EP0830209B1 - Method of depressing non-sulfide silicate gangue minerals - Google Patents
Method of depressing non-sulfide silicate gangue minerals Download PDFInfo
- Publication number
- EP0830209B1 EP0830209B1 EP96915590A EP96915590A EP0830209B1 EP 0830209 B1 EP0830209 B1 EP 0830209B1 EP 96915590 A EP96915590 A EP 96915590A EP 96915590 A EP96915590 A EP 96915590A EP 0830209 B1 EP0830209 B1 EP 0830209B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulfide
- minerals
- depressant
- pva
- amd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 51
- 239000011707 mineral Substances 0.000 title claims abstract description 51
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 33
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000000881 depressing effect Effects 0.000 title description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 66
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 63
- 230000000994 depressogenic effect Effects 0.000 claims abstract description 48
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 26
- 150000004676 glycans Chemical class 0.000 claims abstract description 17
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 17
- 239000005017 polysaccharide Substances 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 63
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 25
- 229920002907 Guar gum Polymers 0.000 claims description 12
- 239000000665 guar gum Substances 0.000 claims description 12
- 235000010417 guar gum Nutrition 0.000 claims description 12
- 229960002154 guar gum Drugs 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000009291 froth flotation Methods 0.000 claims description 6
- -1 vinylalkyl ether Chemical compound 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000013055 pulp slurry Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 description 35
- 238000005188 flotation Methods 0.000 description 26
- 239000012141 concentrate Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 229940068984 polyvinyl alcohol Drugs 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 244000303965 Cyamopsis psoralioides Species 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229940105329 carboxymethylcellulose Drugs 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 description 3
- 229910052611 pyroxene Inorganic materials 0.000 description 3
- 229910052604 silicate mineral Inorganic materials 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052626 biotite Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical class OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YGJMFYMWJXFBFK-UHFFFAOYSA-N 1,2-dihydroxypropyl prop-2-enoate Chemical compound CC(O)C(O)OC(=O)C=C YGJMFYMWJXFBFK-UHFFFAOYSA-N 0.000 description 1
- DELJNDWGTWHHFA-UHFFFAOYSA-N 1-azaniumylpropyl(hydroxy)phosphinate Chemical compound CCC(N)P(O)(O)=O DELJNDWGTWHHFA-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical class CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Chemical class 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical class OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MCSJGXLZPITMIH-UHFFFAOYSA-N 2-aminobutane-1,1,1-triol Chemical class CCC(N)C(O)(O)O MCSJGXLZPITMIH-UHFFFAOYSA-N 0.000 description 1
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 101710145642 Probable Xaa-Pro aminopeptidase P Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- KWKOTMDQAMKXQF-UHFFFAOYSA-N [2-methyl-2-(prop-2-enoylamino)propyl]phosphonic acid Chemical compound OP(=O)(O)CC(C)(C)NC(=O)C=C KWKOTMDQAMKXQF-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229910052891 actinolite Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052885 anthophyllite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052639 augite Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 229910052620 chrysotile Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical class [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical class OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052840 fayalite Inorganic materials 0.000 description 1
- 229910052635 ferrosilite Inorganic materials 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910052899 lizardite Inorganic materials 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AADPGYDUTSGSMI-UHFFFAOYSA-N n-(1-hydroxypropyl)prop-2-enamide Chemical compound CCC(O)NC(=O)C=C AADPGYDUTSGSMI-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052616 serpentine group Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 229940046307 sodium thioglycolate Drugs 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical class CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052889 tremolite Inorganic materials 0.000 description 1
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/016—Macromolecular compounds
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- 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
Definitions
- the present invention relates to froth flotation processes for recovery of value sulfide minerals from base metal sulfide ores. More particularly, it relates to a method for the depression of non-sulfide silicate gangue minerals in the beneficiation of value sulfide minerals by froth flotation procedures.
- Modifiers include, but are not necessarily limited to, all reagents whose principal function is neither collecting nor frothing, but usually one of modifying the surface of the mineral so that it does not float.
