CA3016794C - Use of emulsifier in collector composition - Google Patents
Use of emulsifier in collector composition Download PDFInfo
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- CA3016794C CA3016794C CA3016794A CA3016794A CA3016794C CA 3016794 C CA3016794 C CA 3016794C CA 3016794 A CA3016794 A CA 3016794A CA 3016794 A CA3016794 A CA 3016794A CA 3016794 C CA3016794 C CA 3016794C
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 7
- 150000001875 compounds Chemical group 0.000 claims abstract description 156
- 238000000034 method Methods 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 238000007046 ethoxylation reaction Methods 0.000 claims abstract description 30
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 238000009291 froth flotation Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 125000000129 anionic group Chemical group 0.000 claims abstract description 14
- 150000001298 alcohols Chemical class 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 230000002902 bimodal effect Effects 0.000 claims abstract description 6
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 6
- 238000005188 flotation Methods 0.000 claims description 30
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 22
- 239000011707 mineral Substances 0.000 claims description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 21
- 150000001768 cations Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 235000021317 phosphate Nutrition 0.000 claims description 14
- -1 propyleneoxy unit Chemical group 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 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 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 150000003626 triacylglycerols Chemical class 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 235000010755 mineral Nutrition 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 229910052586 apatite Inorganic materials 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 229920000847 nonoxynol Polymers 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001748 carbonate mineral Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 description 2
- 229910052585 phosphate mineral Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 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
- 101100328895 Caenorhabditis elegans rol-8 gene Proteins 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical group OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052589 chlorapatite Inorganic materials 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000994 depressogenic 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil 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
- 239000010665 pine oil Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 102220079472 rs781825705 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- TYLSDQJYPYQCRK-UHFFFAOYSA-N sulfo 4-amino-4-oxobutanoate Chemical compound NC(=O)CCC(=O)OS(O)(=O)=O TYLSDQJYPYQCRK-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 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
- B03D1/0043—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
- B03D1/001—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
- B03D1/012—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
-
- 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
- B03D2203/06—Phosphate ores
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to secondary collector mixtures containing at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching (DB) of 1-3.5 and their alkoxylates with a degree of ethoxylation (DE) of up to 4, and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds with a degree of ethoxylation of higher than 3 and carbohydrate-based surfactants, wherein if both compounds (i) and (ii) are ethoxylated alcohols, the mixture has a bimodal degree of ethoxylation distribution; to the use of compound (ii) as an emulsifier for compound (i) in a liquid; to collector compositions containing the secondary collector mixtures together with a primary collector that is an amphoteric or anionic surface-active compound; and to the use of the above compositions in a process for froth flotation of non-sulfidic ores.
Description
USE OF EMULSIFIER IN COLLECTOR COMPOSITION
Field of Invention The present invention relates to the use of emulsifiers in branched alcohol and/or alkoxylate-containing secondary collector compositions and the use of such compositions for the froth flotation of non-sulfidic ores, especially phosphate ores, in combination with a primary collector which is an anionic or an amphoteric surface active-compound.
Background of the invention 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.
It is well-known to separate the valuable phosphate minerals from the gangue by using a froth flotation process where the phosphate minerals are enriched in the float.
Good performance in a froth flotation process is achieved by a combination of, on the one hand, a good separation of the valuable mineral from the gangue by using a selective collector and, on the other hand, the froth characteristics.
The froth characteristics include both the amount and the stability of the froth.
It is important in the flotation process that the froth collapses as soon as possible after it leaves the flotation cell for the next step in the beneficiation process. A
too stable froth will cause both entrainment of particles and froth product pumping problems. Entrainment, especially on a large scale, will result in decreased selectivity (grade, recovery). Problems with froth product pumping will make a process of flotation technically impossible.
Field of Invention The present invention relates to the use of emulsifiers in branched alcohol and/or alkoxylate-containing secondary collector compositions and the use of such compositions for the froth flotation of non-sulfidic ores, especially phosphate ores, in combination with a primary collector which is an anionic or an amphoteric surface active-compound.
Background of the invention 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.
It is well-known to separate the valuable phosphate minerals from the gangue by using a froth flotation process where the phosphate minerals are enriched in the float.
Good performance in a froth flotation process is achieved by a combination of, on the one hand, a good separation of the valuable mineral from the gangue by using a selective collector and, on the other hand, the froth characteristics.
The froth characteristics include both the amount and the stability of the froth.
It is important in the flotation process that the froth collapses as soon as possible after it leaves the flotation cell for the next step in the beneficiation process. A
too stable froth will cause both entrainment of particles and froth product pumping problems. Entrainment, especially on a large scale, will result in decreased selectivity (grade, recovery). Problems with froth product pumping will make a process of flotation technically impossible.
2 Collector performance may be improved by using collector combinations of a primary (main) collector and a secondary collector (co-collector). In this document the term "collector composition" shall be used to describe compositions containing both a primary and a secondary collector.
For many decades 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.
US 4,814,070 discloses the flotation of non-sulfidic ores wherein alkyl sulfosuccinates based on propoxylated and ethoxylated C8-C22 fatty alcohols are employed as a collector. However, nowhere in this document are fatty alcohols having a high degree of branching mentioned nor is it disclosed or suggested that they can be used without the sulfosuccinate function.
US 4,789,466 discloses the flotation of apatite ores with a collector composition that contains two components, wherein one is an ethoxylated and propoxylated fatty alcohol and the other is a cationic, anionic or ampholytic surfactant, preferably a sulfosuccinamate surfactant. The surfactant is the primary collector and the alkoxylated fatty alcohol the secondary collector in the apatite ore flotation process. The degree of branching of the used fatty alcohol is either not disclosed or fatty alcohols are applied which are known to have a degree of branching that is 1 or less. US '466 moreover does not disclose mixtures of two alkoxylated alcohols wherein one is relatively highly branched and ethoxylated with 1 to 4 ethylene oxide groups and the other has a higher amount of EO
groups than the first alkoxylated alcohol. Nor does this document disclose the use of such mixtures as secondary collector in the flotation of apatite ores or suggest the benefits thereof.
For many decades 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.
US 4,814,070 discloses the flotation of non-sulfidic ores wherein alkyl sulfosuccinates based on propoxylated and ethoxylated C8-C22 fatty alcohols are employed as a collector. However, nowhere in this document are fatty alcohols having a high degree of branching mentioned nor is it disclosed or suggested that they can be used without the sulfosuccinate function.
US 4,789,466 discloses the flotation of apatite ores with a collector composition that contains two components, wherein one is an ethoxylated and propoxylated fatty alcohol and the other is a cationic, anionic or ampholytic surfactant, preferably a sulfosuccinamate surfactant. The surfactant is the primary collector and the alkoxylated fatty alcohol the secondary collector in the apatite ore flotation process. The degree of branching of the used fatty alcohol is either not disclosed or fatty alcohols are applied which are known to have a degree of branching that is 1 or less. US '466 moreover does not disclose mixtures of two alkoxylated alcohols wherein one is relatively highly branched and ethoxylated with 1 to 4 ethylene oxide groups and the other has a higher amount of EO
groups than the first alkoxylated alcohol. Nor does this document disclose the use of such mixtures as secondary collector in the flotation of apatite ores or suggest the benefits thereof.
