SCHOOL OF ENGINEERS OF PERU REAGENT FLOTATION OF METAL AND NON-oxidized ore VIDALÓN JOSE GALVEZ LIMA, March

2004 Oxidized ore Malachite ....... Azurite ........... .......... Cuprite Chrysocolla Tenorite .. ...... Cerussite ......... Anglesite ........ Smithsonite ... Willemite ........ Hemimorphite or Calamine CuCO3.Cu (OH) 2 2CuCO3.Cu (OH) 2 CuO Cu2O CuO.nSiO2.mH 2O PbCO3 ZnCO3 Zn2SiO4 2ZnO.SiO2.H2O PbSO4 Oxidized ore Cassiterite ....... Chromite .......... Vanadinite ..... SnO2 FeCr2O4 (PbCl) Pb4 V3O12 NON-METAL MINERALS Barite ...... Calcite BaSO4 ....... CaCO3 Dolomite .... (Ca, Mg) CO3 Fluorite .. .... Scheelite CaF2 ... Phosphates CaWO4 .... Na5 (PO4) 3 (F, CO3) SOLUBLE SALTS Halite ......... Sylvite ......... Carnallite .... Langbeinite. Kainit ........ NaCl KCl epsomite KCl.MgCl2.6H2O 2MgSO4.K2SO4 MgSO4.KCl.3H2O MgSO4.7H2O FLOTATION MECHANISMS • The flotation process depends on complex phenomena that occur on the surface o f mineral particles and air bubbles formed in water. • The flotation properties of a mineral depends on its crystalline structure. • Factors that influence the flotation: - Presence of impurities in the ore, in solid solution or adsorbed on colloidal minerals - Grade Release - Hard water affects the relationships between the mine ral and reagents, and sometimes form insoluble compounds with the reagents. CLASSIFICATION OF MINERALS AS FLOAT THEIR PROPERTIES 1. Sulphides (Cu, Pb, Zn, Ni, Hg, Sb) and native metals: They have low wettabili ty. Float with xanthates. 2. Non-polar non-metallic minerals: graphite, sulfur, coal, talc. Have low wettability. Collectors float with very weak and sometimes with just sparkling. 3. Oxidized minerals (Cu, Pb, Zn): float with sulfurization and xanthates, or fatty acids. CLASSIFICATION OF MINERAL ... 4. Mineral Salts polar type Ca, Mg, Ba and Sr: Scheelite, powelita, apatite, pho sphorite, fluorite, calcite, barite, magnesite, dolomite. They float with fatty acids. 5. Oxides, silicates and alumino-silicate: silica, zircon, rutile, cassit erite, ilmenite, feldspar, beryl, mica. Many float with anionic and cationic col lectors, other cation-dependent activators. • 6. Soluble salts: sylvite, halite, langbeinite keinita. Float with fatty acids or saturated brines cationic collec tors. FLOTATION REAGENTS • They are the strongest variable and flexible interaction of the flotation proc ess. • Major advances have been in the development of flotation reagents. • Theo ry of hydrate layers: The effect of flotation reagents, is transferred through h ydrated layers, leading to an active subject of mineral particles to bubbles. CLASSIFICATION OF REAGENTS According to the focus area 1. Reagents which are concentrated at the interface mineral-water, mainly in the mineral surface: collectors and activators. 2. Reagents which are concentrated in the air / water: sparkling and inorganic electrolytes. 3. Affecting the flota

