and the required collector dosage in the foreground stand, the products to be used according to the invention offer considerable advantages over the conventional apatite collector sodium oleate.
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Abstract
Description
Die Erfindung betrifft die Verwendung von grenzflächenaktiven Fettsäureester- und/oder Fettsäurederivaten, die man über die Umsetzung von epoxidierten Fettsäureestern mit Schwefeltrioxid, nachfolgende Reaktion mit nucleophilen Reagenzien und gegebenenfalls Verseifung der Esterbindung erhalten kann, als Sammler bei der Flotation von nichtsulfidischen Erzen.The invention relates to the use of surface-active fatty acid ester and / or fatty acid derivatives, which can be obtained via the reaction of epoxidized fatty acid esters with sulfur trioxide, subsequent reaction with nucleophilic reagents and optionally saponification of the ester bond, as a collector in the flotation of non-sulfidic ores.
Die Abtrennung von Wertmineralien von der Gangart durch Flotation ist ein allgemein angewandtes Sortierverfahren für die Aufbereitung von mineralischen Erzen. Nichtsulfidische Minerale im Sinne der vorliegenden Erfindung sind beispielsweise Apatit, Fluorit, Scheelit, Baryt, Eisenoxide und andere Metalloxide, z. B. die Oxide des Titans und Zirkons, sowie bestimmte Silikate und Alumosilikate. Üblicherweise wird bei flotativen Aufbereitungsverfahren das Erz zunächst zerkleinert und trocken, vorzugsweise aber naß vermahlen und in Wasser suspendiert. Anschließend gibt man normalerweise Sammler, häufig in Verbindung mit Schäumern und gegebenenfalls weiteren Hilfsreagenzien wie Reglern, Drückern (Desaktivatoren) und/oder Belebern (Aktivatoren) zu, die die Abtrennung der Wertminerale von den Gangartmineralen des Erzes bei der anschließenden Flotation unterstützen. Bevor in die Suspension Luft eingeblasen wird (Flotieren), um an ihrer Oberfläche Schaum zu erzeugen, läßt man diese Reagenzien üblicherweise eine gewisse Zeit auf das fein gemahlene Erz einwirken (Konditionieren). Der Sammler sorgt für eine Hydrophobierung der Oberfläche der Minerale, so daß ein Anhaften dieser Minerale an den während der Belüftung gebildeten Gasblasen bewirkt wird. Die Hydrophobierung der Mineralbestandteile erfolgt selektiv in der Weise, daß die unerwünschten Bestandteile des Erzes nicht an den Gasblasen haften bleiben. Der mineralhaltige Schaum wird abgestreift und weiterverarbeitet. Es ist das Ziel der Flotation, das Wertmineral der Erze in möglichst hoher Ausbeute zu gewinnen und dabei gleichzeitig eine möglichst gute Anreicherung des Wertminerals zu erhalten.The separation of valuable minerals from the gangue by flotation is a commonly used sorting process for the processing of mineral ores. Non-sulfidic minerals in the sense of the present invention are, for example, apatite, fluorite, scheelite, barite, iron oxides and other metal oxides, e.g. B. the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates. Usually, in the case of flotative processing methods, the ore is first crushed and dry, but preferably wet-ground and suspended in water. Subsequently, collectors are usually added, often in connection with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), which support the separation of the valuable minerals from the gangue minerals of the ore during the subsequent flotation. Before air is blown into the suspension (flotation) to produce foam on its surface, these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning). 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 undesirable components of the ore 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 and at the same time to obtain the best possible enrichment of the mineral.
Die Verwendung von anionaktiven Tensiden als Sammler bei der Flotation von nichtsulfidischen Erzen ist an sich Stand der Technik. Bekannte anionaktive Sammler sind beispielsweise gesättigte und ungesättigte Fettsäuren, Alkylsulfate, Alkylethersulfate, Alkylsulfosuccinate, Alkylsulfosuccinamate, Alkylbenzolsulfonate, Alkylsulfonate, Petroleumsulfonate, Acyllatylate, Alkylphosphate und Alkyletherphosphate.The use of anionic surfactants as collectors in the flotation of non-sulfidic ores is in itself state of the art. Known anionic collectors are, for example, saturated and unsaturated fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates, acylatylates, alkyl phosphates and alkyl ether phosphates.
Bei der Aufbereitung nichtsulfidischer Erze durch Flotation ist - bedingt durch die je nach Herkunft stark schwankende Zusammensetzung des zu trennenden Rohmaterials - eine Vielzahl von Trennaufgaben zu bewältigen. Die zu trennenden Minerale sind häufig sehr fein miteinander verwachsen und weisen dazu auch noch große chemische Ähnlichkeit auf. Demzufolge besteht für die erfolgreiche Durchführung solcher Flotationsverfahren ein großer Bedarf an selektiv wirkenden Reagenzien, insbesondere von selektiv wirkenden Sammlern.When processing non-sulfidic ores by flotation, a large number of separation tasks have to be mastered due to the composition of the raw material to be separated, which varies greatly depending on the origin. The minerals to be separated are often very finely grown together and also have great chemical similarity. Accordingly, there is a great need for selectively acting reagents, in particular selectively acting collectors, for the successful implementation of such flotation processes.
