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This institution reserves the right to refuse to accept a copying order if, in its judgment, fulfillment of the order would involve violation of Copyright Law. i i| EESSSSESSSTESESETELESTEEETS: LINDA HALL LIBRARY $109 CHERRY STREET KANSAS CITY, MISSOURI. 64110-2498 PHONE (816) 363-4600, FAX: (816) 926.8785, SHIP TO: Library - Interlibrary Loan Georgia Institute of Technology 704 Cherry Street Atlanta, GA 30332-0900 GAT Pairon: Ma, Jun Fax: 404-894-8190 Phone: Ariel: 130.207.50.108 Regular Ariel LAL ccL Max Cost: 25.001FM Notes: Borrowing Notes; ARIEL 130.207.50.108 (version 3.4) Date: 2006 Article/Paper: Chengliang Ji ‘Wang: BK: Parekh; Ores, Flotatio Pages: 31/0 ite OCLC #: 69680056 ISSN: 9780849396151 (set ; ‘num k 6/24/1 1DocSery #: 642692 Shelved as: QD506 .E55 2006 quarto Location: LHL REERQQM Title: Encyclopedia of surface and colloid science / Lender string: TMA,ALM,ALM,*LHL,TXI IL: 79163918 IA DOCSERV / OCLC / PULL SLIPRess Te) Ores, Flotation of CChengliang Jiang Xiang Huai Wang Enzymatic Deinking Technologies (EDN, LLC, Noreross, Georgia, U.S.A B. K. Parekh Center for Applied Energy Research, University of Kentucky, Lexington, Kentucky, U.S.A. INTRODUCTION Froth flotation is one of the most widely used separa- tion process for treating fine-size ores. The flotation process has provided economic recovery of low-grade and complex ores that would have otherwise been classed as worthless, Almost all the supply of copper, lead, zine, and silver minerals is recovered from ores by froth flotation, Froth flotation is a wet separation process that utilizes the difference in the surface physicochemical properties of various minerals to segregate the minerals, in an ore into several products. In most ores, the particles of valuable minerals are closely associated with other minerals, To separate these minerals, the ‘ore is first crushed and then wet ground to the sizes, at which valuable minerals are liberated from the gangue or worthless minerals. Fig. | illustrates the flotation process in a typical Aotation cell!) The aqueous ground ore suspension (Rotation pulp) is stirred in a tank with an impeller. For desirable minerals to float, their surfaces must be rendered hydrophobic. For undesirable minerals, the surfaces should be rendered hydrophilic. To achieve this condition, various chemicals known as flotation reagents are added in the pulp and air or gas is sparged in the tank, The desired mineral particles attaches to the air or gas bubbles. Due to the buoyancy of the bubbles, these mineral particles rise to the surface to form a mineralized froth layer and are removed as the concentrase, and other mineral pacticles remain suspended in the pulp due to their hydrophilic surfaces and are termed the tailing of the separation process, William Haynes in 1869 patented a process for separating sulfide and gangue minerals using oil and called it bulk-oil flotation." The currently used froth Aotation process was invented in 1905 simultaneously by A. H. Higgins in England and by G. A, Chapman in Australia." In the early times, only naturally oocur- ring chemicals such as fatty acids and oils were used as Aotation reagents in a large quantity. ‘The introduction of xanthate in 1925, an organic compound with divalent sulfur, as a collector for sul- fide minerals was a remarkable development in froth flotation technology, which made economic recovery of many minerals [rom ores possible!”! Even today, xanthates play an important role in the recovery of world's mineral resources. Most flotation collectors used today were developed in the early nineties which includes xanthates, dithiophosphates, fatty acids, alkyl sulfates, alkyl sulfonates, and amines. Since the advent of froth flotation, the quantity of ores treated has increased exponentially. Currently, nearly. to billion tons of ore are treated worldwide annually by flotation. The flotation process is widely used for the recovery and concentration of nonferrous sulfide minerals, such as Cu, Pb, Zn, Ni, Mo, $b, Co, ete. as well as nonsul- fide minerals, such as $102, CaCOs, CaF, NaCl, KCL, sulfur, alumina, ZrSiOg, TiO, clays, ete., which are usually used as raw materials in chemical industry Phosphate, coal, and iron ores are also commonly processed by flotation technology. FLOTATION PRINCIPLES AND ‘SURFACE CHEMISTRY In froth flotation, three phases are involved in the process, namely, the solids to be separated, a liquid (usually water), and gas (usually air). Minerals are mostly crystalline inorganic solids; however, some minerals may also be noncrystalline, such as coal and resins, Flotation utilizes the differences in the surface properties of the minerals to achieve the selective separation of one mineral from the other. OF all the surface properties, surface energy (or surface tension) and surface charge are the most important." The relative ease and wide possibility of modifying and controlling the respective surface energy and surface charge of various minerals make froth flotation more versatile than any other separation process. Encyelopedia of Surface and Colloid Science DOI: 10.1081/-ESCS-120000918, 318 Copyright «) 2006 by Taylor & Francis. All ighs reserved| Ee eee eee ee eee ee Soar ee ee eae ee eee | i f (Ores, Flotation of Hs Feats containing hydrophobic ‘00 envrappes materials Tee ‘Suspension seme <= __, containing unfoates material Fig. 1 Schematic diagram ofthe flotation process in a froth flotation cell. (From Ret!"1) ‘The surface properties of minerals can be modified by adding various kinds of inorganic and organie chemicals. Contact Angle and Flotation The relationship among solid, liquid, and gas phases ‘can be characterized by the contact angle (8), which is defined as the angle between the solid surface and the tangent to the liquid surface at the three-phase contact. measured through the liguid. Fig. 2 illustrates