3 PCT/EP2017/056516 SE 409291 discloses a method for foam flotation of calcium phosphate-containing minerals, using an amphoteric surface-active compound as the primary collector. The primary collector's flotating ability may further be strengthened by the presence of a secondary collector, which is described as a polar, water-insoluble, hydrophobic substance having affinity to the mineral particles that have been coated by the primary collector. Examples of the polar components are e.g. water-insoluble soaps, such as calcium soaps, water-insoluble surface-active alkylene oxide adducts, organic phosphate compounds, such as tributyl phosphate, and esters of carbonic acids, such as tributyl ester of nitrilotriacetic acid. In the working examples nonylphenol that has been reacted with two moles of ethylene oxide was used as the secondary collector.
The secondary collector disclosed in SE'291 is still considered a good choice in treating ores, as it provides for an excellent mineral recovery at a P205 grade of higher than 30%. However, due to environmental concerns, an intense search for a replacement of nonylphenol ethoxylates has been ongoing for a long time.
EP 0 270 933 A2 discloses mixtures as collectors for flotation of non-sulfidic ores that contain an alkyl or alkenyl polyethylene glycol ether that is end-capped with a hydrophobic group and an anionic tenside. The end-capped alkyl or alkenyl polyethylene glycol ether in some embodiments is based on a fatty alcohol, preferably a 012 to 018 fatty alcohol. In comparative Examples in EP
270 933 also non-end-capped fatty alcohols are used together with anionic tensides. In EP 0 270 933 no disclosure is made of using fatty alcohols having a degree of branching of 1 to 3, and the molecules exemplified in the EP'933 document, though more environmentally friendly than nonylphenol ethoxylates, do not perform as well as these nonylphenol ethoxylates as collectors for flotation of non-sulfidic ores in terms of mineral recovery at the desired high grades.
Thus, there is still a need for secondary collectors having a better environmental profile than nonylphenol ethoxylates that perform equally well.
The secondary collector disclosed in SE'291 is still considered a good choice in treating ores, as it provides for an excellent mineral recovery at a P205 grade of higher than 30%. However, due to environmental concerns, an intense search for a replacement of nonylphenol ethoxylates has been ongoing for a long time.
EP 0 270 933 A2 discloses mixtures as collectors for flotation of non-sulfidic ores that contain an alkyl or alkenyl polyethylene glycol ether that is end-capped with a hydrophobic group and an anionic tenside. The end-capped alkyl or alkenyl polyethylene glycol ether in some embodiments is based on a fatty alcohol, preferably a 012 to 018 fatty alcohol. In comparative Examples in EP
270 933 also non-end-capped fatty alcohols are used together with anionic tensides. In EP 0 270 933 no disclosure is made of using fatty alcohols having a degree of branching of 1 to 3, and the molecules exemplified in the EP'933 document, though more environmentally friendly than nonylphenol ethoxylates, do not perform as well as these nonylphenol ethoxylates as collectors for flotation of non-sulfidic ores in terms of mineral recovery at the desired high grades.
Thus, there is still a need for secondary collectors having a better environmental profile than nonylphenol ethoxylates that perform equally well.
4 Co-pending patent application PCT appl # EP 2015/071003 discloses the use of a secondary collector, suitable for use with a primary collector of the amphoteric or anionic type, for the froth flotation of non-sulfidic ores to recover oxides, carbonates, phosphates and other salt-type minerals, especially calcium .. phosphate-containing minerals, in which the secondary collector is a branched fatty alcohol-based compound selected from the group of fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3, and their alkoxylates with a degree of ethoxylation of up to 3.
Summary of the invention It has been found in the present invention that a secondary collector which can be used in combination with a primary collector of the amphoteric or anionic type for the froth flotation of non-sulfidic ores to recover oxides, carbonates, phosphates and other salt-type minerals, especially calcium phosphate-containing minerals, wherein the secondary collector is a mixture containing at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5 and their alkoxylates with a degree of ethoxylation (DE) of up to 4, and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds, such as fatty amines, fatty alcohols, fatty (di)ethanolamides, fatty acids, triglycerides, with a degree of ethoxylation (DE) of higher than 3, and carbohydrate-based surfactants, leads to similar good efficiency in recovering apatite in the presence of silicate and/or carbonate minerals as when using a secondary collector only containing compound (i), and to the same good environmental profile especially when compared to nonylphenol ethoxylates, but that additionally compound (ii) has as a benefit that it helps to emulsify compound (i) in the collector composition, enabling compound (i) to be used more efficiently, like in a smaller amount.
Description of the drawings Figure 1 is the distribution of the degree of ethoxylation in a mixture according to the invention Figure 2 is a schematic flow chart of a flotation procedure Detailed description of the invention
Summary of the invention It has been found in the present invention that a secondary collector which can be used in combination with a primary collector of the amphoteric or anionic type for the froth flotation of non-sulfidic ores to recover oxides, carbonates, phosphates and other salt-type minerals, especially calcium phosphate-containing minerals, wherein the secondary collector is a mixture containing at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5 and their alkoxylates with a degree of ethoxylation (DE) of up to 4, and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds, such as fatty amines, fatty alcohols, fatty (di)ethanolamides, fatty acids, triglycerides, with a degree of ethoxylation (DE) of higher than 3, and carbohydrate-based surfactants, leads to similar good efficiency in recovering apatite in the presence of silicate and/or carbonate minerals as when using a secondary collector only containing compound (i), and to the same good environmental profile especially when compared to nonylphenol ethoxylates, but that additionally compound (ii) has as a benefit that it helps to emulsify compound (i) in the collector composition, enabling compound (i) to be used more efficiently, like in a smaller amount.
Description of the drawings Figure 1 is the distribution of the degree of ethoxylation in a mixture according to the invention Figure 2 is a schematic flow chart of a flotation procedure Detailed description of the invention
5 In one aspect, the invention relates to (a secondary collector) mixture of at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5 and their alkoxylates with a degree of ethoxylation of up to 4, and at least one compound (ii) selected from carbohydrate-based surfactants and alkoxylates of nonionic hydrocarbon compounds with a degree of ethoxylation of more than 3, such as alkoxylates of hydrocarbon compounds of the group of fatty alcohols, fatty amines, fatty ethanolamides, fatty diethanolamides, fatty acids, triglycerides with a degree of ethoxylation of more than 3, wherein when both compounds (i) and (ii) are ethoxylated alcohols, the mixture has a bimodal degree of ethoxylation distribution.
It should be noted that the mixture of compounds (i) and (ii) - in the embodiments wherein both compounds are ethoxylated alcohol compounds -has a bimodal DE distribution (bimodal meaning a statistical distribution with two maxima). Or in other words, the mixture is not an inherent mixture of more than .. one molecule that is obtained when a single ethoxylation reaction is performed with a hydrocarbon compound and wherein always some lower and higher ethoxylated molecules are formed and wherein the DE distribution would be unimodal (i.e. have a single maximum). Instead in the present invention the mixture is a mixture obtained by mixing two separately ethoxylated alcohol compounds (i) and (ii).
If both compounds (i) and (ii) are ethoxylated, preferably the degree of ethoxylation of compound (ii) is higher than that of compound (i).