- modifiers more particularly depressants
- a depressant is a modifier reagent which acts selectively on certain unwanted minerals and prevents or inhibits their flotation.
- the depressants commonly used in sulfide flotation include such materials as inorganic salts (NaCN, NaHS, SO2, sodium metabisulfite etc) and small amounts of organic compounds such as sodium thioglycolate, mercaptoethanol etc. These depressants are known to be capable of depressing sulfide minerals but are not known to be depressants for non-sulfide minerals, just as known value sulfide collectors are usually not good collectors for non-sulfide value minerals. Sulfide and non-sulfide minerals have vastly different bulk and surface chemical properties. Their response to various chemicals is also vastly different.
- polysaccharides such as guar gum and carboxy methyl cellulose
- guar gum and carboxy methyl cellulose are used to depress non-sulfide silicate gangue minerals during sulfide flotation.
- Their performance is very variable and on some ores they show unacceptable depressant activity and the effective dosage per ton of ore is usually very high (as much as 1 to 10 lbs/ton).
- Their depressant activity is also influenced by their source and is not consistent from batch to batch.
- these polysaccharides are also valuable sources of food i.e. their use as depressants reduces their usage as food and, storage thereof presents particular problems with regard to their attractiveness as food for vermin.
- US-A-4,902,764 (Rothenberg et al.) describes the use of polyacrylamide-based synthetic copolymers and terpolymers for use as sulfide mineral depressants in the recovery of value sulfide minerals.
- US-A-4,720,339 (Nagaraj et al) describes the use of polyacrylamide-based synthetic copolymers and terpolymers as depressants for silicious gangue minerals in the flotation beneficiation of non-sulfide value minerals, but not as depressants in the remediation of sulfide value minerals.
- the '339 patent teaches that such polymers are effective for silica depression during phosphate flotation which also in the flotation stage uses fatty acids and non-sulfide collectors.
- the patentees do not teach that such polymers are effective depressants for non-sulfide silicate gangue minerals in the recovery of value sulfide minerals. In fact, such depressants do not exhibit adequate depressant activity for non-sulfide silicate minerals during the beneficiation of sulfide value minerals.
- polyhydroxyamines are useful as depressants for gangue minerals including silica, silicates, carbonates, sulfates and phosphates in the recovery of non-sulfide mineral values.
- Illustrative examples of the polyhydroxyamines disclosed include aminobutanetriols, aminopartitols, aminohexitols, aminoheptitols, aminooctitols, pentose-amines, hexose amines, amino-tetrols etc.
- US-A-4,360,425 (Lim et al) describes a method for improving the results of a froth flotation process for the recovery of non-sulfide mineral values wherein a synthetic depressant is added which contains hydroxy and carboxy functionalities. Such depressants are added to the second or amine stage flotation of a double float process for the purpose of depressing non-sulfide value minerals such as phosphate minerals during amine flotation of the siliceous gangue from the second stage concentrate.
- This patent relates to the use of synthetic depressant during amine flotations only.
- AU-B-502457 discloses the use of polyvinyl-alcohol, optionally in combination with cellulose derivatives, as depressant for silicate gangues in the froth flotation of value sulphide minerals.
- US-A-2740522 discloses various anionic linear (co)polymers to be used as gangue depressants.
- the polymer depressants used in the present invention may comprise, as the grafted monomers, such acrylamides as acrylamide per se and alkyl acrylamides such as methacrylamide and ethacrylamide.
