EP4364852A1 - Collector composition and flotation method - Google Patents
Collector composition and flotation method Download PDFInfo
- Publication number
- EP4364852A1 EP4364852A1 EP22205668.1A EP22205668A EP4364852A1 EP 4364852 A1 EP4364852 A1 EP 4364852A1 EP 22205668 A EP22205668 A EP 22205668A EP 4364852 A1 EP4364852 A1 EP 4364852A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- collector composition
- moiety
- flotation
- 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.)
- Pending
Links
- 238000005188 flotation Methods 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 30
- 125000000129 anionic group Chemical group 0.000 claims abstract description 37
- 125000002091 cationic group Chemical group 0.000 claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 54
- 239000010452 phosphate Substances 0.000 claims description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- -1 phosphate ester Chemical class 0.000 claims description 29
- 229920006395 saturated elastomer Polymers 0.000 claims description 28
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002280 amphoteric surfactant Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940117986 sulfobetaine Drugs 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 229930182470 glycoside Natural products 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229940071089 sarcosinate Drugs 0.000 claims description 2
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 244000226021 Anacardium occidentale Species 0.000 abstract description 5
- 235000020226 cashew nut Nutrition 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 235000021317 phosphate Nutrition 0.000 description 51
- KVVSCMOUFCNCGX-UHFFFAOYSA-N cardol Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=CC(O)=C1 KVVSCMOUFCNCGX-UHFFFAOYSA-N 0.000 description 50
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 38
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 32
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 32
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 32
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 32
- UFMJCOLGRWKUKO-UHFFFAOYSA-N cardol diene Natural products CCCC=CCC=CCCCCCCCC1=CC(O)=CC(O)=C1 UFMJCOLGRWKUKO-UHFFFAOYSA-N 0.000 description 25
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 19
- KAOMOVYHGLSFHQ-UTOQUPLUSA-N anacardic acid Chemical compound CCC\C=C/C\C=C/CCCCCCCC1=CC=CC(O)=C1C(O)=O KAOMOVYHGLSFHQ-UTOQUPLUSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 235000014398 anacardic acid Nutrition 0.000 description 11
- ADFWQBGTDJIESE-UHFFFAOYSA-N anacardic acid 15:0 Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1C(O)=O ADFWQBGTDJIESE-UHFFFAOYSA-N 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 10
- 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 10
- 229940072033 potash Drugs 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 235000015320 potassium carbonate Nutrition 0.000 description 10
- 229910052586 apatite Inorganic materials 0.000 description 9
- 230000003750 conditioning effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000007046 ethoxylation reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003784 tall oil Substances 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002367 phosphate rock Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910003827 NRaRb Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 238000009291 froth flotation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 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
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100328895 Caenorhabditis elegans rol-8 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052641 aegirine Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group 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
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 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
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/0043—Organic compounds modified so as to contain a polyether group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—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
- B03D1/01—Organic compounds containing nitrogen
- B03D1/011—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
Definitions
- This invention relates a collector composition comprising anionic, cationic, and/or amphoteric derivatives of cashew nutshell liquid, and the use of those collector compositions in flotation methods.
- Froth flotation is a physico-chemical process used to separate mineral particles considered economically valuable from those considered waste. It is based on the ability of air bubbles to selectively attach to those particles that were previously rendered hydrophobic. The particle-bubble combinations then rise to the froth phase from where the flotation cell is discharged, whilst the hydrophilic particles remain in the flotation cell. Particle hydrophobicity is, in turn, induced by special chemicals called collectors. In direct flotation systems, it is the economically valuable minerals which are rendered hydrophobic by the action of the collector. Similarly, in reverse flotation systems, the collector renders hydrophobicity to those mineral particles considered waste. The efficiency of the separation process is quantified in terms of recovery and grade. Recovery refers to the percentage of valuable product contained in the ore that is removed into the concentrate stream after flotation. Grade refers to the percentage of the economically valuable product in the concentrate after flotation. A higher value of recovery or grade indicates a more efficient flotation system.
- phosphate concentrate with P 2 O 5 grade higher than 30% and recovery of >85-90%.
- the flotation of phosphate allows to reduce to minimal values the content of following gangue minerals: quartz, clay, feldspar, calcite, magnetite, dolomite etc.
- the applicable flotation method is affected by the nature of the phosphate ore.
- the direct flotation is commonly applied for the igneous/magmatic apatite phosphate ores with generally low P 2 O 5 feed grade (5-10%) and the valuable apatite phosphate concentrate is separated with the froth. Meanwhile, the reversed flotation is used for the sedimentary phosphate ores with generally higher P 2 O 5 feed grade. In the latter case the impurities are separated from the phosphate concentrate with the froth whereas the valuable phosphate concentrate is resided in the cell tailings product. In some cases, the direct flotation can be also used to float phosphorous-containing minerals from sedimentary phosphates.
- Anionic collectors can be used in both mentioned cases: for the direct flotation of apatite/phosphate from igneous or sedimentary phosphate ores and for flotation of calcite, dolomite, and other carbonaceous impurities from sedimentary phosphate ores, respectively.
- the process of phosphate flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further flotation.
- the flotation of slime impurities is commonly applied in the beneficiation processes of potash. Both anionic and nonionic collectors can be used in slime flotation, which is commonly performed prior to the flotation of potash. Further the direct flotation of KCI and NaCl is performed for sylvite and halite ores, respectively. Slimes are undesirable in KCI or NaCl flotation stages since they cause elevated consumption of potash collectors and decrease the purity of concentrate. Commonly, slimes contain 2/3 of clay minerals (dolomite, anhydrite, hematite, silica) and 1/3 clay (chlorite, Illite). The content of slimes in the flotation feed commonly varies between 1 and 6%.
- the process of potash slime flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further the flotation desliming.
- WO 2019/007712 A1 and WO2019/007714 A1 disclose a process to treat carbonatitic or siliceous non-sulfidic ores with a collector composition that comprises a phosphate compound of the formula: wherein R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms, A is an alkylene oxide unit; Y is H, Na, K or an ammonium or alkylated ammonium, n is 1 - 3, p is 0 - 25, X is chosen from the same groups as R-Ap or Y. These processes have been shown to provide the required grade of separation of the desired product from the ore and an improvement in recovery and selectivity.
- RU2717862C1 An alternative process for recovering phosphates from phosphate ores is described in RU2717862C1 .
- a collector containing ethoxylated derivatives of cashew nutshell liquid (CNSL) having a degree of ethoxylation from 1 to 100 is used.
- RU2744327C1 discloses flotation desliming of potash ores using a collector containing propoxylated Cardanol (part of CNSL) having a degree of propoxylation from 10 to 70, or a mixture of propoxylated Cardanol and ethoxylated Cardanol having a degree of ethoxylation and propoxylation from 10 to 70.
- collector compositions comprising anionic, cationic, and/or amphoteric (i.e., charge-containing) derivatives of CNSL meet this need. Accordingly, in a first aspect, the present invention relates to a collector composition comprising:
- the compounds of formula (I) are preferably derived from four components of cashew nutshell liquid (CNSL): anacardic acid [A], cardol [B], cardanol [C] and/or methylcardol [D]:
- the R' group is typically a mixture of saturated, monoene, diene and triene linear C15 alkyls, such as (but not necessarily limited to):
- CNSL is a common by-product produced by the cashew industry and is therefore a renewable and sustainable alternative to petrochemically derived alkylaromatic compounds.
- Natural cold extracted CNSL (C-CNSL) contains 60-75% anacardic acid, 15-25% cardol, 3-5% Cardanol and 1-2% methylcardol, respectively.
- technical CNSL (T-CNSL) can be obtained by a heat extraction process where anacardic acid is converted to Cardanol. After removal of undesirable polymeric materials, T-CNSL generally contains >75% Cardanol and ⁇ 4-8% cardol. The production of T-CNSL has been practiced for decades.
- the one or more compounds of formula (I) prefferably be anionic, cationic, or amphoteric derivatives of anacardic acid, cardol, cardanol and/or methylcardol, wherein the anacardic acid, cardol, cardanol and/or methylcardol are preferably obtained from CNSL.