It should be noted that the mixture of compounds (i) and (ii) - in the embodiments wherein both compounds are ethoxylated alcohol compounds -has a bimodal DE distribution (bimodal meaning a statistical distribution with two maxima). Or in other words, the mixture is not an inherent mixture of more than .. one molecule that is obtained when a single ethoxylation reaction is performed with a hydrocarbon compound and wherein always some lower and higher ethoxylated molecules are formed and wherein the DE distribution would be unimodal (i.e. have a single maximum). Instead in the present invention the mixture is a mixture obtained by mixing two separately ethoxylated alcohol compounds (i) and (ii).
If both compounds (i) and (ii) are ethoxylated, preferably the degree of ethoxylation of compound (ii) is higher than that of compound (i).
6 Additionally, the invention relates to the use of the mixture of the above compounds (i) and (ii) as secondary collectors for the froth flotation of non-sulfidic ores, especially to recover calcium phosphate-containing minerals, such as apatite, in combination with a primary collector which is an amphoteric or anionic surfactant and to collector compositions containing such primary and secondary collectors. Examples of other valuable minerals that may be recovered using this combination of primary and secondary collectors include scheelite, fluorspar, calcite and dolomite.
Furthermore, the invention relates to the use of compound (ii) as an emulsifier for compound (i) in a liquid, most prominently a carrier liquid in which a collector composition is present, or alternatively, it relates to a process to emulsify compound (i) in a liquid. This process to emulsify a compound (i) in a liquid contains a step of adding compound (i) to the liquid and a step of adding a compound (ii) to the liquid, wherein the steps may be done one after the other or simultaneously, optionally by premixing compounds (i) and (ii). In a preferred process compounds (i) and (ii) are first mixed and the so obtained mixture is added to the carrier liquid. The carrier liquid for the collector composition is preferably an aqueous liquid.
In preferred mixtures the ratio of compound (i) to compound (ii) on a weight basis is from 30:70 to 99:1, more preferably from 40:60 to 98:2, even more preferably from 50:50 to 90:10.
By "the degree of branching" (DB) as used herein is meant the total number of methyl groups present on the alkyl or alkenyl chain of the alcohol or alkoxylate thereof, minus one. The mean number of methyl groups in the molecules of a sample can easily be determined by NMR spectroscopy. It should be understood that the degree of branching (DB) in the 012-016 branched fatty alcohol that delivers the branched alkyl or alkenyl chain for compound (i) is an average degree of branching for the fatty alcohol used. Fatty alcohols are oftentimes available or applied as a mixture of several components and
Furthermore, the invention relates to the use of compound (ii) as an emulsifier for compound (i) in a liquid, most prominently a carrier liquid in which a collector composition is present, or alternatively, it relates to a process to emulsify compound (i) in a liquid. This process to emulsify a compound (i) in a liquid contains a step of adding compound (i) to the liquid and a step of adding a compound (ii) to the liquid, wherein the steps may be done one after the other or simultaneously, optionally by premixing compounds (i) and (ii). In a preferred process compounds (i) and (ii) are first mixed and the so obtained mixture is added to the carrier liquid. The carrier liquid for the collector composition is preferably an aqueous liquid.
In preferred mixtures the ratio of compound (i) to compound (ii) on a weight basis is from 30:70 to 99:1, more preferably from 40:60 to 98:2, even more preferably from 50:50 to 90:10.
By "the degree of branching" (DB) as used herein is meant the total number of methyl groups present on the alkyl or alkenyl chain of the alcohol or alkoxylate thereof, minus one. The mean number of methyl groups in the molecules of a sample can easily be determined by NMR spectroscopy. It should be understood that the degree of branching (DB) in the 012-016 branched fatty alcohol that delivers the branched alkyl or alkenyl chain for compound (i) is an average degree of branching for the fatty alcohol used. Fatty alcohols are oftentimes available or applied as a mixture of several components and
7 therefore DB does not have to be an integer. Consequently, the degree of branching for compound (i) is an average degree of branching, wherein the average degree of branching is the statistical mean of the degree of branching of the molecules of a sample.
.. In a preferred embodiment the DB in compound (i) is higher than 1, even more preferably it is higher than 1.5, most preferably higher than 2. In another more preferred embodiment the DB is lower than 3.2, most preferred it is 3 or lower.The molecular formula of the secondary collector compounds (i) and (ii) in a preferred embodiment is R-A (I), wherein for compound (i) R is an alkyl or alkenyl group having 12-16, preferably 12-15, carbon atoms and where said alkyl or alkenyl group has a degree of branching of 1-3, and wherein for compound (ii) R is any alkyl, aryl or alkenyl group branched or linear having 8-24 carbon atoms; A is selected from the groups 0-(P0)(E0)y(P0),1-1, for compounds (i) and (ii) (CO)N(CH2CH20(P0)(E0)y(P0),1-1)2, for compound (ii) (CO)NH(CH2CH20(P0)(E0)y(P0),1-1), for compound (ii) (C0)0((P0)(E0)y(P0),1-1), for compound (ii) N(P0)x(E0)y(P0),1-1)2, for compound (ii) (C0)0((P0),;(E0)y(P0),OCH2CH(O(P0),;(E0)y(P0),O(CO)R)CH20((P0),;(E0)y( P0),O(CO)R), for compound (ii), and 0(C6F11105)-(0-(C6H1105))m, for compound (ii) wherein for compound (i) PO is a propyleneoxy unit and EO is an ethyleneoxy unit; x is a number 0-2, preferably 0, y is a number 0-4, preferably 0-3, more
.. In a preferred embodiment the DB in compound (i) is higher than 1, even more preferably it is higher than 1.5, most preferably higher than 2. In another more preferred embodiment the DB is lower than 3.2, most preferred it is 3 or lower.The molecular formula of the secondary collector compounds (i) and (ii) in a preferred embodiment is R-A (I), wherein for compound (i) R is an alkyl or alkenyl group having 12-16, preferably 12-15, carbon atoms and where said alkyl or alkenyl group has a degree of branching of 1-3, and wherein for compound (ii) R is any alkyl, aryl or alkenyl group branched or linear having 8-24 carbon atoms; A is selected from the groups 0-(P0)(E0)y(P0),1-1, for compounds (i) and (ii) (CO)N(CH2CH20(P0)(E0)y(P0),1-1)2, for compound (ii) (CO)NH(CH2CH20(P0)(E0)y(P0),1-1), for compound (ii) (C0)0((P0)(E0)y(P0),1-1), for compound (ii) N(P0)x(E0)y(P0),1-1)2, for compound (ii) (C0)0((P0),;(E0)y(P0),OCH2CH(O(P0),;(E0)y(P0),O(CO)R)CH20((P0),;(E0)y( P0),O(CO)R), for compound (ii), and 0(C6F11105)-(0-(C6H1105))m, for compound (ii) wherein for compound (i) PO is a propyleneoxy unit and EO is an ethyleneoxy unit; x is a number 0-2, preferably 0, y is a number 0-4, preferably 0-3, more
8 preferably 0-2.5, even more preferably 0-2.3 and most preferably 0-2, and z is a number 0-2, preferably 0, and wherein for compound (ii) PO is a propyleneoxy unit and EO is an ethyleneoxy unit; x is a number 0-20, preferably 0, y is a number higher than 3 up to 30, preferably 4-20, more preferably 5-15, even more preferably 7-12, z is a number 0-20, preferably 0, and m is an integer of to 5.
