EP3817860A1 - Verfahren zur schaumflotation - Google Patents
Verfahren zur schaumflotationInfo
- Publication number
- EP3817860A1 EP3817860A1 EP19734426.0A EP19734426A EP3817860A1 EP 3817860 A1 EP3817860 A1 EP 3817860A1 EP 19734426 A EP19734426 A EP 19734426A EP 3817860 A1 EP3817860 A1 EP 3817860A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- collector
- group
- ore
- carbon atoms
- aid
- 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
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000009291 froth flotation Methods 0.000 title claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 34
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- -1 ethoxy, propoxy Chemical group 0.000 claims abstract description 33
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- 230000003750 conditioning effect Effects 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 125000000129 anionic group Chemical group 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 28
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000003784 tall oil Substances 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 230000001143 conditioned effect Effects 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229940071089 sarcosinate Drugs 0.000 claims description 3
- 229910006069 SO3H Chemical group 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 150000002169 ethanolamines Chemical class 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229930182470 glycoside Natural products 0.000 claims description 2
- 150000002338 glycosides Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims 1
- 238000005188 flotation Methods 0.000 description 48
- 235000021317 phosphate Nutrition 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 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 8
- 229910052586 apatite Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000847 nonoxynol Polymers 0.000 description 3
- 229910052585 phosphate mineral Inorganic materials 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ILBONRFSLATCRE-UHFFFAOYSA-N Phosfolan Chemical compound CCOP(=O)(OCC)N=C1SCCS1 ILBONRFSLATCRE-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 229940077441 fluorapatite Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052641 aegirine Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052589 chlorapatite Inorganic materials 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- B03D1/01—Organic compounds containing nitrogen
-
- 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
- B03D1/0043—Organic compounds modified so as to contain a polyether group
-
- 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
-
- 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
- B03D1/02—Froth-flotation processes
- B03D1/021—Froth-flotation processes for treatment of phosphate ores
-
- 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
- B03D2203/06—Phosphate ores
Definitions
- Phosphate rocks contain calcium phosphate minerals largely in the form of apatite, usually together with other minerals (e.g., silicate minerals and carbonate minerals, such as calcite).
- Apatite is a generic name for a group of calcium phosphate minerals also containing other elements or radicals, such as fluorapatite, chlorapatite, hydroxylapatite, carbonate-rich fluorapatite and carbonate-rich hydroxylapatite.
- Collector performance may be improved by using collector combinations of a primary (main) collector and a secondary collector (also called co-collector).
- collector composition shall be used to describe compositions containing a primary collector, or both a primary and a secondary collector, as well as a collector aid.
- secondary collectors have been used together with primary ionic collectors in salt-type mineral flotation to improve the performance of the primary collector.
- Nonylphenol ethoxylates have been the dominating nonionic surfactant used as a co-collector in a combination with sarcosine-type primary collectors in selective flotation of apatite from calcite-containing ores.
- an intense search for a replacement of nonylphenol ethoxylates has been ongoing for a long time.
- collector compositions having a better environmental profile than nonylphenol ethoxylates that perform equally well. Collector compositions aligned with this approach are described herein.
- the Applicant has surprisingly found that employing a primary collector and a collector aid, and optionally a secondary collector, and conditioning a phosphate-containing ore with both these compounds in a froth flotation process will improve froth flotation results such as grade and recovery of the phosphate minerals during such froth flotation process. Further it has been found even more beneficial to pre-mix the primary collector and collector aid, and optionally a secondary collector (to form a collector composition) which will allow the collector composition to be added as a single product to the ore without the need for a separate conditioning step, while at the same time significantly improving the performance of the flotation.
- the present invention relates to a method for froth flotation of an ore to recover phosphate-containing materials from the ore that includes adding a a primary collector and a collector aid to the ore and next performing a conditioning step of the ore in the presence of the primary collector and collector aid, wherein the primary collector is selected from the group consisting of an amphoteric surface-active compound, an anionic surface-active compound and combinations thereof; and the collector aid has the formula R 3 -C0-0-A n -R 4 where R 3 is a linear or branched, alkyl or hydroxyalkyl group having from 3 to 8 carbon atoms, R 4 is a linear or branched, alkyl or hydroxyalkyl group having from 3 to 10 carbon atoms, and at least one of R 3 and R 4 contains a hydroxyl group; and A is either ethoxy, propoxy or butoxy and n is a number from 0-10
- the primary collector and the collector aid can be added to the ore one after the other or simultaneously in one collector composition. Preferably they are added to the ore pre-blended in one collector composition, which collector composition may optionally contain further compounds, such as for example a secondary collector compound.