- the one or more compounds of formula (I) are anionic, cationic, or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are preferably obtained from T-CNSL.
- the collector composition comprises one or more compounds of formula (Ia): wherein:
- the collector composition comprises at least one compound of formula (Ib): wherein:
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic, cationic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic, cationic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the compounds of formulae (I), (Ia) and/or (Ib) are anionic derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb).
- the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- the anionic, cationic, or amphoteric moiety Z of formulae (I), (Ia) and/or (Ib) preferably comprise or consist of a phosphate, a pyrophosphate, a polyphosphate, a phosphonate, a phosphinate, a sulfate, a sulfonate, a carboxylic acid, a sulfosuccinate, a sarcosinate, a polysulfate, a polysulfonate, a betaine, a sulfobetaine, an aminocarboxylate, an aminosulfonate, (alkyl)amines, (alkyl)diamines, etheramines, etherdiamines, esteramines, esterdiamines, and quaternary ammonium moieties.
- the cationic moieties Z comprise or consist of:
- the cationic moiety Z may also comprise or consist of polyester polyamines (PEPA) and/or polyester polyquats (PEPQ). These are polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, a dicarboxylic acid and a hydrophobic precursor (for example, fatty acid or fatty alcohol). In a preferred embodiment, the cationic moiety Z comprises or consists of a PEPA or PEPQ of the formula: wherein:
- Z of formulae (I), (Ia) and/or (Ib) comprises or consists of an anionic moiety or an amphoteric moiety, more preferably an anionic moiety.
- Preferred amphoteric moieties Z comprise or consist of a betaine, a sulfobetaine, an aminocarboxylate, and/or an aminosulfonate.
- Preferred anionic moieties Z comprise of consist of phosphates (cf. formula [E], below), sulfosuccinates (cf. formula [F], below), sarcosinates (cf. formula [G], below), maleates (cf. formula [H], below), amidocarboxylates (cf. formula [I], below), glycinates (cf. formula [J], below), taurates (cf. formula [K], below), hydroxamates (cf. formula [L], below), and/or sulfonates (cf. formula [N], below).
- the anionic moiety Z of formulae (I), (Ia) and/or (Ib) comprises or consists of a phosphate of formula (II): wherein:
- Y is a compound of formula (IIIa): wherein:
- the collector composition comprises a mixture of two or more compounds of formulae [IA1], [IA2], [IA3] and/or [IA4]: wherein:
- the collector composition comprises a mixture of compounds of formulae [IA2], [IA3] and [IA4], wherein the weight ratio of [IA3] to the sum of [IA2] and [IA4] (i.e., [IA3]: ([IA2]+[IA4])) is from about 75:25 to >99:1.
- the collector composition comprises at least one compound of the formula [IA3].
- the collector composition comprises at least one compound of formula [IB]: wherein:
- the cationic counterion X may be any suitable cationic counterion that forms a stable phosphate salt.
- Preferred cationic counterions in that respect include, but are not limited to, Na, K, Ca, Mg, and ammonium cations of the formula NR a R b R c R d , wherein R a , R b , R c and R d are each independently selected from H or C1-C12 alkyl.
- the cationic counterion is Na, K or NR a R b R c R d .
- the A unit as used herein is an alkylene oxide ether.
- alkoxylated products may be produced by procedures well-known in the art by reacting a free OH group with one or more alkylene oxides (e.g., 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 ):
- p in the "Ap” group corresponds to the number of moles of alkylene oxide that was added per mole of alcohol in the alkoxylation reaction. This is the commonly accepted and well understood meaning of this term, because the alkoxylation reaction normally produces a distribution of alkoxylated products (this can be observed, e.g., in WO 2021/140166 ).
- p is defined as the molar equivalents of alkylene oxide added per mole of alcohol in the alkoxylation reaction (this is also referred to as the "degree of alkoxylation”).
- 10 molar equivalents of ethylene oxide was reacted with the alcohol, hence in the below worked example "p” is 10 (i.e., the cardanol has a degree of ethoxylation of 10).
- the collector compositions of the present invention may comprise one or more surfactants. It should be understood, however, that the compounds described above may be successfully used in flotation methods without necessarily requiring an additional surfactant. For the avoidance of any doubt, it should be understood that the optional component (ii) of the collector composition disclosed herein is different to that of component (i),
- the optional surfactant(s) (ii) is not particularly limited, and may be cationic, anionic, non-ionic, amphoteric, or a mixture of two or more of these. Below some examples are given, but these should only be considered as suitable for the invention and are not to be regarded as limiting.
- Suitable amphoteric surfactants include, but are not limited to, those of the formula [C]: wherein R 1 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 0 or 1; q is a number from 0 to 5, preferably 0; R 2 is a hydrocarbyl group having 1-4 carbon atoms, preferably 1, or R 2 is the group wherein R 1 , A, p and q have the same meaning as above; Y is selected from the group consisting of COO - and SO 3 - , preferably COO - ; 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 amphoteric surfactant of formula [C] may also be used in its acid form, where the nitrogen is protonated and no external cation is needed.
- the compounds according to formula [C] can easily be produced in high yield from commercially available starting materials using known procedures.
- US 4,358,368 discloses some ways to produce the compounds where R 1 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 R 2 is attached to the compound of formula [C] via the methylene group, are described.
- amphoteric surfactants have the formula [D]: wherein 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 0-4, preferably 0-3, and most preferably 0-2, and M is hydrogen or a cation, such as sodium or potassium.
- 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 0-4, preferably 0-3, and most preferably 0-2
- M is hydrogen or a cation, such as sodium or potassium.
- the products where D is -CH 2 - are prepared by the reaction between a fatty amine and chloroacetic acid or its salts, and the products where D is -CH 2 CH 2 -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.
- Suitable anionic surfactants include, but are not limited to, fatty acids (such as those with an C8 to C22 acyl group), alkylphosphates, such as those of formula [E],
- esters of the above alkylamidocarboxylates are also contemplated (preferably following the formula [I] of the alkylamidocarboxylates compounds, wherein Y is an alcohol derived hydrocarbon group, such as also described in US20160129456 ),
- suitable anionic surfactants include sulphonated fatty acids, alkylbenzensulphonates, such as those of formula [M], and alkylsulfonates, such as those of formula [N], wherein in formulae [M] and [N]:
- Suitable nonionic surfactants include alkoxylates (such as alkoxylated fatty alcohols RO(A)H, alkoxylated fatty acids RC(O)O(A)H), or alkyl glycosides (e.g., R(C 6 O 6 H 11 ) k ), or alkylethanolamides, such as those of the formulae [O] or [P], wherein R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms; A is an alkylene oxide unit; Y is H, Na, K or an ammonium or alkylated ammonium; Z is -H, -CH 3 or -CH 2 CH 3; f is 1-25, preferably f is 1-15, and most preferable 1-10 and each f is independently 1 to 25; k is 1 or more, preferably about 1-5.
- alkoxylates such as alkoxylated fatty alcohols RO(A)H, alkoxylated fatty acids RC
- nonionic surfactants include ethoxylated and/or propoxylated derivatives of anacardic acid [A], cardol [B], cardanol [C] and/or methylcardol [D], preferably ethoxylated and/or propoxylated derivatives of cardol [B], cardanol [C] and/or methylcardol [D].
- Suitable cationic surfactants include, but are not limited to, fatty amines (preferably C8-C22, linear or branched alkyamines), fatty diamines (preferably C8-C22, linear or branched), alkyl etheramines (preferably C8-C22, linear or branched alky etheramines), alkyl etherdiamines (preferably C8-C22, linear or branched alkyl etherdiamines), alkyl esteramines (preferably C8-C22, linear or branched alkyl esteramines), quaternary ammonium surfactants, polyester polyamines (PEPA), and polyester polyquats (PEPQ).
- fatty amines preferably C8-C22, linear or branched alkyamines
- fatty diamines preferably C8-C22, linear or branched
- alkyl etheramines preferably C8-C22, linear or branched alky etheramines
- PEPA or PEPQ are related to polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, dicarboxylic acid and hydrophobic precursor (for example, fatty acid or fatty alcohol).