The mixture may in addition contain further components such as a liquid. In preferred embodiments such liquid is an aqueous liquid, even more preferably the liquid contains more than 95% of water. In such mixtures compound (ii) acts as an emulsifier for compound (i).
As is evident from formula (I) for compound (i), the alcohols as such, as well as their alkoxylates, may be used in the secondary collector mixtures.
The alkoxylated products according to formula (I) may be produced by procedures well-known in the art by reacting the appropriate starting alcohol, acid, amide, amine or triglyceride with ethylene oxide, or propylene oxide and ethylene oxide, in the presence of a suitable catalyst, e.g. a conventional basic catalyst, such as KOH, or a so-called narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1-37 and 87-107, edited by Nico M. van Os; Marcel Dekker, Inc). If both propylene oxide and ethylene oxide are used, the alkoxides may be added as blocks in either order, or may be added randomly. The products obtained from reaction with only ethylene oxide are the most preferred.
Preferred compounds (i) are alcohol alkoxylates with a degree of ethoxylation of up to 3. Preferred compounds (ii) are alcohol alkoxylates with a degree of ethoxylation of higher than 3, even more preferred higher than 4. In an embodiment their degree of ethoxylation is up to 30, preferably up to 20. For both compounds (i) and (ii) it is preferred that they have a degree of propoxylation of less than 2, even more preferably less than 1, most preferably of about 0.
The mixture may in addition contain further components such as a liquid. In preferred embodiments such liquid is an aqueous liquid, even more preferably the liquid contains more than 95% of water. In such mixtures compound (ii) acts as an emulsifier for compound (i).
As is evident from formula (I) for compound (i), the alcohols as such, as well as their alkoxylates, may be used in the secondary collector mixtures.
The alkoxylated products according to formula (I) may be produced by procedures well-known in the art by reacting the appropriate starting alcohol, acid, amide, amine or triglyceride with ethylene oxide, or propylene oxide and ethylene oxide, in the presence of a suitable catalyst, e.g. a conventional basic catalyst, such as KOH, or a so-called narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1-37 and 87-107, edited by Nico M. van Os; Marcel Dekker, Inc). If both propylene oxide and ethylene oxide are used, the alkoxides may be added as blocks in either order, or may be added randomly. The products obtained from reaction with only ethylene oxide are the most preferred.
Preferred compounds (i) are alcohol alkoxylates with a degree of ethoxylation of up to 3. Preferred compounds (ii) are alcohol alkoxylates with a degree of ethoxylation of higher than 3, even more preferred higher than 4. In an embodiment their degree of ethoxylation is up to 30, preferably up to 20. For both compounds (i) and (ii) it is preferred that they have a degree of propoxylation of less than 2, even more preferably less than 1, most preferably of about 0.
9 Carbohydrate-based surfactants, also referred to above as being of the formula R-0-(C6F11105) in a preferred embodiment, are surfactants that are generally nonionic and that in a preferred embodiment contain at least one unit chosen from the group of carbohydrates, such as sorbitol (sorbitans), glucose .. (glycosides), sucrose and/or their esters, amides.
The primary collectors used in the froth flotation according to the present invention may be either amphoteric or anionic surface-active compounds. Below some examples of formulae for the primary collectors are given, but these should only be considered as suitable for the invention, and are not to be regarded as limiting.
In one embodiment the primary collector for the above-mentioned froth flotation procedure has the formula (II) R C)411 fl\I ¨
1 A ig Y (Mr+)1/r (II) - - n OH
wherein R1 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 a number or 1; q is a number from 0 to 5, preferably 0; R2 is a hydrocarbyl group having 1-4 carbon atoms, preferably 1, or R2 is the group cH2 R1-'1. O4 Arci OH
, wherein R1, A, p and q have the same meaning as above; r is selected from the group consisting of C00- and S03-, preferably C00-; n is a number 1 or 2, preferably 1; M is a cation, which may be monovalent or divalent, and inorganic or organic, and r is a number 1 or 2. The primary collector may also be used in its acid form, where the nitrogen is protonated and no external cation is needed.
The compounds according to formula (II) can easily be produced in high yield from commercially available starting materials using known procedures. US
5 4,358,368 discloses some ways to produce the compounds where R1 is a hydrocarbyl group with 8-22 carbon atoms (col 6, line 9 ¨ col 7, line 52), and in US 4,828,687 (col 2, line 2¨ col 2, line 31) compounds where R2 is R11. 44..-1Arq OH
attached to the compound of formula (II) via the methylene group, are described.
The primary collectors used in the froth flotation according to the present invention may be either amphoteric or anionic surface-active compounds. Below some examples of formulae for the primary collectors are given, but these should only be considered as suitable for the invention, and are not to be regarded as limiting.
In one embodiment the primary collector for the above-mentioned froth flotation procedure has the formula (II) R C)411 fl\I ¨
1 A ig Y (Mr+)1/r (II) - - n OH
wherein R1 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 a number or 1; q is a number from 0 to 5, preferably 0; R2 is a hydrocarbyl group having 1-4 carbon atoms, preferably 1, or R2 is the group cH2 R1-'1. O4 Arci OH
, wherein R1, A, p and q have the same meaning as above; r is selected from the group consisting of C00- and S03-, preferably C00-; n is a number 1 or 2, preferably 1; M is a cation, which may be monovalent or divalent, and inorganic or organic, and r is a number 1 or 2. The primary collector may also be used in its acid form, where the nitrogen is protonated and no external cation is needed.
The compounds according to formula (II) can easily be produced in high yield from commercially available starting materials using known procedures. US
5 4,358,368 discloses some ways to produce the compounds where R1 is a hydrocarbyl group with 8-22 carbon atoms (col 6, line 9 ¨ col 7, line 52), and in US 4,828,687 (col 2, line 2¨ col 2, line 31) compounds where R2 is R11. 44..-1Arq OH
attached to the compound of formula (II) via the methylene group, are described.
10 In another embodiment the primary collector has the formula (III) COOM COOM
D/ D/
N.-.N COOM (III) - k wherein R2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms, D
is ¨CH2- or -CH2CH2- , k is 0-4, preferably 0-3, and most preferably 0-2, and M
is hydrogen or a cation, such as sodium or potassium.
These products are well known and are produced commercially by methods well known in the art. The products where D is ¨CH2- are prepared by the reaction between a fatty amine and chloroacetic acid or its salts, and the products where D is -CH2CH2- are prepared by the reaction between a fatty amine and acrylic acid or esters thereof, in the latter case the reaction is followed by hydrolysis.
D/ D/
N.-.N COOM (III) - k wherein R2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms, D
is ¨CH2- or -CH2CH2- , k is 0-4, preferably 0-3, and most preferably 0-2, and M
is hydrogen or a cation, such as sodium or potassium.
These products are well known and are produced commercially by methods well known in the art. The products where D is ¨CH2- are prepared by the reaction between a fatty amine and chloroacetic acid or its salts, and the products where D is -CH2CH2- are prepared by the reaction between a fatty amine and acrylic acid or esters thereof, in the latter case the reaction is followed by hydrolysis.
