AUXILIARY FLOTATION REAGENT 1. Activating reagents 2. Depressants 3. Others (they modify: pH, coagulation, redox, rheology, etc.) 100 flotation recovery, % 80 60 Fe3+ Al3+ Pb 2+ M n2+ M g2+ Ca 2+ 40 20 0 0 2 4 6 8 10 12 pH Activating action of hydrolyzing cations. Flotation of quartz in the presence of 10–4 M sulfonate (no flotation in the absence of those cations) ber yl f l ot at i on 100 no f l ot at i on w i t h NaF no f l ot at i on 10 1 dodecyl am i ne, m g/3dm ol eat e, m g/ 3 dm 1000 1000 f l ot at i on ber yl flot atio nw ith 100 Na F 10 no f l ot at i on 1 0 2 4 6 pH 8 10 12 14 0 2 4 6 8 10 12 14 pH Fluoric ions may activate and depress flotation of silicates: a – area of depressed flotation in presence of oleate b) area of activation in the presence of dodecylamine as collector (Manser, 1975) Depressing reagents Depressants acting through adsorption Depressants acting through redox reactions Depressants acting through reactions with flotation reagents Depressors acting through adsorption –MC + D = –MD + C D C –MC –MD – depressant ion – collector ion – collector adsorbed or forming surface compound with mineral – depressant adsorbed or forming surface compound with mineral C MD KM D MC equilibrium const. for bulk reactions X OH y k, C MD K const D MC M Barski’s constant (relation) C D y k. X exp FRT S K OH OH 0 2 SMeOH F 0 2 exp SH SMeX MCH 2 O RT equilibrium const. for surface reactions general form of Barski’ relation Depressants acting through adsorption X OH pH modifiers (acids and bases) 3 collector concentration, mg/dm 100 re c ov e ry , % 80 60 c h a lc o c ite KButX 0. 0001M 40 20 0 2 4 6 8 10 12 pH y k p y rite 0 .6 0 .5 g a le n a 0 .4 0 .3 c h a lc o p y rite 0 .2 0 .1 0 4 6 8 10 12 pH too high and low pH depress flotation of minerals based on attachment of partcles to bubble Values of parameter y for selected mineral-collector system (here pH regulator determines concentration of OH- ions (after Chander, 1988) Mineral – collector y pH range Galena/KEX 0.65 9 – 12 Galena/KDEDTP 0.53 6–9 Sphalerite/DEDTC 0.56 6–8 Sphalerite/DBDTC 0.72 7.5 – 10 Sphalerite/DADTC 0.75 8 – 11 Chalcopyrite/NaDEDTP 0.71 8.5 – 11 Chalcopyrite/KEX - 11 – 13 Pyrite/NaDEDTP 0.62 4–6 - 10 – 12 Pyrite/KEX E - ethyl, D – di, T tio, A- amyl , B- butyl, X- xanthate , P - phosphate , C – carbonate, K- potassium, Na - sodium In highly alkaline environment not working X OH y k Redox depressants Normal potential Electrode reaction Short notation Eh0 (V) S2 O82 + 2e = 2 SO 24 S2 O82 / SO 24 2.050 ClO– + 2H+ + 2e = Cl– + H2O ClO–/Cl– MnO 4 + 8H+ +5e = Mn2+ + 12H2O MnO 4 /Mn2+ 1.640 1.510 Cl2 +2e = 2Cl– O2 + 4H+ + 4e = 2H2O Fe3+ + e = Fe2+ O2 + 2e + 2H+ = H2O2 (CN)2 + 2H+ + 2e = 2HCN Cl2/2Cl– O2/O2– Fe3+/Fe2+ O2/H2O2 (CN)2/HCN Fe(CN)36 + e = Fe(CN)64 Fe(CN)36 / Fe(CN)64 Cu2+ + e = Cu+ 2H+ + 2e = H2 Cu2+/Cu+ H+/H2 SO 24 + 2H+ + 2e = SO 32 + H2O SO 24 / SO 32 N2 + 4H+ + 4e = N2H4 (hydrazine) S + 2e = S2– Zn2+ + 2e = Zn N2 /N2– S/S2– Zn2+/Zn 1.360 1.228 0.771 0.680 0.370 0.363 0.167 0.000 –0.103 –0.33 –0.10 –0.63 1 HCuO , CuO 22 2+ Cu 0 .8 CuO - 0 .6 0 10 0 .4 2 potential Eh, V 1 0- 6 10 0 10 -4 10 -2 1 .2 1 0- 6 1 .4 0 .2 -2 -4 10 0 10 Cu 2O -6 10 -0 .2 -0 .4 Cu -0 .6 -0 .8 -1 0 2 4 6 8 pH 10 12 14 re c ov e ry , % 100 80 Cu2S 60 Cu5F e S4 Cu F e S 2 40 F e S2 20 0 -0 . 3 -0 . 2 -0 . 1 0 0 .1 0 .2 0 .3 0 .4 pote ntia l, V Relationship between flotation recovery of sulfides and potential applied to a platinum wire immersed in aqueous suspension of a sulfide containing ethyl xanthate at 1.44·10–5 kmol/m3. After Richardson and Walker, 1985 Depressants acting through reactions with flotation reagents 2C2H5OC(S)SK + 2K2SO3 + 2KHSO3 + 2O2 2C2H5OC(S)SOK 2C2H5OH + 4K2S2O3 + 2CO2 Removal of xathates from sulfides Depressants used in flotation Inorganic depressant Alum Ammonia Calgon Sodium cyanide Sodium dichromate Phosphates Sodium silicate Fluoric acid Sulfuric acid(IV) Sulfuric acid(VI) Hydrochloric acid Sodium sulfate(IV) Zinc sulfate(VI) Caustic soda Oxygen Lime Sodium carbonate Sodium hydrosulfide Formula KAl(SO4)2 NH3 polyphosphates NaCN Na2Cr2O7 various Na2SiO3 HF H2SO3, SO2 H2SO4 HCl Na2SO3 ZnSO4 NaOH O2 Ca(OH)2 Na2CO3 NaHS Organic depressant starch quebracho tannin lignin derivatives synthetic polymers acetic acid dextrin humic acid cellulose derivatives alginate chitin derivatives citric acid hydrazine thioglycolic acid chelating compounds electrons (redox substances) t ur bi di t y, Dispersion modifiers Acids, bases, large organic ions 150 2 × 1 0- 3 Na Cl 130 2 × 1 0- 2 Na Cl 110 Ti O2 90 2 × 1 0- 1 Na Cl 70 iep 50 2 4 6 8 pH 10 12