- Preferred PEPA and PEPQ cationic surfactants include, but are not limited to: wherein:
- PEPQ cationic surfactants include: wherein:
- the collector composition disclosed herein may comprise a mixture of two or more anionic and/or nonionic surfactants.
- the weight ratio of component (ii) to component (i) in the collector composition is preferably from about 15:85 to 99:1, preferably about 20:80 to 98:2, preferably about 25:75 to 97:3.
- the collector composition of the present disclosure comprises component (i) and optional component (ii) in a total amount of about 15 wt.% to about 100 wt.% (relative to the total weight of the collector composition), preferably in the above weight ratio (ii) to (i).
- the collector compositions described above may further comprise a solvent.
- Preferred solvents include, but are not limited to, water, isopropyl alcohol, propylene glycol, polyethylene glycol, diethylene glycol, hydrocarbon oils, C6-C18 alcohols, and mixtures thereof. If a solvent is used, then the collector composition preferably comprises at least 50 wt.%, more preferably at least 60 wt.%, more preferably at least 70wt.%, and most preferably at least 75 wt.% of the solvent (relative to the total weight of the collector composition).
- the present invention relates to a flotation method using the collector composition as described in detail above.
- the collector composition is suitable for treating non-sulfidic ores, such as phosphate-containing ores and/or ores comprising silicate minerals (preferably lithium and/or magnesium silicate minerals).
- the collector composition of the present invention is particularly suitable for treating (1) apatite ores (direct flotation of apatite), (2) sedimentary phosphate ores (direct flotation of sedimentary phosphate rock or direct flotation of carbonate impurities - i.e., in the latter case, reversed flotation of sedimentary phosphate rock) and (3) potash ores (i.e., slime flotation from potash ores).
- the collector composition of the present invention is also particularly suitable for use in the dephosphorization of iron ore, silicates flotation from iron ore and silicates flotation from sedimentary phosphate ore.
- a collector composition comprising component (i) improved the P 2 O 5 recovery and grade in the three abovementioned processes (1) direct flotation of apatite and (2) direct flotation of sedimentary phosphate rock and (3) reversed flotation of sedimentary phosphate rock (i.e. direct flotation of carbonate impurities from sedimentary phosphate).
- the use of a collector composition comprising component (i) improved the slime flotation from potash.
- CNSL components are not estrogenic materials and have better environmental profile comparing to the common nonylphenol ethoxylates if used in these applications.
- CNSL components are based on the renewable raw material source. Overall, the collector composition of the present disclosure provides numerous technical and environmental advantages over the previously known collector compositions.
- the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactant (ii) (most common for this particular application would be a fatty acid).
- surfactant most common for this particular application would be a fatty acid.
- the simultaneous presence of compounds (i) and (ii) or so to say the balance between the two compounds allows to reach the optimal recovery and grade of P 2 O 5 .
- "p" is between 0 and 30, more preferably 5 and 15, yet even more preferably between 8 and 12.
- the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alkyl etheramines) and the balance between the two compounds allows to reach the optimal recovery and grade of P 2 O 5 in the bottom concentrate product.
- surfactants most common for this particular application would be alkyl etheramines
- p is between 0 and 30, more preferably 2 and 10, yet even more preferably between 3 and 8.
- the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alcohol ethoxylate phosphate ester, ethoxylated or propoxylated fatty alcohol, ethoxylated fatty amine, all C8-C22 linear or branched).
- surfactants most common for this particular application would be alcohol ethoxylate phosphate ester, ethoxylated or propoxylated fatty alcohol, ethoxylated fatty amine, all C8-C22 linear or branched.
- the amount of collector composition added to the ore will in general be in the range of from about 10 to about 1000 g/ton dry ore, preferably in the range of from about 20 to about 500 g/ton dry ore, more preferably from about 100 to about 400 g/ton dry ore.
- reagents can be added either at the same time or, preferably, separately during the process and can include 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.
- 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
- inorganic dispersants such as silicate of sodium (water glass) and soda ash, and pH-regul
- the process to treat ores according to the present disclosure preferably comprises the steps of:
- T-CNSL T-CNSL
- Cardanol 96. 2 wt-%
- Methyl Cardol 0.7 wt-%
- the reactor was heated at 120oC for 1.5h under N 2 sparge to reduce water content to 0.04 wt. %.
- the reactor was then heated to 130oC and 622 g (14.12 moles) of ethylene oxide were fed gradually to not exceed the reactor pressure of 55 psig. After ethylene oxide addition was completed, the post-reaction was carried out for 1.5 hours at 130oC until the pressure in the reactor stabilized. Then the reaction mixture was cooled to 80oC and material was discharged.
- Example 2 Flotation tests - Direct flotation of apatite
- 500 g of an igneous phosphate ore containing 42% apatite, 38% nepheline, 5% aegirine, 3% feldspar and 2% sphene was ground in a rod mill with 500 g of synthetic process water and 6.2 kg of stainless-steel rods (grinding to 70% -160 ⁇ m - i.e. a granulometry of 70% through a 160 micron mesh).
- the ore/water slurry was transferred to a 1.3L cell of a flotation machine and conditioned with 200 g/t of sodium silicate solution (2 min) and 100 g/t of the collector blend (containing 40 wt% of tested component and 60 wt% of tall oil fatty acid) (1 min).
- the conditioning was performed at a rotor speed of 1000 min -1 .
- the Rougher - Cleaner 1 - Cleaner 2 flotation set was performed during 4, 3 and 2 min, respectively (at a rotor speed 1000 min -1 and an air flow of 3.0 L/min). Fractions coming from flotation were dried in the oven, weighed, and analyzed by means of XRF analysis. Recovery and Grade values were received.
- Example 1 substantially outperformed the nonionic equivalent (cf. RU2717862C1 ) - P 2 O 5 recovery was improved by 9.5% and the grade of P 2 O 5 was 0.2% higher.
- Figure 1 Improved recovery of apatite in direct flotation with anionic Cardanol ethoxylate phosphate ester (bottom points represent Rougher flotation, middle and top points represent Cleaner 1 and Cleaner 2, respectively).
- Example 3 Flotation tests - direct flotation of carbonates from sedimentary phosphate
- the sedimentary phosphate ore containing 19.0% P 2 O 5 and 8.0% SiO 2 was used for flotation.
- the ore contained 37% of particles ⁇ 74 ⁇ m and 75% ⁇ 215 ⁇ m.
- the ore was transferred to a 1.3L cell of a flotation machine and filled up to the mark with water.
- the water used in flotation was a synthetic made process water that contain 600 ppm Ca 2+ and 1600 ppm SO 4 2- .
- the ore slurry was conditioned with 7000 g/t H 3 PO 4 (30 sec) and 1000 g/t of carbonate collector (2 min). After that the carbonate flotation was performed during 2 min. Further, the pH of the pulp was adjusted to 7 using 10% Na 2 CO 3 .
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The disclosure is directed to collector composition comprising anionic, cationic, and/or amphoteric derivatives of cashew nutshell liquid, and the use of those collector compositions in flotation methods.
Description
- This invention relates a collector composition comprising anionic, cationic, and/or amphoteric derivatives of cashew nutshell liquid, and the use of those collector compositions in flotation methods.
- Froth flotation is a physico-chemical process used to separate mineral particles considered economically valuable from those considered waste. It is based on the ability of air bubbles to selectively attach to those particles that were previously rendered hydrophobic. The particle-bubble combinations then rise to the froth phase from where the flotation cell is discharged, whilst the hydrophilic particles remain in the flotation cell. Particle hydrophobicity is, in turn, induced by special chemicals called collectors. In direct flotation systems, it is the economically valuable minerals which are rendered hydrophobic by the action of the collector. Similarly, in reverse flotation systems, the collector renders hydrophobicity to those mineral particles considered waste. The efficiency of the separation process is quantified in terms of recovery and grade. Recovery refers to the percentage of valuable product contained in the ore that is removed into the concentrate stream after flotation. Grade refers to the percentage of the economically valuable product in the concentrate after flotation. A higher value of recovery or grade indicates a more efficient flotation system.