the tensile forces leading to the formation of a contact, angle between the solid surface and the gas bubble. The three phases can be expressed by Young's equation i160 = Is + 7100088 a Where ys/c. 75/t+ and 76 are the surface free ener gies or surface tensions between solid-gas, solid-liquid and liquid-gas interfaces, respectively. A small contact angle (<20°) indicates that a hydrophilic surface that will be easily wetted by water and gas bubble will not 8 surface. (From Ref.) 419 tus a. Fig. 2 Contact angle between an air bubble and a solid surface im a liguid medium, Liquid Solid attach to the solid surface. A large contact angle (>50") indicates that a hydrophobic surface and gas bubble can displace water and attach to a solid surface. A hydropho- bic mineral is also aerophilic, which has a high affinity for gas or air. This is illustrated in Fig. 3.") In contrast, a hydrophilic mineral has a high affinity for water. Because most of the minerals present in the ore are hydrophilic in nature, flotation reagents must be added to the pulp to make the desirable minerals more hydro- phobic while keeping other minerals hydrophilic. Electrical Double Layer and Surface Charge In the flotation of nonsulfide minerals such as oxides and silicates, the surface charges of the minerals are the dominant properties to affect the interaction between surfactants and the mineral surfaces Fig. 4is a schematic representation of the electrical double layer of @ mineral surface in an aqueous electrolyte solution. The electrical double layer can be divided into two parts, the compact Siem layer between surface and Stern plane, where surface poten- tial fo drops to bs (Stern potential), and the diffuse layer, or Guoy layer. in which potential drops (0 2er0 at infinite distance!" The location of the Stern layer is approximately the magnitude of the hydrated ions’ radius from the surface. A layer of water is bound to the charged surface. When the particle travels in a CZ XI eo SN oy VUZE Ce) Re Liquia 3. Different eases of wetting (A) by placing a drop of water on a dry surface and (B) by blowing an air bubble under a wet,ee eee eee eee eee eee Pee) 70 solution, shear occurs at the shear plane between the surface and the electrolyte solution, and the potential of the particle at shear plane is called zeta potential, (. One of the important parameters of a solid sus- pended in water is point of zero charge (p20), which is defined as the condition such as pH and potential- determining ion concentration under which a direct measurement of surface charge density gives a net zero charge on the particle surface. Table 1 lists pzc’s of a number of oxide and silicate minerals.) The chemisorbed ions in the Stern layer establish the surface charge and are called potential-determining ions. ‘These ions may include the ions forming the minerals, H™ and OH™ ions, surfactant ions that can form inso- Tuble salt on mineral surfaces, and the ions that can Form stable complex ions with surface species. ‘The flotation of nonsulfide minerals such as oxides and silicates can be well explained in terms of electrical Solid surface ‘Stem plane "Shear plane | © Potential determining ions 1@ Hydrated counterions hi Distance Fig. 4 Schematic representation of the electrical double layer and potential drop asa function of distance from surface (Ores, Flotation of Table 1 Point of zero charge (pH) for various minerals Mineral pe Mineral pe Augie 27 Gamat Bentonite 30 Goethite 67 Beryl MM334 Hematite 5.0, 60,67 Boitite 04 Kaolinite 34 Cassterite 45 Magnetite 65 Chromite 56,70,7.2 Pyrolusite 56,74 Chrysocolla. 2.0 Quartz 18 Cormndum 90,94 -RhoWonite 28 Cummingtonite 5.2 Rutile 67 Cuprite 9s Tourmaline 40 Diopside 28 Zircon 58 From RAP ae double-layer theory, when alkyl carboxylate, sulfate and sulfonate surfactants are used.°"" ‘The electrostatic interaction between surfactant ions and goethite mineral surface is well illustrated in Fig. $04 Goethite has a pze at pH 6.7; anionic sur- factants are effective in floating goethite below pze s 9 (© 1x10 MNaG! zo © moa Nec aaa Paerenies Eo Bap 3 oh aie L L rm nm i r00 g Bok g = Eo nsona 2 ook © Asoine 3 mercer esas 0 [ESET Sra HS ASP BAST TE pH Fig. 5 The dependence ofthe flotation properties of goethite (HPe0;) on surface charge, Upper curves are zeta potential 4s a function of pH at different concentrations of sodium chloride, Lower curves are the flotation recovery in 1 x 10? M solutions of dodecylammonium chloride, sodium dodecyl sullate, and sodium dodecyl sulfonate. (From Ret") Beene PEE eHOres, Flotation of (ie., pH 6.7) because the mineral surface is positively charged, whereas cationic surfactants are effective above pzc. In the flotation process, the surface charge property of minerals may be modified by adjusting solution pH with alkali and/or adding polyvalent metal ions, surfactant, etc., so as to achieve the selec- tive separation of one mineral from the other. Surface Reactions on Mineral Surface The interaction of atom, molecules, and ions on the tmineral-water interface with various kinds of chem cals mainly includes:"® 1) surface reactions (surface hydrolysis, formation of coordinative bond with metal ions and with ligands, ete.); 2) hydrophobic sorption (the adsorption of a hydrocarbon substance on the ‘mineral surface due to hydrophobic forces to reduce the mineral surface energy): and 3) adsorption of sur= Factants (molecules that contains both a hydrophobic and hydrophilic end) to reduce surface energy and become adsorbed at the mineral surface. More specifi cally, the major surface interactions taking place on ‘mineral surfaces in the flotation system can be sum- marized as follows, Acid-base reaction In the presence of water, oxide minerals are generally covered with surface hydroxyl groups. The H* and OHL are the potential determining ions on the surface, which control the sign of the charge on surface of the ‘minerals. The