11 In a further embodiment the primary collector is selected from anionic surface-active compounds such as fatty acids (with a 08 to 024-acyl group), sulfonates, alkyl phosphates, alkyl sulfates and compounds of formula (IV) X
/ \
\ 1 P n _ ¨ m (IV) where R is a hydrocarbyl group having from 7-23, preferably 11-21, carbon atoms, optionally substituted; R1 is H or CH3, preferably H; R2 is H or a 01-alkyl group, preferably H; R3 is H or CH3, preferably CH3; n is a number 1-20;
p is a number 1-3, preferably 1; X is H+ or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2, preferably 1.
The cation is preferably selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, ammonium, and a substituted ammonium group having one or more Ci to 03 alkyl and/or hydroxyalkyl groups.
For the production of compounds of formula (IV) see the description in WO
2015/000931 (corresponding to PCT/EP2014/064014).
Also it is possible to have mixtures of the above compounds as a primary collector. In the case of mixing amphoteric and anionic surface-active compounds as the primary collector, it is preferred to have up to 20 weight %
of anionic surfactant on the amount of amphoteric surfactant.
In another aspect, the invention relates to a method for froth flotation of non-sulfidic ores, especially phosphate ores, to recover apatite minerals, in which method the collector mixture described above is used.
Such froth flotation method for phosphate ores may typically comprise the steps of:
/ \
\ 1 P n _ ¨ m (IV) where R is a hydrocarbyl group having from 7-23, preferably 11-21, carbon atoms, optionally substituted; R1 is H or CH3, preferably H; R2 is H or a 01-alkyl group, preferably H; R3 is H or CH3, preferably CH3; n is a number 1-20;
p is a number 1-3, preferably 1; X is H+ or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2, preferably 1.
The cation is preferably selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, ammonium, and a substituted ammonium group having one or more Ci to 03 alkyl and/or hydroxyalkyl groups.
For the production of compounds of formula (IV) see the description in WO
2015/000931 (corresponding to PCT/EP2014/064014).
Also it is possible to have mixtures of the above compounds as a primary collector. In the case of mixing amphoteric and anionic surface-active compounds as the primary collector, it is preferred to have up to 20 weight %
of anionic surfactant on the amount of amphoteric surfactant.
In another aspect, the invention relates to a method for froth flotation of non-sulfidic ores, especially phosphate ores, to recover apatite minerals, in which method the collector mixture described above is used.
Such froth flotation method for phosphate ores may typically comprise the steps of:
12 a) conditioning a pulped ore, wherein the ore comprises a phosphate-containing mineral, and gangue minerals in an aqueous medium, optionally, conditioning the mixture with a flotation aid (in some embodiments a depressant); and optionally, adjusting the pH
b) adding an aqueous composition (in some embodiments an aqueous emulsion) containing the primary and the secondary collector described herein, and, optionally, adjusting the pH
c) optionally, adding a frother; and d) performing a froth flotation process to recover the phosphate-containing mineral(s).
In yet another aspect the invention pertains to a collector composition comprising a primary collector as defined herein and a secondary collector mixture as defined herein.
The weight ratio between the primary collector and the secondary collector in both the collector compositions and the flotation processes is preferably from 15:85, more preferably 20:80, most preferably 25:75 to 99:1, preferably 98:2, most preferably 97:3. All weight ratios herein refer to the ratio of active materials, unless stated otherwise.
The amount of collector composition 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, more preferably from 100 to 400 g/ton dry ore.
Further flotation aids that may 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, inorganic dispersants, such as silicate of sodium (water glass) and soda ash, and pH-regulators.
b) adding an aqueous composition (in some embodiments an aqueous emulsion) containing the primary and the secondary collector described herein, and, optionally, adjusting the pH
c) optionally, adding a frother; and d) performing a froth flotation process to recover the phosphate-containing mineral(s).
In yet another aspect the invention pertains to a collector composition comprising a primary collector as defined herein and a secondary collector mixture as defined herein.
The weight ratio between the primary collector and the secondary collector in both the collector compositions and the flotation processes is preferably from 15:85, more preferably 20:80, most preferably 25:75 to 99:1, preferably 98:2, most preferably 97:3. All weight ratios herein refer to the ratio of active materials, unless stated otherwise.
The amount of collector composition 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, more preferably from 100 to 400 g/ton dry ore.
Further flotation aids that may 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, inorganic dispersants, such as silicate of sodium (water glass) and soda ash, and pH-regulators.
13 The pH during the flotation process will preferably be in the range of 8-11.
The present invention is further illustrated by the following examples.
EXAMPLES
Example 1 General flotation procedure A phosphate ore containing 20-25% of apatite, 30-40% of silicates and c. 20%
of iron oxides was crushed and ground to a desirable flotation size (K80=110pm).
Three alkoxylates were prepared by reacting the alcohol Exxal 13 (ex Exxon), which has a DB of 3, with ethylene oxide in an amount of 1.5, 5 and 8.5 equivalents, respectively, on the molar amount of the alcohol.
500 g of the ore were placed in a 1.4L Denver flotation cell, 500 ml of process water (25mg/I Ca2+, 40mg/I Mg2+) were added and the mixing was started. Then 5 minutes conditioning with 1000g/t of a 1`)/0(w/w) aqueous starch solution was performed, the collector (600g/t (or a mixture of primary acylglycide collector and secondary collectors)) was added to the flotation cell as a 1`)/0 aqueous solution and conditioning was continued for 2.5 minutes. After the conditioning steps tap water was added so that a total volume of 1.4L was obtained, the pH
of the flotation mixture was adjusted to 9.5 with a 10% NaOH aqueous solution and the flotation was started. The experiment was performed at RT (20 1 C).
The rougher flotation, followed by three cleaning steps, was performed. All fractions (tailings, middlings and concentrate) were collected and analysed.
Reference is made to Figure 2 for the general procedure that was followed.
The flotation results and the composition of the collector formulation used are displayed in Table 1.
Table 1. Flotation results presented as P205 recovery and grade.
Amount of Average degree Amount of 2nd cleaner concentrate 3rd cleaner concentrate alcohol+XEO, g/t of ethoxylation acylglycide, 1.5E0 5E0 8.5E0 g/t Recovery, % Grade, %
Recovery, % Grade, %
Comparison 0 0 0 0 600 82.8 32.7 78.6 34.1 Invention 150 0 150 5 300 81.6 33.2 79.5 34.2 Comparison 0 300 0 5 300 76.6 33.4 72.4 35.0 4=, oo As one can see from Table 1, the flotation results can be improved only if use is made of the mixture of two nonionic surfactants as a secondary collector . In Figure 1 the distribution of the degree of ethoxylation for the formulation according to the invention and the comparison 2 formulation are graphically 5 represented. The results clearly show that the double peak distribution plays a crucial role in the flotation. In a combination with the primary collector the mixture of two ethoxylated alcohols with a degree of ethoxylation equal to 1.5 and 8.5, respectively, provides much better recovery than the single ethoxylated alcohol with a degree of ethoxylation equal to 5.
Example 2 The emulsion formation and stability were tested by preparing aqueous 5 w%
solutions as follows: five (5) g of the surfactant or surfactant mixture were added to 150 ml beaker, diluted with 95 g of water and vigorously mixed. After 5 min the mixing was stopped. Visual observation of the prepared solutions was done after 1, 2, 3, 4, 5, 10 and 60 min.