- the comonomers may comprise any monoethylenically unsaturated monomer copolymerizable with the acrylamide monomer such as hydroxyalkylacrylates and methacrylates, e.g. 1,2-dihydroxypropyl acrylate or methacrylate and hydroxyethyl acrylate or methacrylate; glycidyl methacrylate, acrylamido glycolic acid; hydroxyalkylacrylamides such as N-2-hydroxyethylacrylamide, N-1-hydroxypropylacrylamide, N-bis(1,2-dihydroxyethyl)acrylamide and N-bis(2-hydroxypropyl)-acrylamide; acrylic acid; methacrylic acid; alkali metal or ammonium salts of acrylic and/or methacrylic acid; vinyl sulfonate; vinylphosphate; 2-acrylamido-2-methyl propane sulfonic acid; styrene sulfonic acid; maleic acid; fumaric acid; crotonic acid;
- the effective weight average molecular weight range of the polyvinylalcohols is surprisingly very wide but is preferably at least ten thousand, more preferably at least thirty thousand, and up to millions, e.g. 2 million but preferably up to about 1 million.
- polysaccharides useful as an optional component in the depressant compositions used in the process of the present invention include guar gums, modified guar gums, cellulosics such as carboxymethyl cellulose and starches. Guar gums are preferred.
- the ratio of the polysaccharide to the grafted polymer in the depressant composition generally ranges from 9:1 to 1:9, respectively, preferably from 7:3 to 3:7, respectively, most preferably from 3:2 to 2:3, respectively.
- the dosage of depressant useful in the method of the present invention generally ranges from 0.01 to 10 pounds (1 pound ⁇ 0.454 kg) of depressant per ton of ore, preferably from 0.1 to 5 lb/ton, most preferably from 0.1 to 1.0 lb/ton of ore.
- mixtures of the grafted polyvinylalcohol polymers discussed above are used as the depressant, they may be used in ratios of 9:1 to 1:9, preferably 3:1 to 1:3, most preferably 3:2 to 2:3, respectively.
- the weight ratio of the acrylamide to the polyvinyl alcohol in the depressants used herein preferably ranges from 99 to 1 to 1 to 1, more preferably from 10 to 1 to 4 to 1, respectively.
- the concentration of the optional copolymerizable comonomers is preferably less than 50%, as a weight percent fraction, more preferably from 1% to 30% of the total monomers.
- the acrylamide monomer grafted polyvinylalcohol may be prepared by any method known to those skilled in the art such as that taught in EP-A-117978; Melnik et al; Dokl. Akad. Nauk Uter, SSR, Ser B; Geol. Khim. Brol. Nanki (6), 48-51, Russian 1987; and Burrows et al, J. Photochem, Photobiol. A,63(1), 67-73, English, 1992.
- the acrylamide monomer, alone or in conjunction with the optional comonomer may be grafted onto the polyvinylalcohol in the presence of ceric ion catalyst, e.g.
- ceric ammonium nitrate at a temperature ranging from about 10-50° with intermittent cooling for from about 2-6 hours. Termination of the reaction is effected after a constant solution viscosity is reached by raising the pH with diluted caustic solution to neutral or above.
- the amount of catalyst employed should range from about 0.3% to about 5.0%, by weight, based on the combined weight of monomers to be grafted, preferably from about 0.8% to 4.0%, same basis, the preferred range resulting in a grafted polymer having a more effective depressant activity.
- the new method for beneficiating value sulfide minerals employing the synthetic depressants according to the present invention provides excellent metallurgical recovery with improved grade.
- a wide range of pH and depressant dosage are permissible and compatibility of the depressants with frothers and sulfide value mineral collectors is another advantage.
- the present invention is directed to the selective removal of non-sulfide silicate gangue minerals that normally report to the value sulfide mineral flotation concentrate, either because of natural floatability or hydrophobicity or otherwise. More particularly, the instant method effects the depression of non-sulfide magnesium silicate minerals while enabling the enhanced recovery of sulfide value minerals.
- such materials may be treated as, but not limited to, the following:
- graft copolymers of AMD and PVA of higher molecular weight i.e., 20,000 and 50,000 are also prepared.
- a graft terpolymer is prepared by adding 30.9 parts of a 52% acrylamide monomer solution and 7.2 parts of acrylic acid monomer to a solution of 5.0 parts of PVA (mol. wt. 50,000) in 150 parts water. A total of 10 parts of ceric catalyst solution are used for this preparation.