tion reagents, remaining in the water: Activators, pH regulators and depressants . CLASSIFICATION OF REAGENTS According to its function 1. Collectors • Organic acids: - A. Na oleate oleic and - alkyl sulfate Na - alkyl phosphate Na • Thio compounds: mercaptans, xanthates, dithiocarbonatos, dithiofosfatos, merca pto-benzothiazol. • Derived from Ammonia: Amines, salts ammonium salts, pyridine, ethanol amines. • Oils: kerosene, petroleum Organic Acids The most commonly used collectors of the first group contains the carboxylic gro up, which is the anion of the fatty acids. Much less reagents are used with sulf ate and sulfonate groups. Carboxylic group: Sulfate group: O C OH Sulfonate Group: O O O O S O S OH OH Fatty Acids • They are good collectors commonly used for industrial minerals. • They are oft en used as co-collectors for flotation of heavy minerals and feldspar, and apati te in flotation. • Can be fed as fatty acids or as salts of Na in solution or aq ueous dispersion. • They are also mixed with nonionic emulsifiers. There are sel ective and are not used in mineral difficult to float, requiring more specific r eagents. RENT SODIUM SULFATE Flotinor S-72 • Application is especially recommended for the flotation of barit e as occurs with fluorite and calcite. • Can also be used in the flotation of ce lestite, gypsum, kainit, anhydrite and anglesite. If necessary, you can use a fo am. ACID ESTERS OF MONO / diphosphorus • Flotinor SM-15 is used in the flotation of heavy minerals with iron and titani um and glass sand biotite. Can be used in combination with a fatty acid. • Other uses: flotation of carbonates such as calcite,€dolomite and magnesite when the stone is a silicate. Also in reverse flotation of phosphate in combination with a collector eterpropilen alkyl silicate and fatty diamines. • Can be used other phosphonic acid esters of various chain lonitudes and constitution or mixtures o f these with others such as fatty acids, alkenyl succinic acid ester, an alkyl s ulfo succinate succinamato and sulfo. Cationic Collector • They are derived from an ammonium ion complex. N +

The polar group is adsorbed on minerals has a positive charge. • They are used t o float oxides, silicates and aluminosilicates. • Are less selective anionic rea gents. Primary amine: secondary amine R-NH2 R2-NH tertiary Amina: Amina quaterna ry-N R3: R4-N-Cl dodecyl ammonium ion + + + + + + + + ion acetate Hemimicelas of dodecyl ammonium ions on quartz % Recovery 100 90 80 70 60 50 40 30 20 10 100 200 500 Na + Fe3 + 1000 g / t Reagent Effect of Na + and Fe3 + in the flotation of quartz with lauryl amine CLASSIFICATION OF REAGENTS 2. Regulators: • Electrolytes: Cal, NaOH, A. Sulfuric, Na bicarbonate, salts of Cu, Fe, Al, Pb, Zn, Na2S, NaCN, Na silicate • No electrolyte: Dextrin, starch, tannins. 3. Sparkling: Terpineol, phenol, cresol, pyridine, orthotoluidine Oxidized ore flotation A. Mineral surface oxidation First Fleet sulphides and oxides after fatty acid • Flotation: Ac. Oleic not ver y selective. It is applicable only few minerals that are relatively insoluble, b ecause Ca and Mg ions activate the bargain, as well as pyrite and pyrrhotite. • More selective is hydrolyzed palm oil (A. Palmitic with oleic and linoleic). • c arbonate and silicate Na Na soften the water and disperse lamas. Should recycle tailings water. Mineral surface oxidation • Flotation with sulfurization and thio collectors: It is more selective and eff icient. There are difficulties when the mineral is clay and / or pyrite altered. • Reagents: Na2S or NaHS, XmAK, palm oil and petroleum. B. Oxidized ore flotation • Vanadinite: sulphurize fleet without high doses of xanthates or other thio-cat cher (1-2 kg / t) • Malachite and azurite: Sulfurization with Na2S or NaHS and x anthates in dolomitic gangue minerals with Fe without sulfate added sulfurizante ammonium together with the recovery and selectivity improvement • Chrysocolla a nd other copper silicates are solid solutions of Cu in silicate in varying propo rtions, and leaches Na2S • tenorite and Cuprite Cu: Not sulphurize under alkalin e conditions. The fleet cuprite xanthates. 100 Cu% RECOVERY 80 60 40 20 200 400 600 800 1000 1200

pH: Amyl Alcohol 11: 97 mg / L Amil xanthate: 20 mg / L mg / L Na2S.9H2O Effect of Na2S in the flotation of malachite 100 Cu% RECOVERY A B pH: 11 Na2S: 432 mg / L Amil xanthate: 40 mg / LA: α-terpineol B: Amyl Alcohol 80 60 40 20 Sp rkling 10 20 30 40 mg / L 50 60 Effect of fo ming gents in the flot tion of M l chite