dissociation of the hydrated amphoteric surfaces of oxides results in the pH-dependent charge 4s expressed by in the Following reactions: =McOH,* + =MeOH + H* icOH HH") Ki = “TEMeOtt:*) @® =MeOH @ =MeO” + H* xy = {= MeOH") 8) vleOH) where =Me denotes solid surface. [] and {} denote concentrations of species in the aqueous phase (mole/liter) and concentrations of surface species (mol/kg), respectively. KY and 3 are the equilibrium constants of the Eqs. (1) and (2), respectively, The sur- face charge due to specific interaction of H* and OH ions is determined by the difference in protonated and éeprotonated =MeOH concentrations. At pzc con tions of pHpzc, {=MeOH;} is equal to {=MeO™} ant Examples of acid-base reaction on minerals with A and OH” as potential-etermining ions are FeOOH(s) + H* = Fe(OH)*(surface) é e a) FeOOH(s) + OH” = Fe(OH), (surface) Metal ion binding In the presence of metal ions, protons and metal ions compete with each other for the available coordinating sites on the surfaces: =MecOH + MY eo =McOM@)* + HY (5) le - OH) + M* =MeO),M"2* + 2H (6) ‘The extent of reaction is related to the exchange of H* by metal ion, M"*. Examples include Si-OH + Ca?+ = =Si0Ca* +H 5 a i-OH) + Cu = (=Si0),Cu +.2H* Ligand exchange and direct reaction Solid surface exchange with coordinating anions, A’-, results in the release of OH” from the surface or coor- dinating anions directly reacting with the solid surface: =McOH + Ay ee =MeAC# 4 OHH (8) 2(=Me-OH) + AN & (Me), ACH) + 20H 0) Me + A (10) for example, ~ + OH Fe)-OPO; + 20H™ ay Temary surface complex formation ‘The metal complex formed on mineral surfaces may acquire a further ligand (.e., surfactant ions) to form ‘a ternary complex. MeOH + M™ +L 2 =Me-OM-LI* 4 HY (12) MeOH + L> + Mt = =Me-L-M" + OHD (13) Seay| | | | | es) am for example, =Si-OH + Cat + RCOO =Si-O-Ca{OOCR) + Ht A-OH + SiFs + RNH3* ALSiFe--H)NR + OH (1a) Electrochemical reaction The flotation of sulfide minerals by xanthates is strongly related to an electrochemical mechanism. Sul- fides, being electronic conduetors, can act as a source for electrons and hence can support electrode reactions at the surface.""*!") For example, the reaetion of the oxidation of a xanthate to the dixanthogen takes place via two separate and simultaneous electrode processes. ‘The anodic oxidation reaction is expressed as 2ROCSS- = (ROCSS), + 26 (1s) and the cathodic reaction, the reduetion of oxygen, I 2 + 2H + 2e — H:0 (16) As a result, the sulfide surface can catalyze the formation of dixanthogen, which is one of the major species responsible for the Rotation of sulfide minerals. ‘The chemisorption and reaction of xanthate on heavy metal sulfide surfaces involve the electrochemi- cal reactions, For example, POS + 2ROCSS- + Pb(ROCSS), + $ + % (17) and the cathodic reduction of oxygen, reaction.!" CLASSIFICATION OF MINERALS AND FLOTATION REAGENTS Solids can be classified into two categories, namely, high-energy and low-energy surfaces. The surface free energy or, surface tension of water at 25°C is 72.8mJ/m*; solids that have a surface energy higher than water are called hydrophilic solids, whereas those having surface free enetgy lower than water are called hydrophobic solids. Low surface free energy solids are not readily wetted by water Minerals can also be classified into nonpolar and polar types based on their surface hydrophobic Ores, Flotation of Properties. Nonpolar minerals such as tale, sulfur, coal, graphite, diamond, and molybdenite are hydrophobic solids that ate characterized by covalent and weak molecular bonds. The contact angles of water on these solids surfaces range from 60° to 90°; consequently. they possess natural floatability Minerals with strong covalent and ionic bonding belong to polar types with surface energies ranging from 200 t0 $000mJ/m? and are readily wetted by water!" The polar minerals react strongly with water and are naturally hydrophilic. ‘There are various types of mineral classification, Table 2 shows that the most common classification is based on flotation properties of minerals, briefly described below}! © Nonpolar minerals—This group possesses poor wettability by water and high hydrophobicity Flotation of these minerals could be achieved by using frothers only, © Sulfide minerals—This group includes minerals of nonferrous metals such as Cu, Pb, Zn, He, Sb, etc. Thio collectors such as xanthate are most effective for floating these minerals, * Oxide minerals—This group of minerals responds to floatability when anionic coltectors such a alkyl carboxylate, sulfate, and phosphonic acids are used * Oxidized minerals of nonferrous metals—This group of minerals is composed of carbonates and sulfates of Cu, Pb, and Zn derived from oxygenated acids. These minerals are usually floated by first sulfidizing the mineral surface with sodium sulfide solution followed by addition of xanthate collec- tors. These minerals can also be floated using fatty acids /soaps. © Silicate minerats—For these minerals, both anionic and cationic collectors can be used. However, the flotation of many of these minerals with an anionic collector is achieved by adding activating cations such as calcium and magnesium ions in suspension Prior to the collector addition * Salt-type minerals—This group consists of both insoluble and soluble salt minerals, The insoluble salt minerals are the carbonates, sulfates, phos- phates, and others of alkaline earths such as Ca, Mg, Sr, and Ba. They are readily floated by fatty acids. Soluble salt minerals sylvite and halite are floated in their saturated solution using alkyl amine or carboxylate collectors. Naturally occurring minerals usually do not possess enough natural floatability. Accordingly, various flotation reagents classified as collector, frothers, and regulators ate used to achieve satisfactory separation of the minerals. 