Es wurde gefunden, daß sich grenzflächenaktive Fettsäureester-und/oder Fettsäurederivate, wie sie über die Umsetzung von epoxidierten Estern ungesättigter Fettsäuren mit Schwefeltrioxid und nachfolgende Reaktion mit nucleophilen Reagenzien sowie - im Falle der Fettsäurederivate (Di-Salze) - Verseifung der Esterbindung erhalten werden können, bei der Verwendung als Sammler für die Flotation von nichtsulfidischen Erzen hinsichtlich der Selektivität Vorteile gegenüber bekannten anionischen Standard-Flotationssammlern zeigen.It has been found that surface-active fatty acid ester and / or fatty acid derivatives, such as can be obtained via the reaction of epoxidized esters of unsaturated fatty acids with sulfur trioxide and subsequent reaction with nucleophilic reagents and, in the case of the fatty acid derivatives (di-salts), saponification of the ester bond , When used as a collector for the flotation of non-sulfidic ores in terms of selectivity show advantages over known anionic standard flotation collectors.
Gegenstand der Erfindung ist deshalb die Verwendung von grenzflächenaktiven Fettsäureester- und/oder Fettsäurederivaten, die dadurch erhältlich sind, daß man epoxidierte Fettsäureester mit 1 bis 3 Mol Schwefeltrioxid pro Mol Epoxidsauerstoff bei 20 bis 100 °C umsetzt, das Umsetzungsprodukt (A) mit nucleophilen Reagenzien zur Reaktion bringt und gegebenenfalls die Esterbindung verseift; als Sammler bei der Flotation von nichtsulfidischen Erzen.The invention therefore relates to the use of surface-active fatty acid ester and / or fatty acid derivatives which can be obtained by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C, the reaction product (A) with nucleophilic reagents reacting and optionally saponifying the ester bond; as a collector in the flotation of non-sulfidic ores.
Die hier als Sammler vorgeschlagenen Substanzen sind aus der DE-A-36 12 481 bekannt. Die bei ihrer Herstellung als Ausgangsmaterial eingesetzten Epoxyfettsäureester können ihrerseits durch Epoxidation von Estern ungesättigter Fettsäuren, beispielsweise nach dem in J. Am. Chem. Soc. 67 (1945), S. 412-414 beschriebenen Verfahren durch Umsetzung von ungesättigten Fettsäureestern mit Peressigsäure erhalten werden. Geeignete Fettsäureester sind solche aus ungesättigten Fettsäuren mit 14 bis 22 Kohlenstoffatomen und ein- oder mehrwertigen Alkoholen mit 1 bis 6 Kohlenstoffatomen z.B. Methylester, Ethylester, Isopropylester, Ethylenglycolester, Triglyceride, Trimethylolpropanester, Pentaerythritester und Sorbitanester. Bevorzugt werden als Epoxyfettsäureester epoxidierte C₁-C₄-Alkylester der einfach ungesättigten Fettsäuren mit 16 bis 22 Kohlenstoffatomen oder solcher Fettsäuregemische, die überwiegend aus einfach ungesättigten Fettsäuren mit 16 bis 22 Kohlenstoffatomen bestehen, eingesetzt. Geeignet sind aber auch die epoxidierten Ester von technischen Fettsäurefraktionen, die bis zu etwa 20 Gew.-% gesättigte Fettsäuren mit 14 bis 22 Kohlenstoffatomen und/oder bis zu etwa 50 Gew.-% mehrfach ungesättigte Fettsäuren, z.B. Linolsäure, enthalten. Bevorzugt werden Epoxyfettsäureester mit einem Gehalt von 3 bis 5 Gew.-% Epoxidsauerstoff, insbesondere epoxidierter Ölsäuremethylester oder epoxidierte Methylester von Fettsäurefraktionen, die mehr als 50 Gew.-% Ölsäure enthalten.The substances proposed here as collectors are known from DE-A-36 12 481. The epoxy fatty acid esters used as starting materials in their production can in turn be obtained by epoxidation of esters of unsaturated fatty acids, for example according to the method described in J. Am. Chem. Soc. 67 (1945), pp. 412-414 can be obtained by reacting unsaturated fatty acid esters with peracetic acid. Suitable fatty acid esters are those of unsaturated fatty acids with 14 to 22 carbon atoms and mono- or polyhydric alcohols with 1 to 6 carbon atoms, for example methyl esters, ethyl esters, isopropyl esters, ethylene glycol esters, triglycerides, trimethylol propane esters, pentaerythritol esters and sorbitan esters. Preferred epoxy fatty acid esters are epoxidized C₁-C₄ alkyl esters of monounsaturated fatty acids with 16 to 22 carbon atoms or such Fatty acid mixtures consisting predominantly of monounsaturated fatty acids with 16 to 22 carbon atoms are used. However, the epoxidized esters of technical fatty acid fractions which contain up to about 20% by weight of saturated fatty acids with 14 to 22 carbon atoms and / or up to about 50% by weight of polyunsaturated fatty acids, for example linoleic acid, are also suitable. Epoxy fatty acid esters with a content of 3 to 5% by weight of epoxy oxygen, in particular epoxidized methyl oleic acid or epoxidized methyl esters of fatty acid fractions which contain more than 50% by weight of oleic acid, are preferred.