EFFECT OF SULFATE NIO AMO 1 00 95 90 85 80 75 70 65 60 55 50 0 5000 10000 15000 20000 25000 C u [N HS + (NH4) 2SO4] C u [N HS] HS N [g / t] Oxidized ore flot tion • Cerussite nd Anglesite: • Sulfuriz tion with N 2S or N HS nd x nth tes. Shou ld be ground c refully, re fr gile nd e sily produce l m s. The cerussite is m ore flo t ble. The sulfuriz tion becomes the surf ce l yer flo t ble sulphide wi th x nth tes: PbCO3 + N 2S = PbS + N 2CO3 • N HS is more ctive th n N 2S. • The re gent consumption is reduced with strong short-conditioning nd ventil tion i n the cell nd dding N 2CO3. Oxidized ore flot tion • The sulfuriz tion nd flot tion of cerussite nd nglesite is expl ined by the presence of Pb c tions uncompens ted ch rge on the surf ce of cle v ge. • Angle site with difficulty nd w s sulphurize c n be flo ted with x nth tes. You c n lso use f tty cids or lkyl sulfon tes where the ore is cidic nd in the bsen ce of Fe oxides nd other insoluble sulph tes.

Oxidized ore flot tion Re gents in the flot tion of Oxidized Zn (g / t) REAGENTS Amin (s lt) Amin oil emulsion Sp rkling N 2SiO3 N 2S S. Giov nni

 

 

Oxidized ore flot tion Smithsonite, Willemite nd Hemimorphite (C l mine) flo t ste ryl mine cet te nd pine oil, nd / or 8-hydroxyquinoline (oxine), using s dispersing l m s: N 2 S, N 2CO3, N silic te. M ny times, pre desliming 5 or 10 microns, bec use cl ys nd Fe oxides nd fine p rticles consume lot of collector. • N 2S is essent i l bec use it blocks the solubiliz tion of Zn on the surf ce of the miner l. • The concentr te is 30-40% Zn, but the ignition (c rbon te) to> 1000 ° C gives 65 -70% Zn.

 

 

   

 

 

 

       

 

 

     

 

 

 

     

 

   

 

 

 

     

 

 

 

 

 

 

 

 

 

 

 

 

 

 

   

 

 

   

 

 

 

   

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

       

 

 

 

 

   

 

 

 

 

   

 

30 700 110 -2830 Morocco 700 40 2500 -500 % Zn Recovery 100 90 80 70 60 50 40 30 20 10 0.5 0.7 0 9 1.1 1.3 1.5 1 2 1.7 mol / t Flot tion Smithsonite: 1: oct decyl mine 2: oct decyl methyl

Oxidized ore flot tion • Oxides of Al, Sn, Mn nd Fe re concentr ted by gr vity processes, m gnetic n d / or electrost tic. For fine-gr ined miner ls, the flot tion. • Chromite: To s ep r te olivine nd serpentine h s been used gr vimetric methods. • C ssiterite: Collectors studied: lkyl c rboxyl tes, lkyl sulf tes (sodium hex decyl sulf t e), sulfosuccin m to cid, p-tolyl rsonic, phosphonic cid, s licylic ldehyde, nd sulfuriz tion nd ctiv tion le d to flo t with x nth te 100 Sn% RECOVERY 90 80 70 HF IOF IHF TAs IOF = iso octyl phosphonic cid = HF cid n-heptyl phosphonic cid IHF = TAs = i so hexyl phosphonic cid p-tolyl rsonic 60 Collector 200 400 g / t 600 800 Flot tion of c ssiterite with different collectors Oxidized ore flot tion • Fe oxides: • M gnetite is concentr ted by m gnetic sep r tion. • The thin nonm gnetic re tre ted by flot tion of qu rtz nd silic tes, or flo ting specul r hem tite. • M jor collectors: c rboxylic cid nd petroleum sulfon tes, nd occ sion lly, mine s lts of cid circuit. • For the remov l of c tionic re ctive si lic te is used in circuit lk line. • fine concentr tes re pelleted nd sintere d. FLOTATION OF NON-METAL FLOTATION OF NON-METAL • Non-met llic Miner ls: They re used for industri l purposes nd not to remove the met l they cont in. • Fluorite nd B rite: • flo t with f tty cids (oleic nd linoleic A.) with c lcite depress nt: N 2CO3, N silic te, t nnic cid, queb r cho. Quebr cho t nnin depresses c lcite (50 to 1000 g / t). • In flot tion of