- Considering the beneficiation of phosphate, the general requirement for fertilizer industry is the phosphate concentrate with P2O5 grade higher than 30% and recovery of >85-90%. The flotation of phosphate allows to reduce to minimal values the content of following gangue minerals: quartz, clay, feldspar, calcite, magnetite, dolomite etc. The applicable flotation method is affected by the nature of the phosphate ore.
- The direct flotation is commonly applied for the igneous/magmatic apatite phosphate ores with generally low P2O5 feed grade (5-10%) and the valuable apatite phosphate concentrate is separated with the froth. Meanwhile, the reversed flotation is used for the sedimentary phosphate ores with generally higher P2O5 feed grade. In the latter case the impurities are separated from the phosphate concentrate with the froth whereas the valuable phosphate concentrate is resided in the cell tailings product. In some cases, the direct flotation can be also used to float phosphorous-containing minerals from sedimentary phosphates. Anionic collectors can be used in both mentioned cases: for the direct flotation of apatite/phosphate from igneous or sedimentary phosphate ores and for flotation of calcite, dolomite, and other carbonaceous impurities from sedimentary phosphate ores, respectively. The process of phosphate flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further flotation.
- The flotation of slime impurities is commonly applied in the beneficiation processes of potash. Both anionic and nonionic collectors can be used in slime flotation, which is commonly performed prior to the flotation of potash. Further the direct flotation of KCI and NaCl is performed for sylvite and halite ores, respectively. Slimes are undesirable in KCI or NaCl flotation stages since they cause elevated consumption of potash collectors and decrease the purity of concentrate. Commonly, slimes contain 2/3 of clay minerals (dolomite, anhydrite, hematite, silica) and 1/3 clay (chlorite, Illite). The content of slimes in the flotation feed commonly varies between 1 and 6%. The process of potash slime flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further the flotation desliming.
-
WO 2019/007712 A1 andWO2019/007714 A1 , respectively, disclose a process to treat carbonatitic or siliceous non-sulfidic ores with a collector composition that comprises a phosphate compound of the formula: - A problem with the processes of
WO 2019/007712 A1 andWO2019/007714 A1 however, is that they use synthetic non-renewable alcohols to prepare the collector compositions. - An alternative process for recovering phosphates from phosphate ores is described in
RU2717862C1 RU2744327C1 - There is a continued need for sustainable flotation systems that are more efficient in separating desired components and impurities.
- It has now been found that collector compositions comprising anionic, cationic, and/or amphoteric (i.e., charge-containing) derivatives of CNSL meet this need. Accordingly, in a first aspect, the present invention relates to a collector composition comprising:
- (i) one or more compounds of formula (I):
- R1 is a saturated or unsaturated, linear C15 alkyl,
- R2 is selected from H, -C(O)OH, -C(O)-Ap-OH, or -C(O)-Ap-O-Z, preferably H,
- -C(O)OH, or -C(O)-Ap-OH
- R3 is selected from -OH, -O-Z, -Ap-OH, or -Ap-O-Z,
- R4 is selected from H or -CH3,
- R5 is selected from H, -OH, -O-Z, -Ap-OH, or -Ap-O-Z,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12, and
- Z is an anionic moiety, a cationic moiety, or an amphoteric moiety,
- with the proviso that the compound of formula (I) comprises at least one Z group; and
- (ii) optionally one or more surfactants.
-
-
- CNSL is a common by-product produced by the cashew industry and is therefore a renewable and sustainable alternative to petrochemically derived alkylaromatic compounds. Natural cold extracted CNSL (C-CNSL) contains 60-75% anacardic acid, 15-25% cardol, 3-5% Cardanol and 1-2% methylcardol, respectively. In alternative, technical CNSL (T-CNSL) can be obtained by a heat extraction process where anacardic acid is converted to Cardanol. After removal of undesirable polymeric materials, T-CNSL generally contains >75% Cardanol and ~4-8% cardol. The production of T-CNSL has been practiced for decades.
- It is therefore preferable for the one or more compounds of formula (I) to be anionic, cationic, or amphoteric derivatives of anacardic acid, cardol, cardanol and/or methylcardol, wherein the anacardic acid, cardol, cardanol and/or methylcardol are preferably obtained from CNSL.
- More preferably, the one or more compounds of formula (I) are anionic, cationic, or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are preferably obtained from T-CNSL.
-
- R1 is a saturated or unsaturated, linear C15 alkyl,
- R3 is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
- R4 is H or CH3,
- R5 is selected from H, OH, O-Z, Ap-OH, or Ap-O-Z,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12, and
- Z is an anionic moiety, a cationic moiety, or an amphoteric moiety,
- with the proviso that the compound of formula (Ia) comprises at least one Z group.
-
- R1 is a saturated or unsaturated, linear C15 alkyl, and
- R3 is selected from O-Z or Ap-O-Z, preferably Ap-O-Z,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12, and
- Z is an anionic moiety, a cationic moiety, or an amphoteric moiety.
- Preferably, the compounds of formulae (I), (Ia) and/or (Ib) are anionic, cationic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). More preferably the compounds of formulae (I), (Ia) and/or (Ib) are anionic, cationic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). The anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- Preferably still, the compounds of formulae (I), (Ia) and/or (Ib) are anionic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). More preferably the compounds of formulae (I), (Ia) and/or (Ib) are anionic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). The anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- Preferably still, the compounds of formulae (I), (Ia) and/or (Ib) are anionic derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). More preferably the compounds of formulae (I), (Ia) and/or (Ib) are anionic derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (Ia) and/or (lb). The anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
- The anionic, cationic, or amphoteric moiety Z of formulae (I), (Ia) and/or (Ib) preferably comprise or consist of a phosphate, a pyrophosphate, a polyphosphate, a phosphonate, a phosphinate, a sulfate, a sulfonate, a carboxylic acid, a sulfosuccinate, a sarcosinate, a polysulfate, a polysulfonate, a betaine, a sulfobetaine, an aminocarboxylate, an aminosulfonate, (alkyl)amines, (alkyl)diamines, etheramines, etherdiamines, esteramines, esterdiamines, and quaternary ammonium moieties.
- Preferably, the cationic moieties Z comprise or consist of:
- -(CH2)fNH2 (optionally N-ethoxylated or in neutralized form);
- -(CH2)fNH(CH2)fNH2 (optionally N-ethoxylated or in neutralized form);
- esteramines of the formula:
- esterdiamines of the formula:
- The cationic moiety Z may also comprise or consist of polyester polyamines (PEPA) and/or polyester polyquats (PEPQ). These are polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, a dicarboxylic acid and a hydrophobic precursor (for example, fatty acid or fatty alcohol). In a preferred embodiment, the cationic moiety Z comprises or consists of a PEPA or PEPQ of the formula:
- R is a linear or branched, saturated or unsaturated, C2-C20 alkyl;
- R2 is either a link point to a compound of formulae (I), (la), or (Ib) (i.e., R2-O-Z), or is a linear or branched, saturated or unsaturated, C1-C20 alkyl;
- D is a halogen counterion (preferably Cl-, I-, Br- or F-) or an organic counterion (preferably sulfate, sulfonate, phosphate, phosphonate, carboxylate with C1-C10 alkyl);
- p is 0 or 1;
- n is 1 to 10;
- R3 and R4 are each independently:
- For PEPA : H, or a linear or branched, saturated or unsaturated, substituted or unsubstituted C1-C20 alkyl (preferably CH3 or CH2CH2OH),
- For PEPQ : a linear or branched, saturated or unsaturated, substituted or unsubstituted C1-C20 alkyl (preferably CH3 or CH2CH2OH),
- Preferably, Z of formulae (I), (Ia) and/or (Ib) comprises or consists of an anionic moiety or an amphoteric moiety, more preferably an anionic moiety.
- Preferred amphoteric moieties Z comprise or consist of a betaine, a sulfobetaine, an aminocarboxylate, and/or an aminosulfonate.