- Other copolymers are prepared similarly, e.g. using acrylonitrile and vinyl butyl ether.
- An ore containing approximately 3.3% Ni and 16.5% MgO (in the form of Mg silicates) is ground in a rod mill for 5 min. to obtain a pulp at a size of 81% -200 mesh.
- the ground pulp is then transferred to a flotation cell and is conditioned at natural pH ( ⁇ 8-8.5) with 150 parts/ton of copper sulfate for 2 min., 50 to 100 parts/ton sodium ethyl xanthate for 2 min. and then with the desired amount of a depressant and an alcohol frother for 2 min.
- First stage flotation is then conducted by passing air at approximately 3.5-5 l/min. and a concentrate is collected.
- the pulp is conditioned with 10 parts/ton of sodium ethyl xanthate, and specified amounts of the depressant and the frother for 2 min. and a concentrate is collected.
- the conditions used in the second stage are also used in the third stage and a concentrate is collected. All of the flotation products are filtered, dried and assayed.
- a reduction in Ni recovery is to be expected in the process of reducing MgO recovery since there is invariably some mineralogical association of Ni minerals with the Mg-silicates and, when the latter are depressed, some Ni minerals are also depressed.
- the graft copolymers of the present invention are used, there is a much greater reduction in the MgO recoveries compared to that with guar gum.
- the Ni recoveries are also slightly lowered compared with that of guar gum, but the Ni grades in the concentrate are much higher than those obtained with guar gum.
- Example Depressant % Recovery (Gangue Silicate) 11C None 85 12C Polyvinyl alcohol 75 13C Guar 3.4 14 60/40 AMD/PVA 8.9 15 75/25 AMD/PVA 8.7 16 80/20 AMD/PVA 3.0 17 87/13 AMD/PVA 1.3 18 90/10 AMD/PVA 0 19 92.5/7.5 AMD/PVA 7.9 20 97.5/2.5 AMD/PVA 7.8
- a PVA graft copolymer is prepared in accordance with Background Examples 1-5 above, with varying amounts of ceric iron catalyst. The results are shown in Table III, below, following the flotation procedure of Examples 11-20.
- Example Depressant % Recovery (Gangue Silicate) 25 AMD/AN/PVA 80/10/10 7.75 26 AMD/AN/PVA 85/5/10 3.28 27 AMD/AA/PVA 66/24/10 16.60 28 AMD/VBE/PVA 80/10/10 14.70
- An ore containing approximately 3.3% Ni and 16.5% MgO (in the form of Mg silicates) is ground in a rod mill for 5 min. to obtain a pulp at a size of 81% -200 mesh.
- the ground pulp is then transferred to a flotation cell and is conditioned at natural pH ( ⁇ 8-8.5) with 150 parts/ton of copper sulfate for 2 min., 50 to 100 parts/ton sodium ethyl xanthate for 2 min. and then with the desired amount of depressant blend and an alcohol frother for 2 min.
- First stage flotation is then conducted by passing air at approximately 3.5-5 l/min. and a concentrate is collected.
- the pulp is conditioned with 10 parts/ton of sodium ethyl xanthate, and specified amounts of the depressant blend and the frother for 2 min. and a concentrate is collected.
- the conditions used in the second stage are also used in the third stage and a concentrate is collected. All of the flotation products are filtered, dried and assayed.
- a reduction in Ni recovery is to be expected in the process of reducing MgO recovery since there is invariably some mineralogical association of Ni minerals with the Mg-silicates and, when the latter are depressed, some Ni minerals are also depressed.
- AMD/PVA graft copolymer at the same dosage, there is significant reduction in MgO recovery compared with that of guar gum.
- the blend of guar gum and synthetic polymer at the same dosage, however, there is further increase in the depressant activity compared with that of the two components individually.