 

   

 

   

 

 

   

 

 

 

 

 

 

 

 

         

 

   

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

     

     

 

   

 

 

   

 

   

 

 

 

 

 

     

   

 

   

 

 

   

   

     

   

 

 

 

 

 

 

   

     

mine

       

   

   

fluorsp r to 75-85 ° C to depress silic Fluorite

nd c lcite.

8 phosphonic cid (IMPA-8): ide l for sep r ting fluorite collector of other min er ls: Fluorite>> c lcite> fluor p tite FLOTATION OF NON-METAL • Scheelite: Fleet f tty cid (collector) nd N 2CO3 (pH regul tes), nd v rious dispers nts nd depress nts of l m s. It combines with gr vity sep r tion. • Ph osph te: The go l is to flo t c lcite nd dolomite (consumers cid) by oleic ci d, depressing the rougher concentr te phosph tes by orthophosph te or fluorosili c te ions. Other p tite depress nts: Cu nd lum sulph te N OH ctive c rbon te s. Sp rkling: Ethyl Alcohol. Flot tion of phosph te by b cteri • In s mples of pure p tite nd phosph tes Florid g ngue dolomite flot tion re se rch w s conducted using the b cteri Mycob cterium phlei nd B cillus licheni formis JF-2, both s collector nd depress nts in flot tion with nionic colle ctors. • The s mples h d good rele se but very l rge surf ce re so the re ge nt consumption w s l rge, nd low selectivity. • The cell w lls of b cteri cont in surf nt ntes both very ctive, which dr m tic lly reduces the surf ce tensio n of the suspensions nd incre ses the cont ct ngle of miner ls which dsorb to the queous solution. Flot tion of phosph te by b cteri ... • The results of the experiments show th t M.phlei m rkedly dsorbed on the surf ces of dolomite nd p tite, nd show more ffinity for th t p tite dolomite, nd B cillus licheniformis JF-2 h s even more ffinity M. phlei to join the dolo mite. • Both b cteri ct s depress nts of dolomite in the flot tion of phosph te, resulting concentr te with less th n 1% MgO in the flot tion of Florid phos ph te. FLOTATION OF SILICATES • Miner ls of beryllium, lithium, tit nium, zirconium nd niobium silic tes exis t s or ssoci ted with silic tes. • Use of nionic nd c tionic re gents nd fl uoride ion s modifier. SOLUBLE SALT FLOTATION SOLUBLE SALT FLOTATION • Sites cont ining mixtures of pot ssium chloride: H lite, sylvite nd c rn llit e, nd / or sulph tes: L ngbeinbit , k init. • The recovery is done by fr ction l cryst lliz tion. • In first s tur ted brine is sep r ted by cicloneo cl ys (re sulting in high consumption of re gents nd incre sed viscosity of the solution) , sylvite is flo ted with n- lkyl mine or sulfon te, or H lite with n- lkyl c r boxyl te of he vy met ls nd non-oil pol r. • Sep r tion of Mg nd K sulf tes so dium sulf te is less efficient. TOXICITY TOXICITY OF REAGENTS Toxicity is the property of subst nce to c use dverse effects on n org nism. It is rel ted to dose or exposure, nd v ries from one org nism to nother. Tox icity of flot tion re gents nd ions is v ried: - Very toxic: Collectors thiólicos, sulfon tes nd mines, cy nide - Moder te: S p rkling lcoholics - No Toxic polypropylene glycol. The toxicity of met ls in queous solution is ttributed to the concentr tion of ions. E ch met l h s m ny compounds, c / u of which beh ves differently.