- the collector aid was found to boost the overall performance of the collector composition.
- the primary collector and collector aid in embodiments are contained in a single composition that is used for flotation or are added separately to be both present in the conditioning step. If an ore is conditioned with both the primary collector and the collector aid, the froth flotation results were found to be surprisingly better than when the collector aid component is added to the ore already conditioned with a composition that does not contain the collector aid of the present invention.
- recovery can be improved by around 4% by weight using the collector composition to which the collector aid was initially pre- blended as neat compared to a process in which conditioning with the primary collector did not include the collector aid. Meanwhile, poor grade of P2O5 was observed when adding the collector aid after the conditioning of the ore as a frother.
- the collector composition containing both the primary collector and collector aid also yields better frothing characteristics, including improved froth density and stability.
- a process of froth flotating a phosphate-containing ore employing a collector composition that contains an anionic or amphoteric primary collector in combination with a non- ionic ethoxy lated alcohol as a secondary collector.
- a frother is added to the process, that can be 2, 2, 4-trimethyl- l,3-pentanediol monoisobutyrate, but only after the ore was conditioned with the collector composition
- the primary collector disclosed herein is an amphoteric surface-active compound, an anionic surface-active compound or a combination thereof.
- Surface- active compounds or surfactants are compounds that lower the surface tension or interfacial tension between two liquids, between a gas and a liquid, and/or between a solid and a liquid.
- Anionic surface-active compounds typically contain a negatively charged (anionic) head group.
- Amphoteric surface-active compounds contain both cationic (positively charged) and anionic moieties within the same molecule. Below some examples of the primary collectors are provided; these examples should only be considered as suitable and are not to be regarded as limiting.
- the primary collector is an amphoteric surface- active compound having the formula (II)
- Ri is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms
- A is an alkyleneoxy group having 2-4, preferably 2, carbon atoms
- p is the number 0 or 1
- q is a number from 0-5, preferably 0
- R 2 is a hydrocarbyl group having 1-4, preferably 1, carbon atoms or R 2 is the group
- Ri, A, p and q have the same meaning as above; Y is COOH or SO 3 H, preferably COOH; n is the number 1 or 2, preferably 1; M is a cation, which can be monovalent or divalent and inorganic or organic, and r is the number 1 or 2.
- the primary collector can also be used in its acid form, where the nitrogen is protonated and no external cation is needed.
- the primary collector has the formula (III)
- R 2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms
- D is -CH 2 - or -CH 2 CH 2 -
- k is a number from 0-4, preferably 0-3, and most preferably 0-2
- M is hydrogen or a cation such as sodium or potassium.
- the primary collector is an anionic surface- active compound, such as fatty acids having an alkyl group with 8-24 carbon atoms, sulfonates, alkyl phosphates, alkyl sulfates and compounds having the formula (IV)
- R is a hydrocarbyl group having from 7-23, preferably 11-21, carbon atoms, optionally substituted;
- Ri is H or CH 3 , preferably H;
- R 2 is H or an alkyl group having from 1-4 carbon atoms, preferably H;
- R 3 is H or CH 3 , preferably CH 3 ;
- n is a number from 0-20;
- p is a number from 1-3, preferably 1;
- X is H + or a cation, organic or inorganic; and
- m represents the valency of the cation and is the number 1 or 2, preferably 1.
- the cation is preferably an alkali metal cation, an alkaline earth metal cation, ammonium, or a substituted ammonium group having one or more alkyl and/or hydroxyalkyl groups having from 1-3 carbon atoms.
- the primary collector comprises a sodium salt of an alkyl glycinate or sarcosinate having from 12 to 20, more preferably 12 to 16 carbon atoms.