- the grade of the Ni in concentrate also increases. The results also suggest that much lower dosages of the blend can be used; in this case the Ni recoveries would improve while maintaining the low MgO recoveries.
- Feed Assay 3.31% Ni and 17.58% MgO Example Depressant Parts/Ton Ni Rec. Ni Grade MgO Rec. 39C None 0 96.6 4.7 61.4 40C Guar Gum 350+70+80 93.0 7.7 28.3 41C AMD/PVA (23K) 75/25 350+70+80 90.0 8.3 20.7 42 Guar Gum and AMD/PVA (23K) 75/25; 1:1 350+70+80 88.6 9.2 18.7
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Paper (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Feed Assay: 3.31% Ni and 17.58% MgO | |||||
Example | Depressant | Parts/Ton | Ni Rec. | Ni Grade | MgO Rec. |
1C | None | 0 | 96.6 | 4.7 | 61.4 |
2C | Guar Gum | 350+70+80 | 93.0 | 7.7 | 28.3 |
3C | Guar Gum | 300+60+60 | 92.9 | 6.7 | 33.5 |
4 | AMD/PVA (23K) 75/25 | 300+70+80 | 91.6 | 9.2 | 18.7 |
5 | AMD/PVA(23K) 75/25 | 350+85+100 | 90.1 | 9.6 | 14.2 |
6 | AMD/PVA(23K) 75/25 | 350+70+80 | 90.0 | 8.3 | 20.7 |
7 | AMD/PVA(23K) 75/25 | 280+56+64 | 90.6 | 7.5 | 23.0 |
8 | AMD/PVA(50K) 75/25 | 350+70+80 | 88.0 | 9.5 | 16.7 |
9 | AMD/PVA(50K) 75/25 | 280+56+64 | 84.8 | 7.8 | 17.3 |
10C | PVA(50K) | 350+70+80 | 82.9 | 6.4 | 38.1 |
Example | Depressant | % Recovery (Gangue Silicate) |
11C | None | 85 |
12C | Polyvinyl alcohol | 75 |
13C | Guar | 3.4 |
14 | 60/40 AMD/PVA | 8.9 |
15 | 75/25 AMD/PVA | 8.7 |
16 | 80/20 AMD/PVA | 3.0 |
17 | 87/13 AMD/PVA | 1.3 |
18 | 90/10 AMD/PVA | 0 |
19 | 92.5/7.5 AMD/PVA | 7.9 |
20 | 97.5/2.5 AMD/PVA | 7.8 |
Example | Depressant | % Catalyst (Ce) | % Recovery (Gangue Silicate) |
21 | 75/25 AMD/PVA | 0.5 | 44.6 |
22 | 75/25 AMD/PVA | 1.3 | 8.7 |
23 | 75/25 AMD/PVA | 1.96 | 3.0 |
24 | 75/25 AMD/PVA | 2.6 | 2.6 |
Example | Depressant | % Recovery (Gangue Silicate) |
25 | AMD/AN/PVA 80/10/10 | 7.75 |
26 | AMD/AN/PVA 85/5/10 | 3.28 |
27 | AMD/AA/PVA 66/24/10 | 16.60 |
28 | AMD/VBE/PVA 80/10/10 | 14.70 |
Example | Depressant | Molecular Wt. (PVA) | % Recovery (Gangue Silicate) |
35 | 90/10 AMD/PVA | 9-10K | 7.1 |
36 | 90/10 AMD/PVA | 13-23K | 4.6 |
37 | 90/10 AMD/PVA | 31-50K | 3.3 |
Feed Assay: 3.31% Ni and 17.58% MgO | |||||
Example | Depressant | Parts/Ton | Ni Rec. | Ni Grade | MgO Rec. |
39C | None | 0 | 96.6 | 4.7 | 61.4 |
40C | Guar Gum | 350+70+80 | 93.0 | 7.7 | 28.3 |
41C | AMD/PVA (23K) 75/25 | 350+70+80 | 90.0 | 8.3 | 20.7 |
42 | Guar Gum and AMD/PVA (23K) 75/25; 1:1 | 350+70+80 | 88.6 | 9.2 | 18.7 |
Example | Grafted Polymer (GP) | Polysaccharide (PS) | GP:PS Ratio |