Bei der Umsetzung der Epoxyfettsäureester mit Schwefeltrioxid tritt als Nebenreaktion eine gleichzeitige Sulfonierung in alpha-Stellung zur Carboxylgruppe ein. Die Umsetzung verläuft nach folgendem Formelschema
Die Umstzungsprodukte der ersten Stufe des erfindungsgemäßen Verfahrens zeichnen sich dadurch aus, daß sie anstelle der Epoxygruppen nun eine Glykolsulfatgruppe aufweisen. Diese ist reaktiv und läßt sich in der zweiten Stufe mit zahlreichen nucleophilen Reagenzien unter Ausbildung neuer Fettsäureester-Derivate umsetzen. Als nucleophile Reagenzien eignen sich z.B. Hydroxide, Alkoholate, Phenolate oder Carboxylate, Ammoniak, primäre, sekundäre und tertiäre Amine. Bei der Umsetzung mit den nucleophilen Reagenzien tritt eine Öffnung des Glykolsulfatringes unter Ausbildung von beta-substituierten Ethylsulfatgruppierungen nach folgendem Formelschema ein:
Die auf diese Weise zugänglichen Fettsäureesterderivate besitzen aufgrund der wasserlöslichmachenden Sulfatestergruppen -OSO₃(⁻) und gegebenenfalls Sulfonatgruppen -SO₃(⁻) grenzflächenaktive Eigenschaften.The fatty acid ester derivatives accessible in this way have surface-active properties due to the water-solubilizing sulfate ester groups -OSO₃ (⁻) and optionally sulfonate groups -SO₃ (⁻).
Bevorzugt ist die weitere Umsetzung des Umsetzungsproduktes (A) mit Metallhydroxiden, insbesondere Alkalimetallhydroxiden, als nucleophilem Reagenz unter hydrolytischer Aufspaltung der Glykolsulfatgruppe zu beta-hydroxyethansulfatgruppen. Dies läßt sich leicht dadurch erreichen, daß man das Umsetzungsprodukt (A) mit einer wässrigen Lösung von 1 bis 1,3 Mol Alkalimetallhydroxid pro Mol angelagertem Schwefeltrioxid in Kontakt bringt und bis zur Aufspaltung der Glykolsulfatgruppen zu Gruppierungen der Formeln
In den erhaltenen wässrigen Tensidlösungen läßt sich der Gehalt an Aniontensid durch Bestimmung des Gehaltes an Sulfonat-Gruppen und Sulfat-Gruppen nach der sogenannten Zweiphasentitrationsmethode (DGF-Einheitsmethode H-111-10) ermitteln. Die Aufspaltung der Glykolsulfat-Gruppen ist abgeschlossen, wenn der Gehalt an Aniontensid nicht mehr zunimmt.The content of anionic surfactant in the aqueous surfactant solutions obtained can be determined by determining the content of sulfonate groups and sulfate groups by the so-called two-phase titration method (DGF unit method H-111-10). The breakdown of the glycol sulfate groups is complete when the anionic surfactant content no longer increases.
Eine Unterscheidung zwischen Sulfonat- und Sulfat-Gruppen läßt sich durch Zweiphasentitration nach saurer Hydrolyse treffen. Die Sulfat-Gruppen lassen sich durch saure Hydrolyse abspalten, so daß danach nur noch der Gehalt an Sulfonat-Gruppen erfaßt wird.A distinction between sulfonate and sulfate groups can be made by two-phase titration after acid hydrolysis. The sulfate groups can be split off by acid hydrolysis, so that only the content of sulfonate groups is then determined.
Die für die Verwendung im Sinn der Erfindung ebenfalls in Betracht gezogenen grenzflächenaktiven Derivate von freien Fettsäuren (Di-Salze) werden aus den vorstehend beschriebenen Fettsäureesterderivate durch Verseifung der Esterbindung mit mindestens stöchiometrischen Mengen Alkalimetallhydroxid, vorzugsweise Natriumhydroxid, erhalten. Auch hier kann die Reaktion durch höhere Temperatur und Anwendung von Druck beschleunigt werden. In den Fällen, in denen das Umsetzungsprodukt (A) mit Alkalimetallhydroxid als nucleophilem Reagenz umgesetzt wird, kann das Umsetzungsprodukt (A) in einem Schritt in das gewünschte Di-Salz umgewandelt werden, wenn es mit einer Menge Alkalimetallhydroxid zur Reaktion gebracht wird, die sowohl für die hydrolytische Aufspaltung der Glykolsulfat-Gruppen als auch für die Hydrolyse der Esterbindungen ausreicht. Durch geeignete Wahl der Aufarbeitungsbedingungen für das Umsetzungsprodukt (A) können Gemische aus grenzflächenaktiven Fettsäureesterderivaten und Fettsäurederivaten hergestellt werden.The surface-active derivatives of free fatty acids (di-salts) also contemplated for use in the context of the invention are obtained from the fatty acid ester derivatives described above by saponification of the ester bond with at least stoichiometric amounts of alkali metal hydroxide, preferably sodium hydroxide. Here too, the reaction can be accelerated by using a higher temperature and applying pressure. In cases where the reaction product (A) is reacted with alkali metal hydroxide as a nucleophilic reagent, the reaction product (A) can be converted into the desired di-salt in one step if it is reacted with an amount of alkali metal hydroxide which both sufficient for the hydrolytic breakdown of the glycol sulfate groups and for the hydrolysis of the ester bonds. Mixtures can be selected by suitable selection of the working-up conditions for the reaction product (A) be prepared from surface-active fatty acid ester derivatives and fatty acid derivatives.