The results are given in Table 2 below.
Table 2 Emulsion formation and stability results of mixture of the two alcohol ethoxylates Weight Ratio Under 1 min 2 min 3 min 4 min 5 min 10 60 1.5E0:8.5E0 mixing min min 100:0 2p 2p 2p 2p 2p 2p 2p 2 p 90:10 Em Em 2p 2p 2p 2p 2p 2 p 80:20 Em Em Em Em 2 p 2 p 2 p 2 p 50:50 Em Em Em Em Em Em Em 2p Em means emulsion, 2p means 2 phases From Table 2 it is clear that adding a compound having a degree of ethoxylation of higher than 3 to an alcohol ethoxylate that only has a degree of ethoxylation of 1.5 helps considerably to form an emulsion. Adding more of the higher ethoxylated product such as up to 50 wt% makes the emulsion much more stable.
The present invention is further illustrated by the following examples.
EXAMPLES
Example 1 General flotation procedure A phosphate ore containing 20-25% of apatite, 30-40% of silicates and c. 20%
of iron oxides was crushed and ground to a desirable flotation size (K80=110pm).
Three alkoxylates were prepared by reacting the alcohol Exxal 13 (ex Exxon), which has a DB of 3, with ethylene oxide in an amount of 1.5, 5 and 8.5 equivalents, respectively, on the molar amount of the alcohol.
500 g of the ore were placed in a 1.4L Denver flotation cell, 500 ml of process water (25mg/I Ca2+, 40mg/I Mg2+) were added and the mixing was started. Then 5 minutes conditioning with 1000g/t of a 1`)/0(w/w) aqueous starch solution was performed, the collector (600g/t (or a mixture of primary acylglycide collector and secondary collectors)) was added to the flotation cell as a 1`)/0 aqueous solution and conditioning was continued for 2.5 minutes. After the conditioning steps tap water was added so that a total volume of 1.4L was obtained, the pH
of the flotation mixture was adjusted to 9.5 with a 10% NaOH aqueous solution and the flotation was started. The experiment was performed at RT (20 1 C).
The rougher flotation, followed by three cleaning steps, was performed. All fractions (tailings, middlings and concentrate) were collected and analysed.
Reference is made to Figure 2 for the general procedure that was followed.
The flotation results and the composition of the collector formulation used are displayed in Table 1.
Table 1. Flotation results presented as P205 recovery and grade.
Amount of Average degree Amount of 2nd cleaner concentrate 3rd cleaner concentrate alcohol+XEO, g/t of ethoxylation acylglycide, 1.5E0 5E0 8.5E0 g/t Recovery, % Grade, %
Recovery, % Grade, %
Comparison 0 0 0 0 600 82.8 32.7 78.6 34.1 Invention 150 0 150 5 300 81.6 33.2 79.5 34.2 Comparison 0 300 0 5 300 76.6 33.4 72.4 35.0 4=, oo As one can see from Table 1, the flotation results can be improved only if use is made of the mixture of two nonionic surfactants as a secondary collector . In Figure 1 the distribution of the degree of ethoxylation for the formulation according to the invention and the comparison 2 formulation are graphically 5 represented. The results clearly show that the double peak distribution plays a crucial role in the flotation. In a combination with the primary collector the mixture of two ethoxylated alcohols with a degree of ethoxylation equal to 1.5 and 8.5, respectively, provides much better recovery than the single ethoxylated alcohol with a degree of ethoxylation equal to 5.
Example 2 The emulsion formation and stability were tested by preparing aqueous 5 w%
solutions as follows: five (5) g of the surfactant or surfactant mixture were added to 150 ml beaker, diluted with 95 g of water and vigorously mixed. After 5 min the mixing was stopped. Visual observation of the prepared solutions was done after 1, 2, 3, 4, 5, 10 and 60 min.
The results are given in Table 2 below.
Table 2 Emulsion formation and stability results of mixture of the two alcohol ethoxylates Weight Ratio Under 1 min 2 min 3 min 4 min 5 min 10 60 1.5E0:8.5E0 mixing min min 100:0 2p 2p 2p 2p 2p 2p 2p 2 p 90:10 Em Em 2p 2p 2p 2p 2p 2 p 80:20 Em Em Em Em 2 p 2 p 2 p 2 p 50:50 Em Em Em Em Em Em Em 2p Em means emulsion, 2p means 2 phases From Table 2 it is clear that adding a compound having a degree of ethoxylation of higher than 3 to an alcohol ethoxylate that only has a degree of ethoxylation of 1.5 helps considerably to form an emulsion. Adding more of the higher ethoxylated product such as up to 50 wt% makes the emulsion much more stable.
Claims (67)
1. Use of a mixture as secondary collector for the froth flotation of non-sulfidic ores, in combination with a primary collector selected from the group of amphoteric and anionic surface active compounds, wherein the mixture contains at least one compound (i) selected from the group of alkoxylates of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5, with a degree of ethoxylation of up to 4 and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds with a degree of ethoxylation of higher than 3, wherein if both compounds (i) and (ii) are ethoxylated alcohols, the mixture has a bimodal degree of ethoxylation distribution.
2. The use of claim 1 wherein the compound (ii) is selected from the group of alkoxylates of nonionic hydrocarbon compounds from the group of fatty alcohols, fatty amines, fatty ethanolamides, fatty diethanolamides, fatty acids, and triglycerides with a degree of ethoxylation of more than 3.
3. The use according to claim 1 or 2 where the molecular formula of compound (i) and (ii) is of the formula (l) R-A (l) wherein for compound (i) R is an alkyl or alkenyl group having 12-16 carbon atoms, and where said alkyl or alkenyl group has a degree of branching of 1-3 and wherein for compound (ii) R is any alkyl, aryl or alkenyl group branched or linear having 8-24 carbon atoms; A is selected from the groups 0-(PO)x(EO)y(PO)zH, for compounds (i) and (ii) (CO)N(CH2CH2O(P0)x(E0)y(P0)z1-1)2, for compound (ii) (CO)NH(CH2CH20(PO)(EO)y(P0)zH), for compound (ii) (C0)0((P0)x(E0)y(PO)zH), for compound (ii) N(P0)x(E0)y(P0)zH)2, for compound (ii) (C0)0((P0)x(E0)y(P0)zOCH2CH(0(P0)x(E0)y(P0)z0(CO)R)CH20 and ((PO)x(EO)y(PO)O(CO)R), for compound (ii), wherein PO is a propyleneoxy unit and EO is an ethyleneoxy unit and for compound (i); x is a number 0-2, y is a number 0-4, and z is a number 0-2, Date Recue/Date Received 2023-04-18 and for compound (ii)x is a number 0-20, y is a number higher than 3 up to 30, and z is a number 0-20.