- Preferred anionic moieties Z comprise of consist of phosphates (cf. formula [E], below), sulfosuccinates (cf. formula [F], below), sarcosinates (cf. formula [G], below), maleates (cf. formula [H], below), amidocarboxylates (cf. formula [I], below), glycinates (cf. formula [J], below), taurates (cf. formula [K], below), hydroxamates (cf. formula [L], below), and/or sulfonates (cf. formula [N], below).
-
- n is 0 - 3, and
- each X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate,
- wherein Y is a compound of formula (III),
- wherein:
- R6 is a saturated or unsaturated, linear C15 alkyl,
- R7 is selected from H, -C(O)OH, or C(O)-Ap-OH,
- R8 is selected from OH or Ap-OH,
- R9 is selected from H or CH3,
- R10 is selected from H, OH, or Ap-OH,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12,
- wherein at least of one of R7, R8 or R10 contains an OH group that forms a phosphate ester link with the anionic moiety Z of formula (II),
- with the proviso that at least one X of Formula (II) must be selected from H or a cationic counterion.
-
- R6 is a saturated or unsaturated, linear C15 alkyl,
- R8 is selected from OH or Ap-OH,
- R9 is selected from H or CH3,
- R10 is selected from H, OH, or Ap-OH,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12,
- wherein at least of one of R8 or R10 contains an OH group that forms a phosphate ester link with the anionic moiety Z of formula (II).
-
- R1 is a saturated or unsaturated, linear C15 alkyl,
- R2 is selected from C(O)OH, C(O)-Ap-OH, or C(O)-Ap-O-Z, preferably C(O)OH or C(O)-Ap-OH,
- R3 is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
- R5 is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12, and
- Z is an anionic moiety, a cationic moiety, or an amphoteric moiety,
- with the proviso that each compound of formulae [IA1], [IA2], [IA3] and [IA4] must each comprise at least one Z group.
- Preferably, the collector composition comprises a mixture of compounds of formulae [IA2], [IA3] and [IA4], wherein the weight ratio of [IA3] to the sum of [IA2] and [IA4] (i.e., [IA3]: ([IA2]+[IA4])) is from about 75:25 to >99:1.
- In a more preferred embodiment, the collector composition comprises at least one compound of the formula [IA3].
-
- R' is a saturated or unsaturated, linear C15 alkyl,
- A is an alkylene oxide unit, preferably an ethylene oxide unit,
- p is 0 - 30, preferably 2-15, more preferably 3-12
- n is 0 - 3, and
- each X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate, wherein Y is a compound of formula (IIIa),
- wherein:
- R6 is a saturated or unsaturated, linear C15 alkyl,
- R8 is selected from OH or Ap-OH,
- R9 is selected from H or CH3,
- R10 is selected from H, OH, or Ap-OH,
- A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit,
- p is 1 - 30, preferably 2-15, more preferably 3-12,
- wherein at least of one of R8 or R10 contains an OH group that forms a phosphate ester link with phosphate group of formula [IB],
- with the proviso that at least one X must be selected from H or a cationic counterion.
- The cationic counterion X may be any suitable cationic counterion that forms a stable phosphate salt. Preferred cationic counterions in that respect include, but are not limited to, Na, K, Ca, Mg, and ammonium cations of the formula NRaRbRcRd, wherein Ra, Rb, Rc and Rd are each independently selected from H or C1-C12 alkyl. Preferably, the cationic counterion is Na, K or NRaRbRcRd.
- For the avoidance of doubt, the A unit as used herein is an alkylene oxide ether. Such alkoxylated products may be produced by procedures well-known in the art by reacting a free OH group with one or more alkylene oxides (e.g., 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):
- Finally, and again for the avoidance of any doubt, it should be understood that "p" in the "Ap" group corresponds to the number of moles of alkylene oxide that was added per mole of alcohol in the alkoxylation reaction. This is the commonly accepted and well understood meaning of this term, because the alkoxylation reaction normally produces a distribution of alkoxylated products (this can be observed, e.g., in
WO 2021/140166 ). Thus, "p" is defined as the molar equivalents of alkylene oxide added per mole of alcohol in the alkoxylation reaction (this is also referred to as the "degree of alkoxylation"). For example, in the below worked example, 10 molar equivalents of ethylene oxide was reacted with the alcohol, hence in the below worked example "p" is 10 (i.e., the cardanol has a degree of ethoxylation of 10). - In addition to the above compounds, the collector compositions of the present invention may comprise one or more surfactants. It should be understood, however, that the compounds described above may be successfully used in flotation methods without necessarily requiring an additional surfactant. For the avoidance of any doubt, it should be understood that the optional component (ii) of the collector composition disclosed herein is different to that of component (i),
- The optional surfactant(s) (ii) is not particularly limited, and may be cationic, anionic, non-ionic, amphoteric, or a mixture of two or more of these. Below some examples are given, but these should only be considered as suitable for the invention and are not to be regarded as limiting.
- Suitable amphoteric surfactants include, but are not limited to, those of the formula [C]:
US 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 inUS 4,828,687 (col 2, line 2 - col 2, line 31) compounds where R2 is - Further suitable amphoteric surfactants have the formula [D]:
-
- alkylsulfosuccinates, such as those of formula [F],
- alkylsarcosinates, such as those of formula [G],
- alkylmaleates, such as those of formula [H],
- alkylamidocarboxylates, such as those of formula [I],
- alkylglycinates, such as those of formula [J],
- alkyltaurates, such as those of formula [K],
- alkylhydroxamates, such as those of formula [L],
- wherein for each of formulae [E]-[L]:
- R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms;
- A is an alkylene oxide unit;
- Y is H, Na, K or an ammonium or alkylated ammonium;
- p is 0 - 25;
- X is chosen from the same groups as R-Ap or Y;
- m is 0-7;
- B is -H, -CH3, - CH(CH3)2, -CH2 CH(CH3)2, -CH(CH3)CH2CH3;
- Z is -H, -CH3 or -CH2CH3; and
- D is an alkaline metal counterion, preferably Na+, K+, Ca2+, or Mg2+.
- Esters of the above alkylamidocarboxylates are also contemplated (preferably following the formula [I] of the alkylamidocarboxylates compounds, wherein Y is an alcohol derived hydrocarbon group, such as also described in
US20160129456 ),
Further examples of suitable anionic surfactants include sulphonated fatty acids, alkylbenzensulphonates, such as those of formula [M], - R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms; and
- Y is H, Na, K or an ammonium or alkylated ammonium.
- Suitable nonionic surfactants include alkoxylates (such as alkoxylated fatty alcohols RO(A)H, alkoxylated fatty acids RC(O)O(A)H), or alkyl glycosides (e.g., R(C6O6H11)k), or alkylethanolamides, such as those of the formulae [O] or [P],
- Suitable cationic surfactants include, but are not limited to, fatty amines (preferably C8-C22, linear or branched alkyamines), fatty diamines (preferably C8-C22, linear or branched), alkyl etheramines (preferably C8-C22, linear or branched alky etheramines), alkyl etherdiamines (preferably C8-C22, linear or branched alkyl etherdiamines), alkyl esteramines (preferably C8-C22, linear or branched alkyl esteramines), quaternary ammonium surfactants, polyester polyamines (PEPA), and polyester polyquats (PEPQ).
- The terms PEPA or PEPQ are related to polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, dicarboxylic acid and hydrophobic precursor (for example, fatty acid or fatty alcohol). Preferred PEPA and PEPQ cationic surfactants include, but are not limited to:
- R is a linear or branched, saturated or unsaturated, C2-C20 alkyl;
- R2 is a linear or branched, saturated or unsaturated, C1-C20 alkyl;
- D is a halogen counterion (preferably Cl-, I-, Br- or F-) or an organic counterion (preferably sulfate, sulfonate, phosphate, phosphonate, carboxylate with C1-C10 alkyl);
- p is 0 or 1;
- n is 1 to 10;
- R3 and R4 are each independently:
- For PEPA : H, or a linear or branched, saturated or unsaturated, substituted or unsubstituted C1-C20 alkyl (preferably CH3 or CH2CH2OH),
- For PEPQ : a linear or branched, saturated or unsaturated, substituted or unsubstituted C1-C20 alkyl (preferably CH3 or CH2CH2OH).