In einer bevorzugten Ausführungsform der Erfindung werden grenzflächenaktive Fettsäureester- und/oder Fettsäurederivate verwendet, die dadurch erhältlich sind, daß man das Umsetzungsprodukt (A) in wässriger Lösung mit 1 bis 2 Mol Alkalimetallhydroxid pro Mol angelagertem Schwefeltrioxid in Kontakt bringt und bis zur Aufspaltung der Glykolsulfatgruppen bzw. bis zur Hydrolyse der Estergruppen erwärmt.In a preferred embodiment of the invention, surface-active fatty acid ester and / or fatty acid derivatives are used, which are obtainable by contacting the reaction product (A) in aqueous solution with 1 to 2 moles of alkali metal hydroxide per mole of sulfur trioxide added and until the glycol sulfate groups are split up or heated to the hydrolysis of the ester groups.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Abtrennung von nichtsulfidischen Mineralen aus einem Erz durch Flotation, bei dem man gemahlenes Erz mit Wasser zu einer Suspension vermischt, in die Suspension in Gegenwart eines Sammlers Luft einleitet und den entstandenen Schaum zusammen mit dem darin enthaltenen Mineral abtrennt, bei dem man als Sammler Fettsäureester- und/oder Fettsäurederivate einsetzt, die dadurch erhältlich sind, daß man epoxidierte Fettsäureester mit 1 bis 3 Mol Schwefeltrioxid pro Mol Epoxidsauerstoff bei 20 bis 100 °C umsetzt, das Umsetzungsprodukt (A) mit nukleophilen Reagenzien zur Reaktion bringt und gegebenenfalls die Esterbindung verseift.The invention further relates to a process for the separation of non-sulfidic minerals from an ore by flotation, in which ground ore is mixed with water to form a suspension, air is passed into the suspension in the presence of a collector and the resulting foam is separated off together with the mineral contained therein , in which one uses fatty acid ester and / or fatty acid derivatives as collectors, which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C, the reaction product (A) with nucleophilic reagents for the reaction brings and optionally saponified the ester bond.
Um wirtschaftlich brauchbare Ergebnisse bei der Flotation nichtsulfidischer Erze zu erzielen, müssen die Sammler in einer gewissen Mindestmenge eingesetzt werden. Es darf aber auch eine Höchstmenge an Sammler nicht überschritten werden, da sonst die Schaumbildung zu stark wird und die Selektivität gegenüber den Wertmineralen abnimmt. Die Mengen, in denen die erfindungsgemäß zu verwendenden Sammler eingesetzt werden, hängen jeweils von der Art der zu flotierenden Erze und von deren Gehalt an Wertmineralen ab. Demzufolge können die notwendigen Einsatzmengen in weiten Grenzen schwanken. Im allgemeinen werden die erfindungsgemäßen Sammler in Mengen von 50 bis 2000, vorzugsweise 100 bis 1500 g pro metrischer Tonne Roherz eingesetzt.In order to achieve economically useful results in the flotation of non-sulfidic ores, the collectors must be used in a certain minimum amount. However, a maximum amount of collectors must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases. The amounts in which the collectors 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 the necessary quantities vary within wide limits. In general, the collectors according to the invention are used in amounts of 50 to 2000, preferably 100 to 1500 g per metric ton of crude ore.
In der Praxis kann es sich als zweckmäßig erweisen, die erfindungsgemäß zu verwendenden grenzflächenaktiven Fettsäureester- und/oder Fettsäurederivate zur Erzielung spezieller Effekte, insbesondere zur Steigerung der Selektivität, zusammen mit bekannten anionischen, kationischen, ampholytischen oder nichtionogenen Sammlern einzusetzen. Für die Kombination mit den erfindungsgemäß zu verwendenden Substanzen geeignete anionische Sammler sind beispielsweise Fettsäuren, Alkylsulfate, Alkylethersulfate, Alkylsulfosuccinate, Alkylsulfosuccinamate, Alkylbenzolsulfonate, Petroleumsulfonate, Acyllactate, Alkylphosphate, Alkyletherphosphate und Styrolphosphonsäure. Als kationaktive Sammler eignen sich z.B. primäre aliphatische Amine, mit alpha-verzweigten Alkylresten substituierte Alkylendiamine, hydroxyalkylsubstituierte Alkylendiamine und wasserlösliche Säureadditionssalze dieser Amine. Geeignete ampholytische Sammler sind beispielsweise Sarkoside, Tauride, N-substituierte Aminopropionsäuren und N-(1,2-Dicarboxyethyl)-N-alkylsulfosuccinamate. Beispiele für bekannte nichtionogene Sammler sind Anlagerungsprodukte des Ethylenoxids an Alkylphenole oder Fettalkohole, Anlagerungsprodukte von Ethylenoxid und Propylenoxid an Fettalkohole, mit kurzkettigen Alkylresten endgruppenverschlossene Fettalkohol/Ethylenoxidanlagerungsprodukte und Alkylglukoside.In practice, it may prove expedient to use the surface-active fatty acid ester and / or fatty acid derivatives to be used according to the invention in order to achieve special effects, in particular to increase the selectivity, together with known anionic, cationic, ampholytic or nonionic collectors. Anionic collectors suitable for combination with the substances to be used according to the invention are, for example, fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, petroleum sulfonates, acyl lactates, alkyl phosphates, alkyl ether phosphates and styrene phosphonic acid. Suitable cationic collectors are e.g. primary aliphatic amines, alkylene diamines substituted with alpha-branched alkyl radicals, hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines. Suitable ampholytic collectors are, for example, sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates. Examples of known nonionic collectors are adducts of ethylene oxide with alkylphenols or fatty alcohols, adducts of ethylene oxide and propylene oxide with fatty alcohols, fatty alcohol / ethylene oxide adducts end-capped with short-chain alkyl radicals and alkylglucosides.