- the primary collector is N-[2-hydroxy-3-(Cl2-l6- alkyloxy)propyl]-N-methyl glycinate (sodium C14-C15 sarcosinate).
- Suitable fatty acids having an alkyl group with 8-24 carbon atoms include fatty acids based on tall oil and oils of safflower, sunflower, soya, raps, com, lineseed, rapeseed, tallow, coconut, raw coniferous, and raw foliar).
- the primary collector is a phosphate ester.
- phosphate esters have the formulas
- R 2 is an alkyl group having from 6-22 carbon atoms, preferably 16-18 carbon atoms
- n is a number from 0-25 preferably 4
- M is a monovalent cation such as sodium or hydrogen.
- Alcohol ethoxylate phosphate ester (Phospholan type, Akzo Nobel Surface Chemistry LLC) contains the above phosphate esters where R 2 is an alkyl group having 18 carbon atoms, n is 4, and M is sodium or hydrogen.
- Suitable phosphate esters are monophosphate and diphosphate esters containing from 6-22 carbon atoms (linear or branched, degree of branching 1-3) and from 0-25 ethylene oxide (EO) units, and combination thereof.
- “Degree of branching” as used herein means the total number of methyl groups present on the main alkyl chain minus one.
- the collector aid of the collector composition is an ester having the formula
- R 3 is a linear or branched, alkyl or hydroxyalkyl group having from 3 to 8 carbon atoms
- R 4 is a linear or branched, alkyl or hydroxyalkyl group having from 3 to 10 carbon atoms, and at least one of R 3 and R 4 contains a hydroxyl group
- A is either ethoxy, propoxy or butoxy and n is a number from 0-10.
- Suitable collector aids include 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (Eastman Chemical Company); pentanoic acid, 3-hydroxy-4,4- dimethyl-2-(l-methylethyl)-, ethyl ester; heptanoic acid, 3-hydroxy-2, 2, 4-trimethyl-, ethyl ester; hexanoic acid, 4-ethyl-3-hydroxy-2, 2-dimethyl-, ethyl ester; 2-ethylhexane- (l,3)-diol mono-n-butyrate; 2-ethylhexane-(l,3)-diol di-n-butyrate, alkoxylated derivatives of same containing from 0-10 alkoxy units (more preferably 0-3 ethoxy units or 0-10 propoxy units), and combinations thereof.
- the weight ratio between the primary collector and the collector aid is from 999:1 to 1 : 1, preferably from 99:1 to 95:5, and more preferably from 99:1 to 96:4. All weight ratios herein refer to the ratio of active materials, unless stated otherwise.
- the collector composition containing the primary collector and the collector aid can optionally include a solvent.
- Suitable solvents include ethoxylated alcohols having from 3 to 10 EO groups, glycols ( e.g ., propylene glycol, diethylene glycol, etc.), non- ionic surfactants, low molecular weight alcohols, such Cl -Cl 5 alcohols, low molecular weight organic acids, such as Cl -Cl 5 organic acids, low molecular weight ethanolamines (e.g., triethanolamine, methyl diethanolamine, diethanolamine, etc.), water, organic solvents (e.g., toluene, hexane, etc.), aliphatic hydrocarbons, such as isoparaffines, paraffines, cycloparaffines, and their combinations.
- Low molecular weight solvents are in a preferred embodiment defined as solvents that have a molecular weight of up to 120 g/mole.
- the weight ratio between the primary collector and the optional solvent is preferably from 999:1 to 80:20, preferably from 99:1 to 90:10.
- the collector composition may be prepared by adding the primary collector, the collector aid and the optional solvent to a suitable vessel and mixing to combine. Additional flotation aids described herein can also be added to the collector composition before or after the primary collector and collector aid are combined. No special preparation steps (e.g., high shear mixing, heating, etc.) are necessary to prepare the collector composition.
- This disclosure also describes a method for the froth flotation of non- sulfidic ores, especially phosphate ores, to recover apatite minerals, in which method the collector composition described herein is used.