43 | AMD/AN/PVA 80/10/10 | Guar Gum | 9:1 |
44 | AMD/PVA (50K) 75/25 | CMC | 4:1 |
45 | AMD/AA/PVA 66/24/10 | Starch | 1:1 |
46 | AMD/PVA 97.5/2.5 | Guar Gum | 1:9 |
47 | AMD/AN/PVA 85/5/10 | Modified Guar | 2:3 |
48 | AMD/PVA 87/13 | Starch | 3:2 |
49 | AMD/VBE/PVA 80/10/10 | Guar Gum | 2:1 |
50 | AMD/PVA | CMC | 1:1 |
51 | AMD/PVA (9-10K) | Guar Gum | 3:2 |
52 | AMD/PVA(13-23K) | Guar Gum | 3:2 |
53 | AMD/PVA (31-50K) | Guar Gum | 3:1 |
Claims (11)
- A method for beneficiating value sulfide minerals from ores with selective rejection of non-sulfide silicate gangue minerals, comprising:(a) providing an aqueous pulp slurry of finely-divided, liberation-sized ore particles which contain said value sulfide minerals and said non-sulfide silicate gangue minerals;(b) conditioning said pulp slurry with an effective amount of non-sulfide silicate gangue mineral depressant, a value sulfide mineral collector and a frothing agent, said depressant comprising either (1) a polymer of polyvinylalcohol onto which is grafted an acrylamide and, optionally, a comonomer copolymerizable with said acrylamide or a mixture of such grafted polymers, or (2) a blend of said grafted polymer or polymers and a polysaccharide, and(c) collecting the value sulfide mineral having a reduced content of non-sulfide silicate gangue minerals by froth flotation.
- A method according to Claim 1, wherein the weight ratio of the acrylamide to the polyvinyl alcohol ranges from 99 to 1 to 1 to 1, respectively.
- A method according to Claim 2, wherein the weight ratio of the acrylamide to the polyvinyl alcohol ranges from 10 to 1 to 4 to 1.
- A method according to any preceding claim, wherein the graft polymer contains less than 50 weight percent of said comonomer.
- A method according to Claim 4, wherein the graft polymer contains from 1 to 30 weight percent of said comonomer.
- A method according to any preceding claim, wherein the molecular weight of the polyvinyl alcohol is at least 10,000.
- A method according to Claim 6, wherein the molecular weight of said polyvinyl alcohol is at least 30,000.
- A method according to any preceding claim, wherein said comonomer, when present, is selected from acrylonitrile, (meth)acrylic acid and a vinylalkyl ether.
- A method according to any preceding claim, wherein the polysaccharide, when present, is guar gum.
- A method according to any one of Claims 1-8, wherein the polysaccharide, when present, is carboxymethyl cellulose.