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Hal (Ors, Hott upc 1094 4H 109618610 (s1osarp) poe 165019 uw) nuns soypuogins ui] L iowa) sso] (KeUAAXOGHED und send -unsap “y>se1S aroudsoudleyun cumspos seamdsoydsjod tarypos, (2085) sveurouys aunusstiog, (NO) 294 (sen) apuins wumipos Cols'en) avons wmpos, ‘seaneAnap soyoory ype oqusny pu smuuey, somnti20) uunap “pans pean stuBRsoUr Jo SHES usfonyu dumequos qwersryNg Wvoupxy BuruseG09 1 spunodioo sy98, anppojou Wy PUP SOUP, ssomponyTE meyT ) 6 flotation reagents and their applications. Collectors provide a hydrophobicity on the mineral surface to enhance mincral-air bubble attachment. Frothers help produce a froth of adequate stability to allow the removal of minerals by air bubbies. Regulators or ‘modifiers are used to adjust the pH of the pulp and/ or alter the mineral reactivity with the collector so as to control the flotation process. Flotation reagents are the most important and represent the flexible variables of mineral-chemical interaction in the flotation process. They determine the floatability of minerals and the effectiveness of their separation. Major advances in flotation have been due to the development of new flotation reagents, COLLECTORS Collectors are reagents that selectively adsorb on the ‘mineral surface and make them hydrophobic so as to improve their attachment to air bubbles. Taggart, Taylor, and Knoll in 1930 were the first to point out that water-soluble collectors contain both a polar and nonpolar group"! They postulated that the polar group attaches to the mineral surface and the nonpolar group orients into the pulp. The mineral surface acts nonpolar in nature and becomes hydrophobic. The col s a link between the mineral sur faces and air bubbles. The displacement of water by (Ores, Flotation of air from @ mineral surface coated by a collector is the fundamental condition for flotation. ‘Surface Energy and Collector Adsorption According 10 Fowkes, the surface energy or surface tension, 7, can be divided into two parts: the part due to Londoa-van der Waals dispersion energy. yf, and the part due to more specific chemical energies (ee. hydrogen bonding, metalic bonds in metas, pi slec tron interactions in aromatic solvents).° For water, the surface encray is composed of dispersion eneray, 2(H0), and hydrogen bond energy, 4(H20): AT28mI/m?) = 7821.8 mf} 4 54(51 mJ/m?) (is) For mercury, Hg(I), the surface cnergy is composed of dispersion energy, 74(He), and metallic bond enersy rw(He). For liquid hydrocarbons the surface energy i almost entirely due to the dispersion enerey =o (19) ‘The adsorption of surfactants on the mineral sur face reduces the surface free energy of the mineral. Extensive studies have been conducted in this regard. Table 4 gives the surface free energy and dispersion energy of some liquids and solids coated with or Tabled Surface eneray. 7. and surface dispersion enerey. 7 of some liquids and solids wih or without contact with surfactants Surfactant 7A, mill reated Materials, Formula y (enJim?) (milf?) x 10% motetiter) ‘with surfactant) Liquids Water ns 218 Mercury aa 200 n-Hexane 184 184 n-Decane no Bo Benzene 289 ay Solids Paraffin wax 25 25 Silver = 74 Lead = 99 Rutile a 13 Fluorite 120 = Oleic acid 85 2s Goethite 1600 7 Oteie acid 15 3s Barite 350 - Oleic acid a5 285 Sidertte - Oleic acid 13 37 Siderite 7 7 Sodium dodecy! sulfate 30 38 Siderite 7 Sodium dodecyl sulfonate 30 37 Quartz 350 13 Dodecyl ammonium chloride 50 4s Quartz 330 13 Dodeey! ammonium chloride 110 285 Quartz 330 23 Oleic acid and 10pm Cah, 11.0 2 Galena a Amyl xanthate 85 38 From RAYOres, Flotation of without surfactants!!!) The hydrocarbon materials have a surface free energy lower than 72mJ/m*, and they are hydrophobic in nature. ‘Most minerals such as quartz and goethite have sur- face free energies much higher than that of water and are hydrophilic in nature. Upon adsorption of surfac- tant, the surface energy of minerals with high surface nergy is significantly reduced. For example, the dis- persion component of surface free energy of, quartz decreases from 123mn/m® to only 28.5mJ/m? in the presence of dodecyl ammonium chloride. For the solids coated with surfactants, the surface property ‘becomes close to that of hydrocarbons, and the surface energy may be approximated by dispersion energy. Accordingly, the surfactant-coated minerals shown in Table 4 have very low surface energies, and their sur: {aes become hydrophobic. Collectors for Sulfide Minerals Table $ shows the structures of commonly used sulfy- dryl collectors for sulfide minerals, Xanthate collectors are the most popular and powerful collectors used for ‘most of the sulfide minerals. Dithiophosphates are not used as widely and effectively as xanthates, and they are relatively weaker collectors!!! However, dithio- phosphates provide selective separation of copper from lead sulfides and of lead from zinc sulfides at controlled dosages. Both xanthates and dithiophosphates selec- tively adsorb on sulfide minerals but not on nonsulfide ‘minerals. Xanthate is generally adsorbed on the sulfide mineral surface and reacts with metal ions to form hydrophobic metal xanthates. The solubility of metal xanthates of copper, lead, silver, and mercury is very ow, but that of zine and iron is much higher. There: fore, in alkaline solution, xanthate exhibits lower col- lection efficiency for sphalerite and pyrite. However, the flotation of sphalerite can be greatly improved in the presence of a small amount of copper ions. Pyrite floats very well in acidic pH ranges, at which dixan- thogen, an oxidation product of xanthate, is formed fon the surface, which is responsible for its high Aloatability.??) It has been established by numerous studies that moderate oxidation of the sulfide surface plays a very imporiant role for the collection and interaction of sulfide minerals by xanthate. The formation and presence of elemental sulfur also contributed to the hydrophobicity. Strong