- Such froth flotation method for phosphate ores can typically include the following steps: a) conditioning a pulped phosphate-containing ore, wherein the ore includes a phosphate-containing mineral, and gangue minerals, with an effective amount of the collector composition described herein or the primary collector and collector aid separately, and optionally other flotation aids, and b) performing a froth flotation process to recover the phosphate-containing mineral(s).
- the amount of primary collector added to the ore will in general be in the range of from 10 to 1000 g/ton dry ore, preferably in the range of from 20 to 500 g/ton dry ore, more preferably from 100 to 400 g/ton dry ore.
- the amount of collector aid to added to the ore will in general be in the range of from 0.01-50 g/ton dry ore, preferably in the range of from 0.02-25 g/ton dry ore, more preferably from 0.05-20 g/ton dry ore
- a secondary collector can be present during the conditioning step.
- the secondary collector is selected from the group of anionic collector compounds, non- ionic collector compounds or mixtures of two or more of those, wherein the anionic collector is selected from the group of fatty acids, alkylsulfo succinates, alkylmaleates, alkylamidecarboxylate, esters of alkylamidecarboxylates, alkylbenzenesulphonates, alkylsulfonates, and sulfonated fatty acids, and the non-ionic collector compound is selected from the group of ethoxylates, glycosides, and ethanolamides, most preferably the non-ionic collector compound is selected from the group of branched and unbranched ethoxylated Cl 1-C24 alcohols, ethoxylated C10-C24 alkylamines, sugar surfactants, ethoxylated C10-C24 fatty acids
- flotation aids that can be present in the flotation process are depressants such as a polysaccharide, alkalized starch or dextrin; extender oils; frothers/froth regulators such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates, preferably C6-C10 alcohols and ethoxylates thereof; inorganic dispersants such as silicate of sodium (water glass) and soda ash; and pH-regulators (which can be acidic or alkaline compounds to adjust the pH as desired).
- depressants such as a polysaccharide, alkalized starch or dextrin
- extender oils frothers/froth regulators
- frothers/froth regulators such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates, preferably C6-
- the present invention in a preferred embodiment relates to a method for froth flotation of a phosphate ore, the method comprising: optionally, adding a depressant to the ore; adding the primary collector and collector aid as above to the ore; optionally, adding one or more further components to the ore selected from the group of pH adjusting agents, dispersants and secondary collector; wherein the primary collector, the collector aid and optional secondary collector can be added one after the other or simultaneously, optionally preblended in one collector composition; conditioning the ore in the presence of the primary collector, optional secondary collector, and the collector aid; subsequently, optionally adding one or more further components to the conditioned ore selected from the group of pH adjusting agents, dispersants and frothers; and performing a froth flotation process to recover phosphate-containing materials from the ore.
- a frother is added to the conditioned ore in a step subsequent to the conditioning of the ore in the presence of the primary collector and collector aid.
- the pH during the flotation process will normally be in the range of pH 8-11.
- a phosphate ore containing 42% apatite, 38% nepheline, 5% aegirine, 3% feldspar and 2% sphene was crushed and ground to a desirable flotation size (70% -160 pm).
- 500 g of the phosphate ore was placed into a 1.3 L (for rougher), 1.0 L (for cleaner 1) or 0.5 L (for cleaner 2) flotation cell.
- Tap water (Stenungsund municipal water with hardness 4 °dH) was added to the marked level in the cell (1.4L) and mixing was started. Further, 200 g/t water glass as a 1 wt-% solution was added and conditioned for 1 minute.
- Example flotation was performed at room temperature (20 ⁇ l °C), and the rougher flotation, the cleaner 1 flotation and the cleaner 2 flotation were performed for 4 minutes, 3 minutes and 2 minutes, respectively. All fractions (tailings, middlings and concentrate) were collected and analysed.
- alcohol ethoxy late phosphate ester (Phospholan type, Akzo Nobel Surface Chemistry LLC, henceforth “Phosphate Ester”) is a phosphate ester having the general formula R 2 -(0-CH 2 -CH 2 ) n - 0-PO(OM) 2 and (R 2 -(0-CH 2 -CH 2 ) n -0) 2 -P0-0M where R 2 is an alkyl group having 18 carbon atoms, n is 4, and M is sodium or hydrogen.