 

 

 

 

 

 

       

 

 

 

 

 

 

 

 

 

 

 

 

 

 

     

         

   

 

 

   

       

 

 

 

 

 

 

 

 

   

 

 

 

 

 

 

 

 

 

   

   

 

 

 

       

 

 

 

 

 

       

 

     

 

 

 

 

 

 

 

   

 

 

 

                 

 

 

 

 

 

 

   

   

           

     

 

 

 

   

 

 

 

 

 

 

 

 

 

 

 

 

 

   

 

 

 

   

 

 

   

   

 

           

     

 

 

 

 

 

   

 

 

   

 

 

 

 

 

 

         

 

 

 

 

 

 

   

 

 

 

 

 

 

   

 

 

 

 

 

 

 

 

 

       

   

     

DESIGN OF REAGENTS ... • It w s verified the effect of molecul r recognition with miner l fluorite, c lcite nd fluor p tite. • It demonstr ted the cruci l role th t the cryst l str ucture of the surf ce to determine the selectivity of given re gent. • The des ign of re ctive molecules so th t their molecul r rchitecture is comp tible wit h the surf ce of the miner l of interest nd confirming the rel tive ffinity / strength of its inter ction with lo miner l surf ce using molecul r modeling te chniques. (B) © complexes optimized IMPA-8 ( ) Fluorite [111], (b) C lcite [110] nd © flu or p tite [100] (A) Inter ction Energy (kc l / Mol) 915.4 -141.2 97.5 Fluorite C lcite Fluor p tite Qu ntum chemic l c lcul tions IMPA IMPA = n

cid-8-bis methylene phosphonic Iminne

REFERENCES • Dr. Pr dip, T t Rese rch Development nd Design Centre, Pune, Indi ; Prof.JMC ses, L bor toire Environnement et miner l processing, INPL / ENSG V ndoeuvre-le s-N ncy, Fr nce .- "Scientific Design of Flot tion Sep r tion Re gents b sed on Molecul r Recognition t Miner l Surf ces. " December 1998 J. Lej "Surf ce Chem istry of Froth Flot tion", University of British Columbi , Plenum Press, 1983. V .I. Kl ssen / V.A. Mokrousov, "An Introduction to the Theory of Flot tion, Butte rworths, 1963. Quiroz Roberto Lopez, "Flot tion At c mite" Proceedings of the Fi rst L tin Americ n Congress of flot tion. Rese rch & Development GmbH Cl ri nt M ining Chemic ls Division .-

 

 

DESIGN OF REAGENTS ... • To qu ntify the rel tive ffinity of re gent in p rticul r, different miner ls, c n be successfully used molecul r modeling comput tions of specific inter c tions on miner l-re gent. • The correl tion between the order of the response to miner l flot tion re gent b sed on theoretic l c lcul tions is very good comp r ed to th t observed in experiments. • You must know th t the theoretic l c lcul tions of the energy of the miner l-re gent inter ctions must be b sed on knowled ge of the cryst l structure of miner ls nd molecules of re gent.

   

DESIGN OF REAGENTS • Recent b sic rese rch on miner l-re gent inter ctions to identify the molecul r recognition mech nisms nd predict the molecul r structure suit ble for the se p r tion of one miner l from nother. Tools: - - - - Synthesis nd ch r cteriz tion of miner l tests microflot tion dsorptio n studies infr red extern l reflection techniques to determine the composition nd structure of dsorbed l yers t the interf ce re ctive miner l-w ter - molecu l r modeling of the inter ctions miner lre ctivo

 

 

   

 

 

   

   

 

   

 

 

 

 

 

 

     

   

 

 

 

 

 

 

 

 

   

 

   

   

 

 

   

 

   

 

 

     

 

 

 

 

 

 

 

 

 

 

 

 

   

 

 

 

 

 

     

 

 

 

 

 

 

     

 

 

 

 

 

           

 

 

 

 

 

       

           

     

   

 

 

 

 

   

 

 

   

   

 

 

   

 

 

   

 

 

 

 

 

 

 

   

           

   

• • • • Th nk you very much