- A method according to any one of Claims 1-8, wherein the polysaccharide, when present, is starch.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US473422 | 1983-03-09 | ||
US475161 | 1995-06-07 | ||
US08/475,161 US5507395A (en) | 1995-06-07 | 1995-06-07 | Method of depressing non-sulfide silicate gangue minerals |
US08/473,422 US5525212A (en) | 1995-06-07 | 1995-06-07 | Method of depressing non-sulfide silicate gangue minerals |
PCT/US1996/006481 WO1996040439A1 (en) | 1995-06-07 | 1996-05-07 | Method of depressing non-sulfide silicate gangue minerals |
Publications (2)
Publication Number | Publication Date |
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EP0830209A1 EP0830209A1 (en) | 1998-03-25 |
EP0830209B1 true EP0830209B1 (en) | 1999-08-11 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP96915590A Expired - Lifetime EP0830209B1 (en) | 1995-06-07 | 1996-05-07 | Method of depressing non-sulfide silicate gangue minerals |
Country Status (12)
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EP (1) | EP0830209B1 (en) |
CN (1) | CN1186455A (en) |
AT (1) | ATE183115T1 (en) |
AU (1) | AU693029B2 (en) |
BG (1) | BG62124B1 (en) |
BR (1) | BR9609098A (en) |
CA (1) | CA2222871A1 (en) |
DE (1) | DE69603727D1 (en) |
OA (1) | OA10640A (en) |
PL (1) | PL180626B1 (en) |
RU (1) | RU2140329C1 (en) |
WO (1) | WO1996040439A1 (en) |
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ES2816575T3 (en) * | 2008-07-25 | 2021-04-05 | Cytec Tech Corporation | Silicate suppressor for the flotation of sulfide ores or precious metals |
CN101844110B (en) * | 2010-06-11 | 2013-01-09 | 中国地质科学院郑州矿产综合利用研究所 | Sulfide ore flotation layered silicate mineral inhibitor |
CN104399594A (en) * | 2014-11-21 | 2015-03-11 | 广西大学 | Preparation method and application of flotation separation inhibitor of zinc-sulfur minerals |
CN105537004B (en) * | 2015-12-15 | 2018-04-06 | 云南省化工研究院 | A kind of method prepared by ardealite flotation collector |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0117978A1 (en) * | 1983-02-07 | 1984-09-12 | American Cyanamid Company | Novel process for polymers |
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US2740522A (en) * | 1953-04-07 | 1956-04-03 | American Cyanamid Co | Flotation of ores using addition polymers as depressants |
AU502457B2 (en) * | 1971-06-02 | 1979-07-26 | Ici Australia Limited | Depressants |
US4360425A (en) * | 1981-09-14 | 1982-11-23 | American Cyanamid Company | Low molecular weight copolymers and terpolymers as depressants in mineral ore flotation |
US4720339A (en) * | 1985-03-15 | 1988-01-19 | American Cyanamid Company | Flotation beneficiation process for non-sulfide minerals |
US4744893A (en) * | 1985-08-28 | 1988-05-17 | American Cyanamid Company | Polymeric sulfide mineral depressants |
-
1996
- 1996-05-07 EP EP96915590A patent/EP0830209B1/en not_active Expired - Lifetime
- 1996-05-07 DE DE69603727T patent/DE69603727D1/en not_active Expired - Lifetime
- 1996-05-07 CA CA002222871A patent/CA2222871A1/en not_active Abandoned
- 1996-05-07 PL PL96323918A patent/PL180626B1/en unknown
- 1996-05-07 RU RU98100227A patent/RU2140329C1/en active
- 1996-05-07 AT AT96915590T patent/ATE183115T1/en not_active IP Right Cessation
- 1996-05-07 CN CN96194427A patent/CN1186455A/en active Pending
- 1996-05-07 WO PCT/US1996/006481 patent/WO1996040439A1/en active IP Right Grant
- 1996-05-07 AU AU57332/96A patent/AU693029B2/en not_active Ceased
- 1996-05-07 BR BR9609098A patent/BR9609098A/en active Search and Examination
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EP0830209A1 (en) | 1998-03-25 |
BG102113A (en) | 1998-06-30 |
PL180626B1 (en) | 2001-03-30 |
AU5733296A (en) | 1996-12-30 |
OA10640A (en) | 2002-09-16 |
CN1186455A (en) | 1998-07-01 |
CA2222871A1 (en) | 1996-12-19 |
BG62124B1 (en) | 1999-03-31 |
PL323918A1 (en) | 1998-04-27 |
AU693029B2 (en) | 1998-06-18 |
DE69603727D1 (en) | 1999-09-16 |
WO1996040439A1 (en) | 1996-12-19 |
RU2140329C1 (en) | 1999-10-27 |
BR9609098A (en) | 1999-02-02 |
ATE183115T1 (en) | 1999-08-15 |
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