- Example 1 (Comparative): Collectors added individually- No collector aid
- Example 2 (Comparative): Collectors pre-mixed - No collector aid
- a collector composition containing 50 wt-% tall oils, 17 wt-% alkylbenzene sulfonate, and 33 wt-% Phosphate Ester was prepared.
- the collector composition was diluted in deionized water to a 1 wt-% solution.
- Example 1 and Example 2 results show, in the absence of the collector aid, a collector composition in which the composition components were separately added to the flotation showed no significant differences with respect to the same collector composition in which the components were pre-mixed and added to the flotation all at once.
- Example 3 (Comparative): Collector aid added as frother after conditioning
- the pH of the flotation mixture was adjusted to 9.9 with a 5% aqueous NaOH solution and quantities of the 1 wt-% solutions of tall oils and Phosphate Ester (the same as in Example 1) were mixed together and added to the flotation cell as a single stock solution to be equivalent to 145.5 g/t of a collector composition containing 61.8 wt-% tall oils and 38.2 wt-% Phosphate Ester.
- a conditioning step was carried out at 1000 rpm and room temperature for two minutes.
- Example 4 Collector aid, pre-mixed with primary collector
- a collector composition containing 60 wt-% tall oils, 37 wt-% Phosphate Ester, and 3 wt-% collector aid (2, 2, 4-trimethyl- l,3-pentanediol monoisobutyrate) was prepared.
- the collector composition was diluted in deionized water to a 1 wt-% solution.
- collector compositions containing the collector aid described herein e.g ., 2, 2, 4-trimethyl- l,3-pentanediol monoisobutyrate
- collector aid added to conditioning separately
- the pH of the flotation mixture was adjusted to 9.9 with a 5% aqueous NaOH solution and quantities of the 1 wt-% solutions of tall oils and Phosphate Ester (the same as in Example 1) were mixed together and added to the flotation cell to be equivalent to 145.5 g/t of a collector composition containing 61.8 wt-% tall oils and 38.2 wt-%
- the collector aid (2, 2, 4-trimethyl- l,3-pentanediol monoisobutyrate) was added to the conditioning step separately from the main collector stock solution to be equivalent to 4.5 g/t.
- a conditioning step was carried out at 1000 rpm and room temperature for two minutes.
- the flotation 1000 rpm and 3 L/min rougher; 1500 rpm, 1.3 L/min cleaner 1; and 1500 rpm and 0.6 L/min cleaner 2 was started.
- the flotation results are shown in Table 5.
- Example 5 shows that when the collector was added separately from the main collector solution before the conditioning step of the ore, the grade of P2O5 remained higher than in the Example 3 demonstrating that the collector aid if present during the conditioning step improves the results. Pre-blending the collector aid with the other collector compounds is however preferred as visible from the results obtained in Example 4.
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- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Degasification And Air Bubble Elimination (AREA)
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EP18182117 | 2018-07-06 | ||
PCT/EP2019/067975 WO2020007971A1 (en) | 2018-07-06 | 2019-07-04 | Process for froth flotation |
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BR (1) | BR112021000181A2 (de) |
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Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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SU1309904A3 (ru) | 1981-05-13 | 1987-05-07 | Берол Кеми Аб (Фирма) | Способ пенной флотации апатит-карбонатной руды |
SE452120B (sv) | 1984-04-04 | 1987-11-16 | Berol Kemi Ab | Forfarande for skumflotation samt flotationsmedel herfor |
DE4016792A1 (de) * | 1990-05-25 | 1991-11-28 | Henkel Kgaa | Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation |
US5443158A (en) * | 1992-10-02 | 1995-08-22 | Fording Coal Limited | Coal flotation process |
RU2288040C1 (ru) * | 2005-03-24 | 2006-11-27 | Станислав Николаевич Титков | Способ флотации хлористого натрия |
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 |
EA033037B9 (ru) | 2014-09-18 | 2020-02-19 | Норион Кемикалз Интернэшнл Б.В. | Применение алкоксилатов разветвленных жирных спиртов в качестве вторичных коллекторов для пенной флотации |
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- 2019-07-04 EP EP19734426.0A patent/EP3817860B1/de active Active
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