-
- R is a linear or branched, saturated or unsaturated, C1-C20 alkyl;
- R' is H or C(O)R;
- R" is -CH2CH2N(CH3)2CH2CH2-;
- n is 1 to 10;
- m is 0 to 2; and
- k is 1 to 6.
- Anionic and nonionic surfactants, such as those detailed above, are preferred. The collector composition disclosed herein may comprise a mixture of two or more anionic and/or nonionic surfactants.
- For embodiments of the collector composition of the present disclosure that comprise one or more surfactants (ii), the weight ratio of component (ii) to component (i) in the collector composition is preferably from about 15:85 to 99:1, preferably about 20:80 to 98:2, preferably about 25:75 to 97:3.
- Preferably, the collector composition of the present disclosure comprises component (i) and optional component (ii) in a total amount of about 15 wt.% to about 100 wt.% (relative to the total weight of the collector composition), preferably in the above weight ratio (ii) to (i).
- The collector compositions described above may further comprise a solvent. Preferred solvents include, but are not limited to, water, isopropyl alcohol, propylene glycol, polyethylene glycol, diethylene glycol, hydrocarbon oils, C6-C18 alcohols, and mixtures thereof. If a solvent is used, then the collector composition preferably comprises at least 50 wt.%, more preferably at least 60 wt.%, more preferably at least 70wt.%, and most preferably at least 75 wt.% of the solvent (relative to the total weight of the collector composition).
- In a second aspect, the present invention relates to a flotation method using the collector composition as described in detail above. The collector composition is suitable for treating non-sulfidic ores, such as phosphate-containing ores and/or ores comprising silicate minerals (preferably lithium and/or magnesium silicate minerals).
- The collector composition of the present invention is particularly suitable for treating (1) apatite ores (direct flotation of apatite), (2) sedimentary phosphate ores (direct flotation of sedimentary phosphate rock or direct flotation of carbonate impurities - i.e., in the latter case, reversed flotation of sedimentary phosphate rock) and (3) potash ores (i.e., slime flotation from potash ores). The collector composition of the present invention is also particularly suitable for use in the dephosphorization of iron ore, silicates flotation from iron ore and silicates flotation from sedimentary phosphate ore.
- It was found that the use of a collector composition comprising component (i) improved the P2O5 recovery and grade in the three abovementioned processes (1) direct flotation of apatite and (2) direct flotation of sedimentary phosphate rock and (3) reversed flotation of sedimentary phosphate rock (i.e. direct flotation of carbonate impurities from sedimentary phosphate). In addition, the use of a collector composition comprising component (i) improved the slime flotation from potash. In addition, CNSL components are not estrogenic materials and have better environmental profile comparing to the common nonylphenol ethoxylates if used in these applications. In addition, CNSL components are based on the renewable raw material source. Overall, the collector composition of the present disclosure provides numerous technical and environmental advantages over the previously known collector compositions.
- For flotation of igneous or sedimentary phosphates, the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactant (ii) (most common for this particular application would be a fatty acid). Advantageously, the simultaneous presence of compounds (i) and (ii) or so to say the balance between the two compounds allows to reach the optimal recovery and grade of P2O5. In a preferred embodiment "p" is between 0 and 30, more preferably 5 and 15, yet even more preferably between 8 and 12.
- For the reversed phosphate flotation of sedimentary phosphate, the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alkyl etheramines) and the balance between the two compounds allows to reach the optimal recovery and grade of P2O5 in the bottom concentrate product. In a preferred embodiment "p" is between 0 and 30, more preferably 2 and 10, yet even more preferably between 3 and 8.
- For the slime flotation from potash, the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alcohol ethoxylate phosphate ester, ethoxylated or propoxylated fatty alcohol, ethoxylated fatty amine, all C8-C22 linear or branched). By means of the novel component (i) slimes can be efficiently floated from the potash concentrate product, which stay in the flotation tails. In a preferred embodiment "p" is between 0 and 30, more preferably 2 and 10, yet even more preferably between 3 and 8.
- The amount of collector composition added to the ore will in general be in the range of from about 10 to about 1000 g/ton dry ore, preferably in the range of from about 20 to about 500 g/ton dry ore, more preferably from about 100 to about 400 g/ton dry ore.
- Other additives can be also involved in the flotation process together with the collector composition of the current invention. These reagents can be added either at the same time or, preferably, separately during the process and can include 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.
- The process to treat ores according to the present disclosure preferably comprises the steps of:
- conditioning of the mixture of a pulped mineral ore under stirring in aqueous solution.
- adding a flotation depressant, flotation activator or flocculant to the mixture with further conditioning (optional).
- adjusting the pH of the mixture with further conditioning (optional).
- adding the collector composition of the invention with further conditioning.
- adding a frother to the mixture with further conditioning (optional).
- performing a froth flotation by introducing air into the mixture. The froth is skimmed off to recover targeted minerals.
- It is noted that various elements of the present invention, including but not limited to preferred ranges for the various parameters, can be combined unless they are mutually exclusive.
- The invention will be elucidated by the following examples without being limited thereto or thereby.
- A sample of T-CNSL was obtained and was found to consist primarily of Cardanol (96. 2 wt-%), with minor amounts of Cardol (3.1 wt-%) and Methyl Cardol (0.7 wt-%) also being present.
- T-CNSL (Cardanol, 425.0g, 1.41 moles, Mw = 301.0 eq/g) and KOH (3.0g of 45 % aq. solution) were charged to a Parr reactor (2L). The reactor was heated at 120ºC for 1.5h under N2 sparge to reduce water content to 0.04 wt. %. The reactor was then heated to 130ºC and 622 g (14.12 moles) of ethylene oxide were fed gradually to not exceed the reactor pressure of 55 psig. After ethylene oxide addition was completed, the post-reaction was carried out for 1.5 hours at 130ºC until the pressure in the reactor stabilized. Then the reaction mixture was cooled to 80ºC and material was discharged.
- Cardanol ethoxylate (T-CNSL+10EO) (1000 g, 1.35 moles, Mw = 741.5 g/mole) was placed into 2 L glass flask and heated at 60ºC for 1h under N2 sparge. Then polyphosphoric acid (126.65 g, 1.06 moles) was added over a period of 0.5h, keeping the temperature of the reaction mixture at 65ºC. The reaction was carried out at 65ºC for additional 4h.
- Then P2O5 (49.12 g, 0.346 moles, Mw = 142.0 g/mole) was added over 0.5h at 60-65ºC. Thereafter the temperature was increased to 75ºC and the reaction was carried out for 4h more. After the reaction was completed, 14.81g of deionized water was added and unreacted P2O5 and polyphosphoric acid were hydrolysed keeping the reaction mixture at 90ºC for 3h. Then the reaction was cooled to 75ºC and the product was discharged. Monoalkylphosphate:dialkylphosphate ratio of this compound was 4.1 (determined by 31P NMR).
- 500 g of an igneous phosphate ore containing 42% apatite, 38% nepheline, 5% aegirine, 3% feldspar and 2% sphene was ground in a rod mill with 500 g of synthetic process water and 6.2 kg of stainless-steel rods (grinding to 70% -160µm - i.e. a granulometry of 70% through a 160 micron mesh). The ore/water slurry was transferred to a 1.3L cell of a flotation machine and conditioned with 200 g/t of sodium silicate solution (2 min) and 100 g/t of the collector blend (containing 40 wt% of tested component and 60 wt% of tall oil fatty acid) (1 min). The conditioning was performed at a rotor speed of 1000 min-1.
- The Rougher - Cleaner 1 - Cleaner 2 flotation set was performed during 4, 3 and 2 min, respectively (at a rotor speed 1000 min-1 and an air flow of 3.0 L/min). Fractions coming from flotation were dried in the oven, weighed, and analyzed by means of XRF analysis. Recovery and Grade values were received.
- Tested reagents:
- Alkylphosphate ester with C16-C18 alkyl chain having a degree of ethoxylation of 4 (40 wt-%) and tall oil fatty acid sodium salt (60 wt-%) [comparative].