4. The use of claim 3, wherein for compound (i), R is an alkyl or alkenyl group having 12-15 carbon atoms.
5. The use of claim 3 or 4, wherein for compound (i), x is 0.
8. The use of any one of claims 3-5, wherein for compound (i), y is a number 0-3.
7. The use of any one of claims 3-6, wherein for compound (i), y is a number 0-2.5.
8. The use of any one of claims 3-7, wherein for compound (i), y is a number 0-2.3.
9. The use of any one of claims 3-8, wherein for compound (i), y is a number 0-2.
10. The use of any one of claims 3-9, wherein for compound (i), z is 0.
11. The use of any one of claims 3-10, wherein for compound (ii), x is 0.
12. The use of any one of claims 3-11, wherein for compound (ii), y is a number 4-20.
13. The use of any one of claims 3-12, wherein for compound (ii), y is a number 5-15.
14. The use of any one of claims 3-13, wherein for compound (ii), y is a number 7-12.
15. The use of any one of claims 3-14, wherein for compound (ii), z is 0.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
16. The use of any one of claims 1 to 15 wherein the mixture additionally contains a liquid wherein compound (ii) is an emulsifier for compound (i) in the liquid.
17. The use according to any one of claims 1 to 16 wherein said primary collector is an amphoteric surface-active compound selected from the group consisting of compounds having the formula (II) wherein Ri is a hydrocarbyl group with 8-22 carbon atoms; A is an alkyleneoxy group having 2-4 carbon atoms; p is a number 0 or 1; q is a number from 0 to 5, R2 is a hydrocarbyl group having 1-4 carbon atoms, or R2 is the group wherein Ri, A, p and q have the same meaning as above, Y- is selected from the group consisting of coa and SO3-; n is a number 1 or 2; M is a cation which may be monovalent or divalent and inorganic or organic, and r is a number 1 or 2; or where the compound (II) is in its acidic protonated form without an external cation (Mr+) 1/r; and compounds having the formula (III) wherein R2 is a hydrocarbyl group with 8-22 carbon atoms, D is ¨CH2- or -CH2CH2- , k is 0-4, and M is hydrogen or a cation, and anionic surface-active compound selected from the group consisting of fatty acids, sulfonates, alkyl phosphates, alkyl sulfates and compounds of formula (IV) Date Recue/Date Received 2023-04-18 wherein R is a hydrocarbyl group having from 7-23 carbon atoms, optionally substituted; R1 is H or CH3; R2 is H or a C1-C4 alkyl group; R3 is H or CH3; n is a number 1-20; p is a number 1-3; X is H+ or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2, and mixtures thereof.
18. The use according to claim 17, wherein for the compound of formula (II), Ri is a hydrocarbyl group with 12-18 carbon atoms.
19. The use according to claim 17 or 18, wherein for the compound of formula (II), q is 0.
20. The use according to any one of claims 17-19, wherein for the compound of formula (II), R2 is a hydrocarbyl group having 1 carbon atom.
21. The use according to any one of claims 17-20, wherein Y- is COO-.
22. The use according to any one of claims 17-21, wherein n is 1.
23. The use according to any one of claims 17-22, wherein for the compound of formula (111), R2 is a hydrocarbyl group with 12-18 carbon atoms.
24. The use according to any one of claims 17-23, wherein for the compound of formula (III), k is 0-3.
25. The use according to any one of claims 17-24, wherein for the compound of formula (III), k is 0-2.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
26. The use according to any one of claims 17-25, wherein for the compound of formula (III), the cation is sodium or potassium.
27. The use according to any one of claims 17-26, wherein for the compound of formula (IV), R is a hydrocarbyl group having from 11-21 carbon atoms, optionally substituted.
28. The use according to any one of claims 17-27, wherein for the compound of formula (IV), R1 is H.
29. The use according to any one of claims 17-28, wherein for the compound of formula (IV), R2 is H.
30. The use according to any one of claims 17-29, wherein for the compound of formula (IV), R3 is CH3.
31. The use according to any one of claims 17-30, wherein for the compound of formula (IV), p is 1.
32. The use according to any one of claims 17-31, wherein for the compound of formula (IV), m is 1.
33. The use according to any one of claims 1 to 32 wherein the weight ratio between the primary collector and the secondary collector is between 15:85 and 99:1.
34. The use according to any one of claims 1 to 33 wherein the non-sulfidic ore is a calcium phosphate-containing ore.
35. A process for the froth flotation of non-sulfidic ores using a collector composition comprising a primary collector selected from the group of amphoteric and anionic surface-active compounds, and a secondary collector that contains a mixture containing at least one compound (i) selected from the group of alkoxylates of branched fatty alcohols with 12-16 carbon atoms Date Recue/Date Received 2023-04-18 having a degree of branching of 1-3.5, with a degree of ethoxylation of up to and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds, with a degree of ethoxylation of higher than 3, wherein if both compounds (i) and (ii) are ethoxylated alcohols, the mixture has a bimodal degree of ethoxylation distribution.
36. The process for the froth flotation of non-sulfidic ores according to claim 35 wherein the compound (ii) is selected from the group of alkoxylates of nonionic hydrocarbon compounds from the group of fatty alcohols, fatty amines, fatty ethanolamides, fatty diethanolamides, fatty acids, and triglycerides with a degree of ethoxylation of more than 3; and carbohydrate-based surfactants.
37. The process according to claim 35 or 36 wherein the molecular formula of compound (i) and (ii) is of the formula (l) R-A (l) wherein for compound (i) R is an alkyl or alkenyl group having 12-16 carbon atoms, and where said alkyl or alkenyl group has a degree of branching of 1-3 and wherein for compound (ii) R is any alkyl, aryl or alkenyl group branched or linear having 8-24 carbon atoms; A is selected from the groups 0-(P0)x(E0)y(P0)zH, for compounds (i) and (ii) (CO)N(CH2CH20(PO)(EO)y(P0)zH)2, for compound (ii) (CO)NH(CH2CH20(PO)(EO)y(P0)zH), for compound (ii) (C0)0((P0)x(E0)y(P0)zH), for compound (ii) N(P0),(E0)y(P0)zH)2, for compound (ii) (C0)0((P0)x(E0)y(P0)zOCH2CH(0(P0)x(E0)y(P0)z0(CO)R)CH20, and ((PO)(EO)y(P0)z0(CO)R), for compound (ii), wherein PO is a propyleneoxy unit and EO is an ethyleneoxy unit and for compound (i); x is a number 0-2, y is a number 0-4, and z is a number 0-2, and for compound (ii)x is a number 0-20, y is a number higher than 3 up to 30, and z is a number 0-20.
38. The process according to claim 37, wherein for compound (i), R is an alkyl or alkenyl group having 12-15 carbon atoms.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
39. The process according to claim 37 or 38, wherein for compound (i), x is 0.
40. The process according to any one of claims 37-39, wherein for compound (i), y is a number 0-3.
41. The process according to any one of claims 37-40, wherein for compound (i), y is a number 0-2.5.
42. The process according to any one of claims 37-41, wherein for compound (i), y is a number 0-2.3.
43. The process according to any one of claims 37-42, wherein for compound (i), y is a number 0-2.
44. The process according to any one of claims 37-43, wherein for compound (i), z is 0.
45. The process according to any one of claims 37-44, wherein for compound (ii), x is 0.
46. The process according to any one of claims 37-45, wherein for compound (ii), y is a number 4-20.
47. The process according to any one of claims 37-46, wherein for compound (ii), y is a number 5-15.
48. The process according to any one of claims 37-47, wherein for compound (ii), y is a number 7-12.
49. The process according to any one of claims 37-48, wherein for compound (ii), z is O.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
50. The process according to any one of claims 35 to 49 which comprises the steps i) conditioning a pulped non-sulfidic ore, wherein the ore comprises a phosphate-containing mineral, and gangue minerals, with the collector composition , and optionally other flotation aids and ii) performing a froth flotation process to recover the phosphate-containing mineral.