Die erfindungsgemäß zu verwendenden grenzflächenaktiven Fettsäureester- und/oder Fettsäurederivate werden in den bekannten Flotationsverfahren für nichtsulfidische Erze anstelle von bekannten Sammlern eingesetzt. Dementsprechend werden auch hier neben den beschriebenen Sammlern die jeweils gebräuchlichen Reagenzien wie Schäumer, Regler, Aktivatoren, Desaktivatoren usw. den wässrigen Aufschwämmungen der vermahlenen Erze zugesetzt. Die Durchführung der Flotation erfolgt unter den Bedingungen der Verfahren des Standes der Technik. In diesem Zusammenhang wird auf die folgenden Literaturstellen zum technologischen Hintergrund der Erzaufbereitung verwiesen: H. Schubert, Aufbereitung fester mineralischer Stoffe, 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.The surface-active fatty acid ester and / or fatty acid derivatives to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of known collectors used. Accordingly, in addition to the collectors described, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous sponges 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 the technological background of ore processing: H. Schubert, Processing of Solid Mineral Substances, Leipzig 1967; B. Wills, Mineral Processing Technology Plant Design, New York, 1978; DB Purchas (ed.), Solid / Liquid Separation Equipment Scale-up, Croydon 1977; ES Perry, CJ van Oss, E. Grushka (ed.) Separation and Purification Methods, New York, 1973-1978.
Ein bevorzugtes Einsatzgebiet für die erfindungsgemäß zu verwendenden Sammlergemische ist die Aufbereitung von Erzen wie Scheelit, Baryt oder Apatit.A preferred area of use for the collector mixtures to be used according to the invention is the processing of ores such as Scheelite, Barite or Apatite.
In einem Labor-Standreaktor wurden im Verlauf von 50 Minuten 40 g (0,5 Mol) gasförmiges Schwefeltrioxid über ein Tauchrohr in 148 g (0,5 Mol) eines epoxidierten technischen Ölsäuremethylesters (Epoxidsauerstoffgehalt 3,5 Gew.-%) eingeleitet. Die Reaktionstemperatur betrug 30°C.In a laboratory standing reactor, 40 g (0.5 mol) of gaseous sulfur trioxide were introduced into 148 g (0.5 mol) of an epoxidized technical grade oleic acid methyl ester (epoxy oxygen content 3.5% by weight) over a dip tube over the course of 50 minutes. The reaction temperature was 30 ° C.
140 g (0,37 Mol) des erhaltenen rohen Sulfierproduktes (Sulfiergrad 65,9 %) wurden mit 15 g (0,38 Mol) Natriumhydroxid in 330 ml Wasser neutralisiert. Das neutralisierte Gemisch wurde zur Hydrolyse 4 Stunden lang auf 90°C erhitzt. Die dabei auftretende pH-Verschiebung wurde durch laufende Zugabe von insgesamt 3,1 g (0,08 Mol) Natriumhydroxid kompensiert. Nach der Hydrolyse zeigte die wässrige Lösung (Produkt A) folgende Kenndaten:
In einem Labor-Standreaktor wurden im Verlauf von 50 Minuten 40 g (0,5 Mol) gasförmiges Schwefeltrioxid über ein Tauchrohr in 148 g (0,5 Mol) eines epoxidierten technischen Ölsäuremethylesters (Epoxid-Sauerstoffgehalt 3,5 Gew.-%) eingeleitet. Die Reaktonstemperatur betrug 30°C.In a laboratory stand reactor, 40 g (0.5 mol) of gaseous sulfur trioxide were introduced into 148 g (0.5 mol) of an epoxidized technical grade oleic acid methyl ester (epoxy oxygen content 3.5% by weight) over a dip tube over the course of 50 minutes . The reaction temperature was 30 ° C.
140 g (0,37 Mol) des erhaltenen rohen Sulfierproduktes (Sulfiergrad: 62,6 %) wurden mit 29,8 g (0,75 Mol) Natriumhydroxid in 660 ml Wasser versetzt. Das alkalische Gemisch wurde zur Hydrolyse 4 Stunden lang auf 90°C erhitzt. Danach zeigte das in Wasser klar gelöste Produkt B folgende Kenndaten:
Analog den Herstellungsbeispielen A und B wurde Schwefeltrioxid mit dem dort beschriebenen epoxidierten Ölsäuremethylester in Molverhältnissen von 0,8 bis 1,2 bei 60 bis 80 °C im Verlauf von 50 Minuten umgesetzt.Analogous to preparation examples A and B, sulfur trioxide was reacted with the epoxidized methyl oleic ester described therein in molar ratios of 0.8 to 1.2 at 60 to 80 ° C. over the course of 50 minutes.
Durch nachfolgende Neutralisation und Hydrolyse mit wässriger Natriumhydroxidlösung bei 90 °C wurden die Produkte C bis F in Form ihrer wässrigen Lösungen erhalten.Subsequent neutralization and hydrolysis with aqueous sodium hydroxide solution at 90 ° C. gave products C to F in the form of their aqueous solutions.
Die Reaktionsbedingungen der Sulfierreaktion, der jeweils erzielte Sulfiergrad, die für die Aufbearbeitung eingesetzte Menge sulfiertes Epoxid und die Gesamtmenge des verwendeten Natriumhydroxids in den Herstellungsbeispielen C bis F sind zusammen mit den Analysendaten der entsprechenden Produkte C bis F in der nachstehenden Tabelle I wiedergegeben. Die Tabelle 1 enthält auch die entsprechenden Angaben für die Herstellungsbeispiele A und B und die Produkte A und B.
Als Flotationsaufgabe wurde ein Scheeliterz aus Österreich eingesetzt, das bezüglich seiner Hauptbestandteile die nachstehende chemische Zusammensetzung hatte:
0,33 Gew.-% WO₃
8,8 Gew.-% CaO
55,8 Gew.-% SiO₂
A Scheelite ore from Austria was used as the flotation task, which had the following chemical composition with regard to its main components:
0.33 wt .-% WO₃
8.8 wt% CaO
55.8% by weight of SiO₂
Die Korngröße der Flotationsaufgabe lag unter 200 µm.The grain size of the flotation task was less than 200 µm.