- Alkylphosphate ester with C16-C18 alkyl chain having a degree of ethoxylation of 10 (40 wt-%) and tall oil fatty acid sodium salt (60 wt-%) [comparative].
- Ethoxylate of Example 1 without phosphate ester (40 wt-%) and tall oil fatty acid sodium salt (60 wt-%) [comparative].
- Phosphate ester of Example 1 (40 wt-%) and tall oil fatty acid sodium salt (60 wt-%) [inventive].
- The results are shown in Figure 1. A surprising finding was that P2O5 recovery was improved by 3.5% and grade by 0.5% using phosphate ester of Example 1 compared to a phosphate ester based on a linear alcohol with 4 EO and with 10 EO (the linear alcohol-based phosphate esters are currently used in the industry).
-
- Figure 1. Improved recovery of apatite in direct flotation with anionic Cardanol ethoxylate phosphate ester (bottom points represent Rougher flotation, middle and top points represent Cleaner 1 and Cleaner 2, respectively).
- 320 g of the sedimentary phosphate ore containing 19.0% P2O5 and 8.0% SiO2 was used for flotation. The ore contained 37% of particles <74µm and 75% <215µm. The ore was transferred to a 1.3L cell of a flotation machine and filled up to the mark with water. The water used in flotation was a synthetic made process water that contain 600 ppm Ca2+ and 1600 ppm SO4 2-. The ore slurry was conditioned with 7000 g/t H3PO4 (30 sec) and 1000 g/t of carbonate collector (2 min). After that the carbonate flotation was performed during 2 min. Further, the pH of the pulp was adjusted to 7 using 10% Na2CO3. 1000 g/t of isotridecyl alkylethermonoamine acetate was added to the pulp and conditioning was carried out for 1 min. At the next step the silicate flotation was performed (2 min). All flotation steps were performed at 800 min-1 and 3.5 L/min air.
Fractions coming from flotation were dried in the oven, weighed, and analyzed by means of XRF analysis. - Tested reagents (carbonate flotation):
- Nonionic Cardanol derivative having a degree of ethoxylation of 10 (comparative).
- Anionic phosphate ester of Example 1 (inventive).
- The results are shown in Table 1. The nonionic Cardanol ethoxylate resulted in no improvement in P2O5 grade after the flotation. Conversely, the anionic phosphate ester of Example 1 improved the P2O5 grade; the flotation of carbonates with the phosphate ester of ethoxylated Cardanol was more selective since the final grade of P2O5 was improved.
Table 1. Improved performance in reversed flotation of sedimentary phosphate with Cardanol ethoxylate phosphate ester 10 EO. Reagent P2O5 grade in the feed to flotation, % Final P2O5 grade of the tailings concentrate, % Ethoxylated Cardanol 10EO 19.0 19.2 Phosphate ester of Example 1 19.4 21.5 - In this specification, unless expressly otherwise indicated, the word 'or' is used in the sense of an operator that returns a true value when either or both of the stated conditions is met, as opposed to the operator 'exclusive or' which requires that only one of the conditions is met. The word 'comprising' is used in the sense of 'including' rather than to mean 'consisting of'. All prior teachings acknowledged above are hereby incorporated by reference. No acknowledgement of any prior published document herein should be taken to be an admission or representation that the teaching thereof was common general knowledge in Europe or elsewhere at the date hereof.
Claims (15)
- A collector composition comprising:(i) one or more compounds of formula (I):R1 is a saturated or unsaturated, linear C15 alkyl,R2 is selected from H, -C(O)OH, C(O)-Ap-OH, or C(O)-Ap-O-Z,R3 is selected from OH, O-Z, Ap-OH, or Ap-O-Z,R4 is selected from H or CH3,R5 is selected from H, OH, O-Z, Ap-OH, or Ap-O-Z,A is an alkylene oxide unit,p is 1 - 30, andZ is an anionic moiety, a cationic moiety, or an amphoteric moiety,with the proviso that the compound of formula (I) comprises at least one Z group; and(ii) optionally one or more surfactants.
- The collector composition of claim 1, wherein the one or more compounds of formula (I) are selected from compounds of formula (Ia):R1 is a saturated or unsaturated, linear C15 alkyl,R3 is selected from OH, O-Z, Ap-OH, or Ap-O-Z,R4 is H or CH3,R5 is selected from H, OH, O-Z, Ap-OH, or Ap-O-Z,A is an alkylene oxide unit,p is 1 - 30, andZ is an anionic moiety, a cationic moiety, or an amphoteric moiety,with the proviso that the compound of formula (Ia) comprises at least one Z group.
- The collector composition of claims 1 or 2, wherein the one or more compounds of formula (I) comprises at least one compound of formula (Ib):R1 is a saturated or unsaturated, linear C15 alkyl, andR3 is selected from O-Z or Ap-O-Z,A is an alkylene oxide unit,p is 1 - 30, andZ is an anionic moiety, a cationic moiety, or an amphoteric moiety.
- The collector composition of any one of claims 1 to 3, wherein the anionic, cationic, or amphoteric moiety Z of formulae (I), (Ia) and/or (Ib) comprises or consists of a phosphate, a pyrophosphate, a polyphosphate, a phosphonate, a phosphinate, a sulfate, a sulfonate, a carboxylic acid, a sulfosuccinate, a sarcosinate, a glycinate, a polysulfate, a polysulfonate, a betaine, a sulfobetaine, an aminocarboxylate, an aminosulfonate, (alkyl)amines, (alkyl)diamines, etheramines, etherdiamines, esteramines, esterdiamines, and quaternary ammonium moieties.
- The collector composition of any one of claims 1 to 4, wherein Z of formulae (I), (Ia) and/or (Ib) is an anionic moiety or an amphoteric moiety, preferably an anionic moiety.
- The collector composition of claim 5, wherein anionic moiety Z of formulae (I), (Ia) and/or (Ib) comprises or consists of a phosphate of formula (II):n is 0 - 3, andeach X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate,wherein:R6 is a saturated or unsaturated, linear C15 alkyl,R7 is selected from H, -C(O)OH, or C(O)-Ap-OH,R8 is selected from OH or Ap-OH,R9 is selected from H or CH3,R10 is selected from H, OH, or Ap-OH,A is an alkylene oxide unit,p is 1 - 30,wherein at least of one of R7, R8 or R10 contains an OH group that forms a phosphate ester link with the anionic moiety Z of formula (II),with the proviso that at least one X of Formula (II) must be selected from H or a cationic counterion.
- The collector composition of any one of claims 1 to 6, wherein the one or more compounds of formula (I) comprises at least one compound of formula [IB]:wherein:R' is a saturated or unsaturated, linear C15 alkyl,A is an alkylene oxide unit,p is 0 - 30,n is 0 - 3, andeach X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate,wherein:R6 is a saturated or unsaturated, linear C15 alkyl,R8 is selected from OH or Ap-OH,R9 is selected from H or CH3,R10 is selected from H, OH, or Ap-OH,A is an alkylene oxide unit, andp is 1 - 30,wherein at least of one of R8 or R10 contains an OH group that forms a phosphate ester link with phosphate group of formula [IB],with the proviso that at least one X must be selected from H or a cationic counterion.
- The collector composition of any one of claims 1 to 7, wherein the collector composition comprises one or more surfactants (ii) selected from cationic, anionic, non-ionic and/or amphoteric surfactants.
- The collector composition of claim 8, wherein the collector composition comprises one of more surfactants (ii) selected from:a) anionic surfactants selected from fatty acids, alkylphosphates, alkylsulfosuccinates, alkylsarcosinates, alkylglycinates, alkyltaurates, alkylmaleates, alkylamidocarboxylates and esters thereof, alkylhydroxamates, sulphonated fatty acids, alkylbenzensulphonates, or alkylsulfonates;b) amphoteric surfactants selected from those of formula [C]:
or amphoteric surfactants selected from those of formula [D]:c) nonionic surfactants selected from alkoxylates, alkyl glycosides, or alkylethanolamides;d) cationic surfactants selected from fatty amines, fatty diamines, alkyl etheramines, alkyl etherdiamines, alkyl esteramines, quaternary ammonium surfactants, polyester polyamines (PEPA), or polyester polyquats (PEPQ). - The collector composition of any one of claims 1 to 9, wherein the collector composition comprises one or more surfactants (ii), and wherein the weight ratio of component (ii) to component (i) in the collector composition is from about 15:85 to 99:1.