oxidation and long exposure to the ait may destroy the foatability of sulfide minerals, Due to the importance of oxidation, the electrochemical reaction of sulfide minerals and their interaction with xamthate hnave been extensively studied. "61724 on Collectors for Nonsulfide Minerals Table 6 lists the commonly used collectors for non- sulfide minerals and their structures. Fatty acid and carboxylate alkali soaps are most commonly used as joint flotation collectors, use for floating nonsultide minerals. Among fatty acids, oleic acid and its salt are the most widely used collectors. Others with hydrocarbon chain length of Crz to Cig (saturated and unsaturated) include stearic, palmitic, lauric, and linoleic acids and their soaps. Tall oil, which is a mixture of fatty acids and resin acids, is a by product in the kraft process of wood pulping and is widely used in phosphate flotation, Fatty acid and carboxylate can react with most polyvalent metal ions such as Ca?*, Mg", Sr", Mn", AL", Fe'', and Fe'* to form insoluble products. There- fore, they can float most nonsulfides and sulfides Most alkyl sulfate and sulfonate reagents used in flotation are derived from petroleum distillates. They are normally used as collectors for some metal oxides such as hematite and alumina, and for the separation of salttype minerals such as barite and sheelite.!"" Alkyl sulfates and sulfonates have not been used as Widely and effectively as fatty acids, Cationic surfactants such as amines have been extensively used in the flotation of silicates, potash, and some oxides. The cationic surfactants are usually used as salts of hydrochloric or acetic acids. It is believed that amines adsorb on the mineral surface mainly through the electrostatic attraction between the positively charged polar part and the charge in the eleetrical double layer of the minerals. Cationic surfactants are very sensitive to the solution pH and slimes (particles of less than 10m size), To obtain good separation, the pulp must be deslimed before adding the cationic surfactants.” FROTHERS others are reagents used to provide a stable froth just sufficient to facilitate the attachment of floated ‘minerals to air bubble and the their removal from flotation cells. Ideal frothers should serve only as @ foaming chemical and not affect the collector-mineral interaction?” In reality, however, one surfactant would act both as a collector and as a frother, For example, collectors such as fatty acid soaps are also powerful frothers. ‘Similar to collectors, frothers are generally hetcro- polar surfactants, which adsorb on the water-air inter- face to reduce the interfacial energy. In the flotation pulp, the polar part of frothers orients toward the water, and nonpolar part orients toward the air so as to stabilize the air bubbles. Frothers usually have resee Se rr aE a EEE Peres) an ‘Table § Common sulfydeyl collectors for sulfide minerals Ores, Flotation of Name Formola ‘Structure Wentification Alkyl dithiocarbonates (wanthates) R=G0G Diatkyl dithioptiosphates s R= Crocs Dialkyl thionocarbamates toCs Dali dithiocarbamate R Mercaptobenzothiazole Mecaptans ROSH certain solubility in the water. Alcohols are the most widely used frothers because they have practically no collecting properties. Besides alcohols, alkyl carboxy: late, sulfates, sulfonates, and amines are also good frothers. However, these frothers with collecting powers sometimes reduce the selectivity of the desired ‘mineral flotation.**2" Synthetic frothers are now being widely used in flotation, which include alcohols and nonionic surfac~ tants. Their composition is more stable than natural produets, and their performance can be easily co trolled. Among them, methyl isobutyl carbinol (MIBC) js the most common frother. Nonionie surfactants used ‘as frothers include polyglycols (H(OCH3H),OH or R= Cyto Cr H(OCHH,),OH}, polyglycol ether [R(OC3H,).OH], and ethylene and propylene copolymers.*7! Pine oil obtained from wood has terpineol, (CoH OH), as the major component and is also used as a frother. REGULATORS Regulators or modifiers are widely used t0 modify or control the hydrophobie/hydrophilic and surface charge properties of the minerals. The regulators either tenhance or reduce the interaction of collectors with the mineral surface. Regulators can be classified as pH modifiers, activators, and depressants. The regulatorOres, Fl Table 6 Common oxyhydryl collectors for nonsulfide minerals 439 Name Formula Structure idenication Alkyl carboxylate ° = C410 Cap Ona? Ps lk sulfonate ° = Cito Cin ¢ R— i 0 Nat cS) ° Atk slate = Cpu Alkyl phosphate = Cato R—0—Pp— 0 —— nat Nev Alkyl hydroxamate = C.t0C owe Primary amine = C0 Cis Secondary amine R— NIT vo = Cyto Cis aC, to Cy (Contned)S vi 2 430 ‘Table 6 Common oxyhydryl collectors for nonsulfide minerals (Continued } Name Formula ~"Sirocture Mentification Tertiary amine R= Cyto Cu, RC OC RNY cr Quaternary amine R R= Cpl Cy, R=C) to Cr R Set —a R Alkyl pyridinium sale actions consist of pH control of the flotation system, adjusting the charge density at the mineral-water inter- face, and regulating the oxidation states of ion species in solution and on the surface, the concentration of metallic ions, ete. pH Modifiers pH modifiers include hydrochloric acid, sulfuric aci, sodium hydroxide, sodium carbonate or soda ash (NaCO3), lime [Ca(OH),], ete. The control of flotation system pH is often of paramount significance. In prac- tice, the separation selectivity is frequently dependent fon a delicate balance between the reagent and pH. pH modifiers affects many aspects of the flotation sys- tem: 1) the surfaces of the minerals such as their hydration, charge density, zeta potential, ete; 2) solu- bility and ionization of # surfactant and its reaction with mineral surface; 3) the concentration of inorganic ions; and 4) the electrochemical or redox potentials. By carefully adjusting pH and collector concentration, the selectivity of flotation can be significantly improved, Activators Activators are generally inorganic cations or anions that alter the surface of a mineral so that it can more readily adsorb a collector and float. The activator ions Cito Ce usually carry opposite charges to that of the collector. When an anionic collector is used, polyvalent metal ions such as Cu?