Als Sammler wurden die in den Herstellungsbeispielen beschriebenen Produkte C, D, E und F eingesetzt. Den Flotationstrüben wurden die Produkte C und E in einer Dosierung von 300 g/t und die Produkte D und F in einer Dosierung von 200 g/t zugesetzt. Als Vergleichssammler wurde Natriumoleat (Produkt X) in einer Dosierung von 500 g/t eingesetzt. (Alle Angaben zur Sammlerkonzentration beziehen sich auf Aktivsubstanz).The products C, D, E and F described in the production examples were used as collectors. Products C and E were added to the flotation slurries in a dosage of 300 g / t and products D and F in a dosage of 200 g / t. Sodium oleate (product X) in a dosage of 500 g / t was used as a reference collector. (All information on the collector concentration relates to active substance).
Die Flotationsversuche wurden in einer modifizierten Hallimond-Röhre (Mikroflotationszelle) nach B. Dobias, Colloid & Polymer Science, 259 (1981) Seiten 775-776 mit jeweils 2 g Erz bei 23 °C und dem natürlich sich einstellenden pH Wert durchgeführt. Zur Herstellung der Flotationstrübe wurde destilliertes Wasser verwendet. Die Konditionierungszeit betrug jeweils 15 Minuten. Während der Flotation wurde ein Luftstrom mit einer Durchflußgeschwindigkeit von 4 ml/min durch die Trübe geleitet. Die Flotation dauerte in allen Versuchen 2 Minuten.The flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Science, 259 (1981) pages 775-776, each with 2 g of ore at 23 ° C. and the naturally occurring pH value. Distilled water was used to prepare the flotation slurry. The conditioning time was 15 minutes each. During the flotation, an air stream was passed through the slurry at a flow rate of 4 ml / min. The flotation lasted 2 minutes in all experiments.
Die Ergebnisse der Flotationsversuche mit dem erfindungsgemäß zu verwendenden Substanzen sind in der Tabelle 1 zusammengefaßt und den Werten gegenübergestellt, die mit Natriumoleat als Vergleichssubstanz erhalten wurden.
Im Vergleich zu Natriumoleat führen die erfindungsgemäß zu verwendenden Substanzen bei geringer Dosierung zu höhere Werten für das WO₃-Ausbringen. Der WO₃-Gehalt im Flotationskonzentrat liegt trotz des höheren Ausbringens nicht entscheidend niedriger. Da für eine wirtschaftliche Aufbereitung von Erzen in der ersten Flotationsstufe bei ausreichender Selektivität mit niederer Sammlerdosierung ein möglichst hohes Ausbringen erzielt werden muß, bieten die erfindungsgemäß zu verwendenden Produkte deutliche Vorteile.Compared to sodium oleate, the substances to be used according to the invention, at low doses, lead to higher values for the WO₃ output. The WO₃ content in the flotation concentrate is not significantly lower despite the higher output. Since the highest possible yield must be achieved for an economical processing of ores in the first flotation stage with sufficient selectivity with a low collector dosage, the products to be used according to the invention offer clear advantages.
Als Flotationsaufgabe wurde ein Baryterz aus Mexiko eingesetzt, das bezüglich der Hauptbestandteile die nachstehende chemische Zusammensetzung hatte:
69 Gew.-% BaSO₄
24 Gew.-% SiO₂
3 Gew.-% AL₂O₃A baryter ore from Mexico was used as the flotation task, which had the following chemical composition with regard to the main components:
69% by weight BaSO₄
24% by weight SiO₂
3 wt .-% AL₂O₃
Die Flotationsaufgabe hatte folgende Korngrößenverteilung:
39 Gew.-% < 25 µm
45 Gew.-% 25 - 100 µm
16 Gew.-% > 100 µmThe flotation task had the following grain size distribution:
39% by weight <25 µm
45% by weight 25-100 µm
16% by weight> 100 µm
Als Sammler wurden die in den Beispielen beschriebenen Produkte A und B in Dosierungen von 230 bzw. 170 g/t eingesetzt. Als Vergleichssammler wurde Natriumdodecylbenzolsulfonat (Produkt Y), in einer Dosierung von 500 g/t verwendet.Products A and B described in the examples were used as collectors in doses of 230 and 170 g / t, respectively. Sodium dodecylbenzenesulfonate (product Y), in a dosage of 500 g / t, was used as a reference collector.
Die Flotationsversuche wurden in einer Laborflotationsmaschine (Typ D 2 der Fa. Denver Equipment mit einer 1 l Flotationszelle) durchgeführt. Zur Herstellung der Flotationstrüben wurde Wasser mit einem Ca²⁺-Ionengehalt von 144 mg/l verwendet. Die Trübedichte betrug 500 g/l. Als Drücker wurde in allen Versuchen Natronwasserglas mit einer Dosierung von 1000 g/t eingesetzt. Die Flotation erfolgte bei pH 9,5. Der Drücker wurde, ebenso wie der jeweils eingesetzte Sammler, 5 Minuten lang bei 1100 UpM konditioniert. Das Vorkonzentrat wurde in der 1 l-Zelle ohne weitere Reagenzzugabe zweimal nachgereinigt. Für das Vorkonzentrat und in den Reinigungsstufen wurde jeweils 6 Minuten lang bei 1000 UpM flotiert.The flotation experiments were carried out in a laboratory flotation machine (type D 2 from Denver Equipment with a 1 l flotation cell). Water with a Ca²⁺ ion content of 144 mg / l was used to produce the flotation turbidity. The cloud density was 500 g / l. Soda water glass with a dosage of 1000 g / t was used as the pusher in all experiments. The flotation took place at pH 9.5. The pusher, like the collector used, was conditioned at 1100 rpm for 5 minutes. The preconcentrate was cleaned twice in the 1 l cell without further reagent addition. For the The preconcentrate and the cleaning stages were each floated at 1000 rpm for 6 minutes.