- The collector composition of any one of claims 1 to 10, further comprising a solvent.
- A flotation method comprising the use of a collector composition according to any one of claims 1 to 11.
- The flotation method of claim 12, wherein the method is for the treatment of non-sulfidic ores.
- The flotation method of claim 12, wherein the method is a flotation method to recover slime particles from potash salts
- The flotation method of claim 12, wherein the method is for the dephosphorization of iron ore, silicates flotation from iron ore, or silicates flotation from sedimentary phosphate ore.
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Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4358368A (en) | 1979-03-02 | 1982-11-09 | Berol Kemi Ab | Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor |
US4514290A (en) * | 1982-03-05 | 1985-04-30 | Kenogard Ab | Flotation collector composition and its use |
US4828687A (en) | 1984-04-04 | 1989-05-09 | Berol Kemi Ab | Froth flotation process and collector therefor |
US20160129456A1 (en) | 2013-07-05 | 2016-05-12 | Akzo Nobel Chemicals International B.V. | The Synthesis of New Anionic Surfactants and Their Use as Collectors in Froth Flotation of Non-Sulphidic Ores |
CN105906797A (en) * | 2016-06-16 | 2016-08-31 | 常熟耐素生物材料科技有限公司 | Pentadecane (ene) naphthalenediol polyoxyethylene ether sulfo succinate monoester disodium salt and preparation method and application thereof |
CN106117539A (en) * | 2016-06-16 | 2016-11-16 | 常熟耐素生物材料科技有限公司 | Cardanol polyoxyethylene ether mono sulfosuccinates and its preparation method and application |
WO2017060451A1 (en) * | 2015-10-09 | 2017-04-13 | Clariant International Ltd | Cashew nutshell liquid alkoxylate carboxylate as a new renewable surfactant composition for enhanced oil recovery applications |
CN108530307A (en) * | 2018-05-18 | 2018-09-14 | 上海邦高化学有限公司 | Functional group's type Anacardol cationic surface active agent and the preparation method and application thereof |
CN109158050A (en) * | 2018-09-10 | 2019-01-08 | 上海邦高化学有限公司 | Cashew nut phenolic anion-nonionic surfactant and the preparation method and application thereof |
WO2019007714A1 (en) | 2017-07-04 | 2019-01-10 | Akzo Nobel Chemicals International B.V. | Process to treat siliceous non-sulfidic ores and collector composition therefor |
WO2019007712A1 (en) | 2017-07-04 | 2019-01-10 | Akzo Nobel Chemicals International B.V. | Process to treat carbonatitic non-sulfidic ores and collector composition therefor |
CN110013794A (en) * | 2018-01-10 | 2019-07-16 | 中国石油天然气股份有限公司 | Temperature-resistant and anti-salt type anacardol zwitterionic surfactant and its preparation method and application |
RU2717862C1 (en) | 2019-09-20 | 2020-03-26 | Публичное акционерное общество "Уралхимпласт" | Use of oxyethylated derivatives of cashew nutshells liquid as reagent-foaming agent for beneficiation of apatite-containing ores |
RU2718880C1 (en) * | 2019-09-20 | 2020-04-15 | Публичное акционерное общество "Уралхимпласт" | Use of oxyethylated derivatives of cashew nutshells liquid as reagent-foaming agent for beneficiation of diamond-containing ores |
RU2744327C1 (en) | 2020-03-24 | 2021-03-05 | Публичное акционерное общество "Уралкалий" (ПАО "Уралкалий") | Method for flotation enrichment of potassium ore |
CN112500299A (en) * | 2020-11-27 | 2021-03-16 | 华东理工大学 | Cardanol quaternary ammonium salt type cationic surfactant and application thereof |
WO2021140166A1 (en) | 2020-01-09 | 2021-07-15 | Basf Se | Method for flotation of a phosphate-containing ore |
CN113774510A (en) * | 2021-08-26 | 2021-12-10 | 浙江恒澜科技有限公司 | Preparation method of expanded graphite polyester flame-retardant fabric |
-
2022
- 2022-11-04 EP EP22205668.1A patent/EP4364852A1/en active Pending
-
2023
- 2023-10-24 WO PCT/EP2023/079600 patent/WO2024094486A1/en unknown
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4358368A (en) | 1979-03-02 | 1982-11-09 | Berol Kemi Ab | Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor |
US4514290A (en) * | 1982-03-05 | 1985-04-30 | Kenogard Ab | Flotation collector composition and its use |
US4828687A (en) | 1984-04-04 | 1989-05-09 | Berol Kemi Ab | Froth flotation process and collector therefor |
US20160129456A1 (en) | 2013-07-05 | 2016-05-12 | Akzo Nobel Chemicals International B.V. | The Synthesis of New Anionic Surfactants and Their Use as Collectors in Froth Flotation of Non-Sulphidic Ores |
WO2017060451A1 (en) * | 2015-10-09 | 2017-04-13 | Clariant International Ltd | Cashew nutshell liquid alkoxylate carboxylate as a new renewable surfactant composition for enhanced oil recovery applications |
CN105906797A (en) * | 2016-06-16 | 2016-08-31 | 常熟耐素生物材料科技有限公司 | Pentadecane (ene) naphthalenediol polyoxyethylene ether sulfo succinate monoester disodium salt and preparation method and application thereof |
CN106117539A (en) * | 2016-06-16 | 2016-11-16 | 常熟耐素生物材料科技有限公司 | Cardanol polyoxyethylene ether mono sulfosuccinates and its preparation method and application |
WO2019007714A1 (en) | 2017-07-04 | 2019-01-10 | Akzo Nobel Chemicals International B.V. | Process to treat siliceous non-sulfidic ores and collector composition therefor |
WO2019007712A1 (en) | 2017-07-04 | 2019-01-10 | Akzo Nobel Chemicals International B.V. | Process to treat carbonatitic non-sulfidic ores and collector composition therefor |
CN110013794A (en) * | 2018-01-10 | 2019-07-16 | 中国石油天然气股份有限公司 | Temperature-resistant and anti-salt type anacardol zwitterionic surfactant and its preparation method and application |
CN108530307A (en) * | 2018-05-18 | 2018-09-14 | 上海邦高化学有限公司 | Functional group's type Anacardol cationic surface active agent and the preparation method and application thereof |
CN109158050A (en) * | 2018-09-10 | 2019-01-08 | 上海邦高化学有限公司 | Cashew nut phenolic anion-nonionic surfactant and the preparation method and application thereof |
RU2717862C1 (en) | 2019-09-20 | 2020-03-26 | Публичное акционерное общество "Уралхимпласт" | Use of oxyethylated derivatives of cashew nutshells liquid as reagent-foaming agent for beneficiation of apatite-containing ores |
RU2718880C1 (en) * | 2019-09-20 | 2020-04-15 | Публичное акционерное общество "Уралхимпласт" | Use of oxyethylated derivatives of cashew nutshells liquid as reagent-foaming agent for beneficiation of diamond-containing ores |
WO2021140166A1 (en) | 2020-01-09 | 2021-07-15 | Basf Se | Method for flotation of a phosphate-containing ore |
RU2744327C1 (en) | 2020-03-24 | 2021-03-05 | Публичное акционерное общество "Уралкалий" (ПАО "Уралкалий") | Method for flotation enrichment of potassium ore |
CN112500299A (en) * | 2020-11-27 | 2021-03-16 | 华东理工大学 | Cardanol quaternary ammonium salt type cationic surfactant and application thereof |
CN113774510A (en) * | 2021-08-26 | 2021-12-10 | 浙江恒澜科技有限公司 | Preparation method of expanded graphite polyester flame-retardant fabric |
Non-Patent Citations (1)
Title |
---|
"Nonionic Surfactants: Organic Chemistry in Surfactant Science Series", vol. 72, 1998, MARCEL DEKKER, INC, pages: 1 - 37 |
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