*, Pb°*, Zn?*, Ca’*, Ma, Al", and Fe" usually serves us activators. Similarly, silicate and phosphate ions can act as activators with the cationic quaternary ammonium reagents. Anionic ions such as and F- also serve as activators for certain minerals ‘The most widely used activator is copper sulfate. Addition of copper sulfate is added to make the flotation of sphaterite (ZnS) by ethyl xanthate much casier, which otherwise does not float well. This is because the zine xanthate formed has relatively high solubility under normal flotation conditions and can- not provide sufficient hydrophobicity for flotation. Addition of a small amount of copper sulfate (CuSO, -5H;0) significantly activates the flotation of sphalerite due to the formation of copper sulfide on the surface through the following reaction!"?#"""! ZiS.usoce + Cu™ Zn (20) CuSwrtce = Because copper xanthate is insoluble, the reaction of xanthate with the copper sulfide (CuS) film renders the sphaterite surface hydrophobic. “The other important example of activation is the sulfdization of oxidized minerals of nonferrous metals. ‘The flotation of these minerals with xanthates is poor and requires huge amount of collectors because the metal ions dissolved from the mineral surface mustOrs, Flotation of, be precipitated as metal xanthate before the collector react with the surface. However, the addition of sodium sulfide (Nax8) or sodium hydrosulfide (NaHS) to these mineral suspensions followed by xanthate addition improves their flotation significantly. For example, in the sulfidization of cerusite with sodium sulfide, whe following reaction take place at the surface!” PbCOsurice + NaaS = PbSvartce + NaxCOs au) A lead sulfide coating is formed on the surface first, then xanthates can easily adsorb thereafter. The amount of the sodium sulfide must be strictly con- trolled, and, if overdosed, it will depress activated oxi dized minerals, Other examples include activation of quartz (SiO2) by Ca", Mg?", Fe™’, and AP* as well as the activation of stibnite (Sb3S3)" Depressants Depressants are reagents used to improve the selective separation of minerals by rendering certain minerals hydrophilic or nonfloatable. Depressants are either inorganic or organic chemicals that prevent the adsorption of collectors onto some minerals. Many of these depressants are used in the flotation process. ‘The most widely used ones are discussed below. + Sodium silicate is widely used as a depressant ot dispersant in the flotation of nonsulfide minerals. Its also called water glass and has a composition expressed by mNaxO-nSiO2, The ratio n/m is referred to as the modulus of sodium silicate. The sodium silicate frequently used in Rotation has a modules varying from 2.2 to 3.0."!In aqueous solu- tion, silicates have three major species: SiOH}. (uncharged silica gel) at pH < 94, (SiO(OH)5] at pH > 9.4, and (SiOMOH),7] at pH > 1268"! ‘The latter two negatively charged species function as the major species for the depression of silica oxide, and salt minerals!" The selectivity of sodium silicate can be increased by combined use with sodium carbonate and polyvalent cations in the pulp. For example, a combined use of sodium silicate with AI”? is used for the separation of fuor- ite and calcite. ‘© Zinc sul fate is used as a depressant for sphalerite in the selective flotation of lead-zine and copper-zine cores. Its depressing action works only in alkaline pH. This could be duc to: 1) Zn(OH)2 precipitates or adsorbs on the sphalerite surface and prevents xanthate absorption and 2) Zn(OH); oceludes on copper ions in the pulp and Keeps them from adsorbing on the sphalerite surface!” + Sodium cyanide contains anion, CN, and is an effective depressant in the selective separation of galena {com sphalerite and pyrite or of pyrite from Sphalerite or of copper minerals from sphalerite and pyrite, To use eyanide, pulp must be maintained in the alkaline pH. Because cyanide ions can form extremely stable complexes with many heavy imetals, this interaction makes cyanide a very useful seagent in the flotation of nonferrous metal ore. Cyanide is usually used to depress sphalerite, pyrite, and certain copper minerals." # Lime is the most widely used depressant for pyrite ‘The strong depression of pyrite by lime is elated to the formation of a mixed film of Fe(OH)s, FcOOH, CaSO, and CaCO om the pyrite surface ‘+ Sulfur dioxide is one of the most versatile reagents for sulfide ores. It is used as a galena depressant in copper-lead separation, 11 has the advantage over toxic cyanide in sphalerite depression and exhibits litle depression on copper minerals. Potassium dichromate is used to depress galena in the copper-lead separation. The depression is due to the formation of @ hydrophilic film of PbCrOx con the galena surface + Sodium polyphosphates include orthophosphate, pyrophosphate. tripolyphosphate, metaphosphate, etc. They can form stable complexes with poly. valent metal ions and ean be used as a depressant for iron-containing minerals Cyclic hexa- metaphosphate is widely used as @ depressant and dispersant for slimes and clay minerals. FACTORS AFFECTING FLOTATION ‘The efficiency and performance of flotation separation are affected by many factors such as pH, temperature, mineral liberation, etc. Particle size—The selective and efficient separation can be applied to only those mineral mixtures in which mineral particles are liberated from each other, For ores, both crushing and grinding are employed to reduce the ore particle to the size at which