51. The process according to any one of claims 35 to 50 wherein said primary collector is an amphoteric surface-active compounds selected from the group consisting of compounds having the formula (II) wherein Ri is a hydrocarbyl group with 8-22 carbon atoms; A is an alkyleneoxy group having 2-4 carbon atoms; p is a number 0 or 1; q is a number from 0 to 5, R2 is a hydrocarbyl group having 1-4 carbon atoms, or R2 is the group wherein IR1, A, p and q have the same meaning as above, r is selected from the group consisting of C00- and S03-, n is a number 1 or 2, M is a cation which may be monovalent or divalent and inorganic or organic, and r is a number 1 or 2; or where the compound (II) is in its acidic protonated form without an external cation (MI 1/r; and compounds of formula (III) wherein R2 is a hydrocarbyl group with 8-22 carbon atoms, D is ¨CH2- or -CH2CH2- , k is 0-4, and M is hydrogen or a cation; or.
an anionic surface-active compound selected from the group consisting of fatty acids, sulfonates, alkyl phosphates, alkyl sulfates and compounds of formula (IV) wherein R is a hydrocarbyl group having from 7-23 carbon atoms, optionally substituted; Ri is H or CH3, R2 is H or a C1-C4 alkyl group, R3 is H or CH3, n is a number 1-20; p is a number 1-3, X is H+ or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2;
and mixtures thereof.
an anionic surface-active compound selected from the group consisting of fatty acids, sulfonates, alkyl phosphates, alkyl sulfates and compounds of formula (IV) wherein R is a hydrocarbyl group having from 7-23 carbon atoms, optionally substituted; Ri is H or CH3, R2 is H or a C1-C4 alkyl group, R3 is H or CH3, n is a number 1-20; p is a number 1-3, X is H+ or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2;
and mixtures thereof.
52. The process according to claim 51, wherein for the compound of formula (II), Ri is a hydrocarbyl group with 12-18 carbon atoms.
53. The process according to claim 51 or 52, wherein for the compound of formula (II), q is 0.
54. The process according to any one of claims 51-53, wherein for the compound of formula (11), R2 is a hydrocarbyl group having 1 carbon atom.
55. The process according to any one of claims 51-54, wherein Y- is COO-.
56. The process according to any one of claims 51-55, wherein n is 1.
57. The process according to any one of claims 51-56, wherein for the compound of formula (111), R2 is a hydrocarbyl group with 12-18 carbon atoms.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
58. The process according to any one of claims 51-57, wherein for the compound of formula (III), k is 0-3.
59. The process according to any one of claims 51-58, wherein for the compound of formula (III), k is 0-2.
60. The process according to any one of claims 51-59, wherein for the compound of formula (III), the cation is sodium or potassium.
61. The process according to any one of claims 51-60, wherein for the compound of formula (IV), R is a hydrocarbyl group having from 11-21 carbon atoms, optionally substituted.
62. The process according to any one of claims 51-61, wherein for the compound of formula (IV), RI is H.
63. The process according to any one of claims 51-62, wherein for the compound of formula (IV), R2 is H.
64. The process according to any one of claims 51-63, wherein for the compound of formula (IV), R3 is CH3.
65. The process according to any one of claims 51-64, wherein for the compound of formula (IV), p is 1.
66. The process according to any one of claims 51-65, wherein for the compound of formula (IV), m is 1.
67. The process according to any one of claims 35 to 66 wherein the weight ratio between the primary collector and the secondary collector is from 15:85 to 99:1.
Date Recue/Date Received 2023-04-18
Date Recue/Date Received 2023-04-18
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US20210197211A1 (en) | 2018-08-30 | 2021-07-01 | Basf Se | Beneficiation of phosphate from phosphate containing ores |
WO2020083793A1 (en) | 2018-10-23 | 2020-04-30 | Basf Se | Collector composition and flotation process for beneficiation of phosphate |
EP4087686A1 (en) | 2020-01-09 | 2022-11-16 | Basf Se | Method for flotation of a phosphate-containing ore |
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SE409291B (en) | 1978-03-03 | 1979-08-13 | Berol Kemi Ab | PROCEDURE FOR PHOSPHATE-MINERAL FOAM FLOATING |
OA06199A (en) | 1981-05-13 | 1981-06-30 | Berol Kemi Ab | Process for the flotation of phosphate minerals and a compound intended for this process. |
SE452120B (en) | 1984-04-04 | 1987-11-16 | Berol Kemi Ab | PROCEDURE FOR FOOT FLOTING AND FLOTING AGENTS |
DE3517154A1 (en) | 1985-05-11 | 1986-11-13 | Henkel KGaA, 4000 Düsseldorf | USE OF SURFACTANT MIXTURES AS AUXILIARIES FOR THE FLOTATION OF NON-SULFIDIC ORES |
DE3641447A1 (en) | 1986-12-04 | 1988-06-09 | Henkel Kgaa | TENSIDE MIXTURES AS COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES |
DE3641870A1 (en) * | 1986-12-08 | 1988-06-16 | Henkel Kgaa | ALKYLSULFOSUCCINATES BASED ON PROPOXYLATED AND PROPOXYLATED AND ETHOXYLATED FATTY ALCOHOLS AS COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES |
PT687726E (en) * | 1994-06-17 | 2000-09-29 | Procter & Gamble | BLEACHING COMPOSITIONS |
DE69703351T2 (en) * | 1996-06-20 | 2001-04-05 | High Point Chemical Corp., High Point | METHOD FOR THINKING OLD PAPER |
WO2000050560A1 (en) * | 1999-02-22 | 2000-08-31 | Cognis Corporation | Low viscosity high active blends of alkyl polyglycosides and alcohol ethoxylates |
SE0302986D0 (en) * | 2003-11-13 | 2003-11-13 | Akzo Nobel Nv | Use of a derivative of aspartic acid as a collector in froth flotation processes |
US7393462B2 (en) * | 2004-05-13 | 2008-07-01 | Cytec Technology Corp. | Process and reagent for separating finely divided titaniferrous impurities from Kaolin |
CN103260765B (en) * | 2010-12-28 | 2015-08-05 | 阿克佐诺贝尔化学国际公司 | For froth flotation silicate reverse from iron ore containing amine preparaton |
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EA033476B1 (en) * | 2013-07-05 | 2019-10-31 | Akzo Nobel Chemicals Int Bv | Synthesis of anionic surfactants and their use as collectors in froth flotation of non-sulphidic ores |
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EP3433021A2 (en) | 2019-01-30 |
ZA201804773B (en) | 2019-05-29 |
BR112018015843A2 (en) | 2018-12-26 |
CA3016794A1 (en) | 2017-09-28 |
EP3433021B1 (en) | 2022-06-15 |
RU2019107595A3 (en) | 2019-08-01 |
BR112018015843B1 (en) | 2022-06-07 |
RU2702044C2 (en) | 2019-10-03 |
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