Die Ergebnisse der Flotationsversuche mit den erfindungsgemäß zu verwendenden Substanzen sind in der Tabelle III zusammengefaßt und den Werten gegenübergestellt, die mit Natriumdodecylbenzolsulfonat als Vergleichssubstanz erhalten wurden.
Im Vergleich zu Natriumdodecylbenzolsulfonat kann bei Verwendung des Produktes B mit einem Drittel der Dosierung ein im Konzentratgehalt und BaSO₄-Ausbringen vergleichbares Ergebnis erzielt werden. Produkt A flotiert ein entsprechendes Konzentrat mit einer im Vergleich zu Produkt Y auf die Hälfte reduzierten Dosierung.Compared to sodium dodecylbenzenesulfonate, using product B with a third of the dosage can achieve a result comparable in concentrate content and BaSO₄ application. Product A floats a corresponding concentrate with a dosage reduced by half compared to product Y.
Als Flotationsaufgabe wurde ein Apatiterz aus Schweden eingesetzt, das bezüglich seiner Hauptbestandteile die nachstehende chemische Zusammensetzung hatte:
11 Gew.-% P₂O₅
35 Gew.-% SiO₂
7 Gew.-% Fe₂O₃
21 Gew.-% CaOAn apatite ore from Sweden was used as the flotation task, which had the following chemical composition with regard to its main components:
11% by weight of P₂O₅
35% by weight SiO₂
7 wt .-% Fe₂O₃
21 wt% CaO
Die Flotationsaufgabe hatte folgende Korngrößenverteilung:
42,9 Gew.-% < 25 µm
48,7 Gew.-% 25 - 200 µm
8,4 Gew.-% > 200 µmThe flotation task had the following grain size distribution:
42.9% by weight <25 µm
48.7% by weight 25-200 µm
8.4% by weight> 200 µm
Als Sammler wurden die in den Beispielen beschriebenen Produkte A und B in einer Dosierung von 200 g/t eingesetzt. Als Verlgeichssammler wurde Natriumoleat (Produkt X) in einer Dosierung von 700 g/t verwendet.Products A and B described in the examples were used as collectors in a dosage of 200 g / t. Sodium oleate (product X) in a dosage of 700 g / t was used as the comparison collector.
Die Flotationsversuche wurden in der im Beispiel 2 erwähnten Laborflotationsmaschine Typ D 2 durchgeführt. Die Vorflotation erfolgte in 2 l-Zellen, die Reinigungsflotation in 1 l-Zellen. Die Trübedichte betrug 36 Gew.-% Feststoff in Wasser mit einer Gesamthärte von 27 °dH. Als Drücker wurde jeweils Natronwasserglas mit einer Dosierung von 400 g/t verwendet. Flotiert wurde bei einem pH-Wert von ca. 8, wie er sich durch die Wasserglaszugabe einstellte. Drücker und Sammler wurden jeweils bei 1400 UpM 5 Minuten lang konditioniert. Flotiert wurde jeweils 6 Minuten lang bei 1200 UpM.The flotation experiments were carried out in the laboratory flotation machine type D 2 mentioned in Example 2. The preflotation took place in 2 l cells, the cleaning flotation in 1 l cells. The cloud density was 36% by weight of solids in water with a total hardness of 27 ° dH. Sodium water glass with a dosage of 400 g / t was used as the pusher. Flotation was carried out at a pH of approx. 8, as established by the addition of water glass. Pushers and collectors were conditioned at 1400 rpm for 5 minutes each. The flotation was carried out at 1200 rpm for 6 minutes.
Die Ergebnisse der Flotationsversuche mit den erfindungsgemäß zu verwendenden Substanzen A und B sind in der Tabelle IV wiedergegeben und den Werten gegenübergestellt, die mit Natriumoleat als Vergleichssubstanz erhalten wurden.