valuable minerals are sufficiently liberated from other ganguc minerals. Fig. 6 is a typical example showing the effect of particle size on otation of the same mineral, The optimum particle size for flotation is 20 to 150 4m. The particle sizes suitable for froth flotation range from 10 to 300m" The particles below 10um are usually called slimes, and flotation becomes much less effec: tive for slimes. SayeS z i) 42 100 40 Flotation recovery (%) 2 © 50 100150200250 300 Size (mm) Fig. 6 Flotability of a typical mineral of various sizes, ‘© Slimes—Slimes may worsen the selectivity of collec tor reaction with desired minerals, especially in the flotation of nonsulfide minerais using cationic sur- factants. The slimes produced during the grinding. process also exhibit some degree of depressing action because it may coat the minerals, prevent collector adsorption, and depress their flotation, Especially in the flotation of nonsulfide minerals, slimes are usually removed before flotation reagents are added because they possess very large specific surface area and consume large quantities of collectors. ‘© Temperanure—Temperature plays an important role in determining the kinetics and extent of sur- face reaction between mineral and reagents. For example, in the flotation of fluorite using fatty acids, elevated temperature (75° to 85°C) is needed to achieve the desired selectivity of separation from silica and calcite, ‘© Solurion plt—This is probably the most important factor in controlling the flotation process. Because most minerals and flotation reagent ionize in water, the slight pH variations can change the properties of the minerals and reagents as well as their interac- tion. To obtain selective separation, pulp pH needs to be carefully controlled. * Pulp densiy—High pulp densities generally increase the recovery of floated minerals and reduce the concentrate grade. It also affects the capacity of the flotation machine. * Water chemistry—Apart from differences in ore, differences in the composition of water have to be taken into account. It is well known that the effect of calcium and magnesium ions on flotation of non- sulfide minerals is profound. Recirculation of water within various sections of a flotation plant will affect the plant performance. (Ores, Flotation of Rougher Final Feed tailings tatioge Roughers Scavenger | Roughor ‘Scavenger concentrate concentrate Micaings ‘Gleanere — “Gleaner talings Final * concentrate Fig. 7 A. typical roughers-scavengers cleaners. Hotation circuit ‘* Flotation circuit—Commercial flotation is cartied ‘out in flotation cells arranged in series, Fig. 7 shows typical roughers-cleaners-scavengers flowsheet used in flotation plants, Flotation pulp enters the first flotation cells or roughers where valuable minerals are floated out as rougher concentrate and the hydrophilic minerals called rougher tailing go to next stage. Rougher tailings are further floated in the last flotation cells or scavengers in the flowsheet to inerease the recovery of the desired minerals. Rougher concentrates are refloated in cleaners to produce a high-grade coneentrate. In jeneral, scavenger concentrates and cleaner tailings, which contain middling particles, are often recircu- lated to the head of the flowsheet. Due to the complexity of the ores, different types of flotation circuits are used in practice. Suitable flotation cit- cuits are designed based on both the properties of res and the (ypes of flotation reagents used FLOTATION SCHEME ‘The selection of optimal flotation scheme is: mainly determined by the properties of minerals present in an ore, which may differ greatly forthe very similar types of ores from different geographic locations. ‘The most basie scheme for three major mineral classes is abbreviated in Table 7. For specific ore types, ‘Table 7 Basie otation scheme of major types of minerals Flotation reagents als Frother Regulator Nonpolar ‘Aleohot Sulfide Xanthate Pine oil, Lime, eyanide, MIBC copper sulfate Nonsulfide Oleic acid Alcohol Soda ash and sodium silicatefollowing paragraphs. Lead-Zine Ores Lead and zine minerals are usually associated in most ores, The main lead minerals present include galena (PbS), cerussite (PBCO,), and anglesite (PbSO3). The main zine minerals are composed of sphalerite (ZnS), marmatite {(Zn, Fe)S}, smithsonite (2nCO3), and zin- cite (ZnO), Pyrite and pyrrhotite are the frequently encountered sulfide-gangue minerals, whereas calcite, dolomite, quartz, oxides, and silicates form nonsulfide gangue minerals. The Pb-Zn ores treated have a com- bined grade ranging from 3 to 20%, Galena is floated between pH 8 and 10 along with any copper sulfide that may be present using xanthates or dithiophos- phates as collectors and alcohols as a frothers. Sodium sulfite and/or ZnSO, is used in the flotation to depress zinc minerals, After galena is removed, lime is added 0 increase the pH to 11 to 12 for depressing iron sulfides, and CuSO,-$H30 is added to activate sphalerite and marmatite flotation. A Pb concentrate containing higher than 55% Pb and a Zn concentrate containing 50% or higher are the target of flotation. Copper Ores ‘The main copper sulfide minerals are chalcopyrite (CaFeS;), chaleocite (Cus), covellite (CuS), and bor- nite (CusFeS,). The oxidized copper minerals include cuprite (Cu;0), malachite [2CuCOs-CulOH)], and azurite [2CuCOy-Cu(OH);]. The major associated minerals are iron sulfides composed of pyrite and pyrthotite. If the iron sulfide content is not too high, copper sulfide minerals are readily floated using a small amount of xanthate or isopropyl ethyl thionocarba- mate. However, if iron sulfide content is high in the ore, lime (CaO) is generally added to raise pH to 10 to 12 together with conditioning of the slurry with air for depressing iron sulfides. The most difficult sul- fide flotation separation is Cu-Pb-Zn-Fe ores. This is because the copper ions produced in the slurry ‘may activate zine and iron sulfide, making the separa~ tion extremely difficult. In a concentrated product, 25% or higher Cu content is usually required if chaleo- pyrite is the major mineral. Oxidized Minerals of Nonferrous Metals The most common oxidized sulfide minerals include cerussite (PbCOs), anglesite (PbSO,), malachite [CuCOs-Cu(OH);], azurite _ 2CuCOs-Cu(OH)a, smithsonite (ZnCO,), and willemite (Zn,Si0,). Cerus- on site, malachite, and azurite can be easily sutfidized by [NaS and subsequently floated using xanthates!) Oxidized zine minerals cannot be effectively floated using sulfidization. They are usually treated using cationic amine or §-hydroxyquinoline as. collector land pine oil as frother in the presence of regulating agents such as NazCOj, Na;SiO., Na»SOs, and NaCN to disperse/depress slime or very fine particles. Nonsulfide Oxides ‘Aluminum, tin, manganese, and magnetic iron oxide minerals are gencrally recovered by nonflotation tech: niques such as gravity, magnetic and electrostatic separations. For flotation of cassiterite (SnO2) alkyl carboxylates, alkyl sulfates, ulkyl phosphonic acids, and alkyl arsonic acids have been used as collectors."4 Nonmagnetic oxides such as hematite and taconite, often associated with quartz and silicates, can be upgraded by flotation using carboxylic acids and pet roleum sulfonates. Cationic amines are occasionally used to float silicate minerals Silicate Minerals Oxide and silicate minerals can be floated using anioni collectors, such as fatty acids/soaps, sulfonates, sulfates, hydroxamate, etc. Both cationic and anionic collectors are used in the flotation of silicate minerals, with fluoride ion as the most active modifying agent." Fluorides in acidic medium can activate some silicates such as beryl and feldspars, which can then be foated using cationic collectors, whereas quartz will float under these conditions!" Typical silicate flotation products include quartz for glass man ufacture, feldspar for ceramic use, and spodumene for production of Li!! When cationic collectors are used, slimes should be removed before flotation because slimes will adsorbs most of the collectors. Insoluble Salts The main insoluble salt minerals consist of fluorite (CaF.), scheelite (CaWO,), barte (BaSO.), and phos- phates [Cas(PO4)(F, Cl, OH)]. Fluorite and barite are tsually floated with oleic or linoleic acids as eollector in the presence of regulating agents such as Na,COs, NasSiOs, tannic acid, oF quebracho (used to depress calcite).! A temperature of 75° to 80°C is generally employed to increase the separation selectivity of fuor- ite from quartz and calcite. For phosphate ores, the separation of apatite from calcite and dolomite is very important but also difficult because fatty acids can float all these mineruls. Reverse flotation is often peedEe yTI) ou employed in which phosphate minerals are depressed by orthophophate or fluorosilicate, whereas calcite and dolomite are removed using inexpensive tall oil fatty acid collectors. Soluble Salts Potassium salts are an important source of fertilizer (potash). Potash deposit is a primary source of sylvite (KCI) and halite (NaCl), which also contains carnallite, KCI-MgCly-6H;0, MgSO,-KCI3H30, camallite, kainite, MgSO,: KCI-3H,0, etc. Sylvite (KCI) can be separated from halite (NaCl) using long-chain amines such as dodeey] ammonium salts in Kel or Nacl saturated solutions." Saturated brine solution repre- sents 7 to 10-moles/liter concentrations of electrolytes (K* Nav, C1", SOF, etc.) Selective flotation of sylvite in a saturated brine solution is preceded by removal of clays and slimes with hydrocyclones With ores contsining sylvinite and carnallite, the selective flotation of sylvite is conducted using alkyl amines (12 to 15 carbons) or sulfonates. For halite flotation alkyl carboxylates of heavy metal ions and a nonpolar oil Naturally Hydrophobic Minerals A number of minerals exhibit naturally hydrophobic Properties. The minerals may be either organic, such as coals, graphite, or bitumen, or inorganic, stich as sulfur, tale, molybdenite, and diamond, In floating such minerals usuaily only a frother such as pine oi is required. The common collectors such as soap and xanthate do not exercise any significant coliecting func tion toward such minerals.” Reagents that depress gangue minerals are helpful for the flotation, which include starch, casein, and sodium silicates. CONCLUSIONS ‘The application of various synthetic surfactants to the flotation of ores is a promising area, A large num- ber of synthetic surfactants are available in the market, and being used in other industries. The polymeric surfactants with various structures ean be synthesized at will, which provides flotation engineers much flexibility to control the selective separation of miner- als, With the use of these chemicals. it is postulated that many difficult separation problems may be solved readily. Although many chemicals used in a conven- tional fotation process are very effective, they may be toxic and cause pollution to the environment. ‘The development of environmentally benign chemicals Ores, Flotation of for flotation should also be emphasized. The mineral fines generated from grinding ores are difficult to ‘reat with common flotation reagents. Before they can be floated, it is necessary to selectively floceulate them to form a particle size large enough for efficient flotation. The development of various kinds of poly mers used for the selective flocculation of mineral fines will allow us to recover and utilize more mineral resources. REFERENCES: 1. Somasundaran, P. Interfacial chemistry of particulate Rotation, AICHE Symp. Ser. 1978, 77 (150), 2. 2 Gaudin. AM. Floraiion; McGraw-Hill: New York, 1957, 3. Sutherland. K.L: Wark, LW. Principles af Flotation Australian [M.M.: Melbourne, 1955 4. Fuctstenau, M.C. 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