Im Vergleich zu Natriumoleat führen die erfindungsgemäß zu verwendenden Substanzen bei einer erheblich verminderten Dosierung zu einem wesentlich höheren Wertmineralausbringen. Das sehr hohe P₂O₅-Ausbringen erklärt auch den etwas geringeren Wertmineralgehalt im Konzentrat. Da für eine wirtschaftliche Aufbereitung von Erzen das Wertmineralausbringen und die dafür benötigte Sammlerdosierung im Vordergrund stehen, bieten die erfindungsgemäß zu verwendenden Produkte erhebliche Vorteile gegenüber dem herkömmlichen Apatit-Sammler Natriumoleat.Compared to sodium oleate, the substances to be used according to the invention result in a substantially higher value mineral yield with a considerably reduced dosage. The very high P₂O₅ output also explains the somewhat lower mineral value in the concentrate. Because for an economical processing of ores, the extraction of valuable mineral and the required collector dosage in the foreground stand, the products to be used according to the invention offer considerable advantages over the conventional apatite collector sodium oleate.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3836891A DE3836891A1 (en) | 1988-10-29 | 1988-10-29 | BORDER-ACTIVE FAT-ACID STARTER AND / OR FAT-SAFER DERIVATIVES AS COLLECTORS IN THE FLOTATION OF NON-SULFIDIC ORNAMENTS |
DE3836891 | 1988-10-29 |
Publications (2)
Publication Number | Publication Date |
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EP0368061A1 true EP0368061A1 (en) | 1990-05-16 |
EP0368061B1 EP0368061B1 (en) | 1993-03-17 |
Family
ID=6366156
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Application Number | Title | Priority Date | Filing Date |
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EP89119493A Expired - Lifetime EP0368061B1 (en) | 1988-10-29 | 1989-10-20 | Surface-active derivatives of fatty-acid esters and/or fatty acids as collectors in the flotation of non-sulfidic ores |
EP89913082A Pending EP0440746A1 (en) | 1988-10-29 | 1989-10-20 | Surface-active fatty acid ester and/or fatty acid derivatives as collectors in the flotation of non-sulphidic ores |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP89913082A Pending EP0440746A1 (en) | 1988-10-29 | 1989-10-20 | Surface-active fatty acid ester and/or fatty acid derivatives as collectors in the flotation of non-sulphidic ores |
Country Status (10)
Country | Link |
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EP (2) | EP0368061B1 (en) |
AU (1) | AU627805B2 (en) |
BR (1) | BR8907743A (en) |
CA (1) | CA2001736A1 (en) |
DE (2) | DE3836891A1 (en) |
ES (1) | ES2041939T3 (en) |
PT (1) | PT92128B (en) |
TR (1) | TR24025A (en) |
WO (1) | WO1990004459A1 (en) |
ZA (1) | ZA898203B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2036465A1 (en) * | 1990-08-10 | 1993-05-16 | Kali & Salz Ag | Rock salt from ocean deposits |
CN107442294A (en) * | 2017-09-04 | 2017-12-08 | 江西理工大学 | A kind of method that flotation at normal temperatures obtains qualified white tungsten fine ore |
CN108543631A (en) * | 2018-05-10 | 2018-09-18 | 江西理工大学 | A kind of beneficiation method of skarn type scheelite |
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CN111804442A (en) * | 2019-04-10 | 2020-10-23 | 杨立 | Reverse flotation method based on low-temperature saponification reaction |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE670048C (en) * | 1935-11-07 | 1939-01-10 | Erz & Kohleflotation Gmbh | Process for the swimming treatment of non-sulphidic minerals with the addition of a salt of a sulphurized fatty acid |
GB589800A (en) * | 1939-07-03 | 1947-07-01 | Thorbjorn Heilmann | Improvements relating to the separation of calcium carbonate by froth flotation |
DE3612481A1 (en) * | 1986-04-14 | 1987-10-15 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF INTERFACE-ACTIVE FATTY ACID ESTER DERIVATIVES |
-
1988
- 1988-10-29 DE DE3836891A patent/DE3836891A1/en not_active Withdrawn
-
1989
- 1989-10-20 TR TR89/0839A patent/TR24025A/en unknown
- 1989-10-20 BR BR898907743A patent/BR8907743A/en not_active Application Discontinuation
- 1989-10-20 WO PCT/EP1989/001256 patent/WO1990004459A1/en not_active Application Discontinuation
- 1989-10-20 EP EP89119493A patent/EP0368061B1/en not_active Expired - Lifetime
- 1989-10-20 ES ES198989119493T patent/ES2041939T3/en not_active Expired - Lifetime
- 1989-10-20 AU AU46313/89A patent/AU627805B2/en not_active Ceased
- 1989-10-20 EP EP89913082A patent/EP0440746A1/en active Pending
- 1989-10-20 DE DE8989119493T patent/DE58903805D1/en not_active Expired - Fee Related
- 1989-10-27 PT PT92128A patent/PT92128B/en not_active IP Right Cessation
- 1989-10-27 ZA ZA898203A patent/ZA898203B/en unknown
- 1989-10-30 CA CA002001736A patent/CA2001736A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE670048C (en) * | 1935-11-07 | 1939-01-10 | Erz & Kohleflotation Gmbh | Process for the swimming treatment of non-sulphidic minerals with the addition of a salt of a sulphurized fatty acid |
GB589800A (en) * | 1939-07-03 | 1947-07-01 | Thorbjorn Heilmann | Improvements relating to the separation of calcium carbonate by froth flotation |
DE3612481A1 (en) * | 1986-04-14 | 1987-10-15 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF INTERFACE-ACTIVE FATTY ACID ESTER DERIVATIVES |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2036465A1 (en) * | 1990-08-10 | 1993-05-16 | Kali & Salz Ag | Rock salt from ocean deposits |
CN107442294A (en) * | 2017-09-04 | 2017-12-08 | 江西理工大学 | A kind of method that flotation at normal temperatures obtains qualified white tungsten fine ore |
CN108543631A (en) * | 2018-05-10 | 2018-09-18 | 江西理工大学 | A kind of beneficiation method of skarn type scheelite |
Also Published As
Publication number | Publication date |
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DE58903805D1 (en) | 1993-04-22 |
DE3836891A1 (en) | 1990-05-03 |
ZA898203B (en) | 1990-07-25 |
ES2041939T3 (en) | 1993-12-01 |
CA2001736A1 (en) | 1990-04-29 |
AU4631389A (en) | 1990-05-14 |
PT92128A (en) | 1990-04-30 |
EP0440746A1 (en) | 1991-08-14 |
BR8907743A (en) | 1991-08-20 |
PT92128B (en) | 1995-07-03 |
AU627805B2 (en) | 1992-09-03 |
WO1990004459A1 (en) | 1990-05-03 |
EP0368061B1 (en) | 1993-03-17 |
TR24025A (en) | 1991-02-04 |
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