Minerals Engineering 15 (2002) 139 155 www.elsevier.

com/locate/mine

Overview of otation as a wastewater treatment technique

J. Rubio
a

a,*

, M.L. Souza , R.W. Smith

Departamento de Engenharia de Minas-PPGEM, Laboratorio de Tecnologia Mineral e Ambiental, Universidade Federal do Rio Grande do Sul, Av. Osvaldo Aranha 99/512, 90035-190, Porto Alegre, RS, Brazil b Metallurgical and Materials Engineering, Mackay School of Mines, University of Nevada-Reno, USA Received 7 October 2001; accepted 12 December 2001

Abstract The treatment of aqueous or oily euents is one of thepowders, most serious environmental issues by and the some minerals metallurgy industries. Main pollutants are is residual reagents, chemicals, ions, oils, faced organic mayand be valuable (Au, Pt, Ag). The use of otation showing a great potential due to available. the metal high throughput of modern equipment, low sludge generation and the high eciency of the separation schemes already It is concluded that this process will be soon incorporated as a technology in the minerals industry to treat these wastewaters and, when possible, to recycle process water and materials. In this paper, the use of otation environmental applications is fully discussed. Examples of promising techniques and are reported andin some recent Science advances inAll the treatment of heavy metal containing emerging waters and emulsied oil devices wastes are discussed. 2002 Elsevier Ltd. rights reserved.
Keywords: Flotation machines; Pollution; Flocculation; Flotation bubbles; Environmental; Wasteprocessing

1. Introduction 1.1. Background Process waters exiting from mining, petroleum and metallurgical operations are contaminated widespread throughout the world and can become by various chemicals, pollu- tants. These substances include powders, metal ions, oils, organic and others, sometimes rendering thedangerous water useless for recycling as process water, often for the environment, and sometimes causing losses of valuable materials (Galvin et al., 1994). Sources of water contamination may be found at mines, mills, o shore platforms, processing plants, tailing ponds, etc. ^as and (Smith, Villas1996). Bo Barreto, 1996; Warhurst1996; and Bridge, Sometimes, due to process their chemical complexity and/or volume, these cannot be treated economically evenFurther, in waters cases where they contain valuable materials. when organic uids are discharged,
*

Corresponding author. Tel.: +55-51-3316-3540; fax: +55-51-33163530. E-mail addresses: jrubio@vortex.ufrgs.br; http://www.lapes.ufrgs. br/Laboratorios/ltm/ltm.html (J. Rubio), smithrw@scs.unr.edu (R.W. Smith).

the oil/water separation becomes and dicult especially when the oil is emulsied, worse when the are mean droplet size is (Beeby small and or if the emulsions chemically stabilized Nicol, 1993). Smithand (1996) showed in from detailmineral characteristics of liquid solid wastes processing plants. Various techniques and technologies available were discussed and the quality and quantity of typical pollutants were listed. Thus, current andwith future technologies will eventually have to deal areas such as: process water treatment and recycling (reuse); removal and/or recovery of ions: heavy and/or precious metals, anions, residual organic chemicals, complexes or chelates; cyanide and arsenic emission control, recovery or destruction; oil spills separation (including recovery of solvent extraction liquors); acid mine waters containing considerable amounts of harmful base metals such as nickel, copper, zinc, lead in addition to ferrous iron and sulfate; control and removal of residual chemical reagents such as frothers, otation collectors and modiers (activators or depressing agents, pH regulators); separation of various wasted plastics; radioactive control in aqueous euents and soils.

0892-6875/02/$ see front Elsevier reserved. PII: S-0 89 2- 6 matter 8 7 5 ( 0 1 2002 )002 1 6 - 3 Science Ltd. All rights

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J. Rubio et al. / Minerals Engineering 15 (2002) 139155

1.2. Conventional treatment processes The conventional process ions for is treating liquid euents containing metals precipitation aggregation (coagulation/occulation)-settling as hydroxides or insoluble salts. However, this method, from a technical certain limitations, namely: point of view, presents the formation of metal hydroxide is ineective in di- lute metal bearing euents; the hydroxo precipitate tends to re-dissolve, m depend ing on the metal, via the reaction MOH OH OH
m

1.4. Flotation process in wastewater treatment Flotation had as its beginning in mineral (ore) processing and such has been used for a using long time in solid/ solid separation applications stable froths to selectively separate dierent minerals from each ofother (Kitchener, 1985). Regarding applications otation in wastewater and domestic sewage treatment, civil and chemical engineers have used dissolved air otation (DAF) for a number years (Hooper, 1945). Main applications haveof been in the removal of the solids, ions, macromolecules and bers, and other materials from water (Matis, 1995; Mavros and Matis, 1992; Lemlich, 1972; Clarke and Wilson, 1983; Zabel, 1992). More, otation is also practiced in other elds (Kitchener, 1985; Roe, 1983; Cundeva and Stalov, 1997; Kim et al., 1999; Schugerl, 2000), such as: analytical chemistry; protein separation; treatment of spent photography liquors; odor removal; plastics separation and recycling; harvesting or removal of algae; deinking of printed paper; separation or harvesting of micro-organisms; removal of sulfur dyes, seed hulls, serum, resins and rubber, impurities in cane sugar; and clarication of fruit juices. The main dierences between conventional otation of ores and otation applied to water treatment are the following: The method of producing the gas bubbles in order to generate micro, medium or macro-bubbles. It is now widely accepted that medium size and large bubble diameters (3001500 lm) are optimal for otation of minerals (nes and coarse particles). Yet, conventional otation devices do not generate a sucient number of bubbles smaller than 600 lm. Main uses of micro-bubbles (<100 lm) is in applications of otation to solid/liquid or liquid/liquid separation. Thus, the distinguishing feature between conventional mineral otation and otation in waste treatment is that, where extremely small (or even colloidal) particles have to be oated, microbubbles are required. Because the species oating are usually aggregated colloids rather than dispersed ones, high shear rates

the pH of minimum solubility of hydroxides is dierent for the various metals present. For example, the minimum solubility for cupric hydroxide occurs at a pH value around 9.5 while for cadmium hydroxide it occurs at pH around 11; precipitation of metals becomes incomplete when complexing or chelating agents are present; volumes of sludge formed are too large and with a high water content; ltration may be dicult as a result of the precipitates neness, and; due to kinetic and scale problems, the treatment by coagulation and settling of euent ow-rates of about 24 m3 s 1 is very dicult and costly. This constitutes a great challenge for the modern mining industry. 1.3. Flotation processes The potential use of owing otation has shown to have a great to the high throughput and eciency of modern equipment now available (Zabel, 1992; Matis, 1995; Rubio et al., 1996; Rubio, 1998a,b; Voronin and Dibrov, 1999; Parekh and Miller, 1999). Other advantages of such otation are the selective recovery ofare valuable ions as gold, palladium, silver (which also pollutants), the new separation schemes now available and the low sludge generation in this pro- cess. paper summarizes general in This environmental applications and features is aimed of to:otation treatshowment the technique potential of otation as a wastewater and present some advances; depresent vices; novel separation concepts and otation otaserve tion as aactivities bridgebeing providing information on conducted various engineeringmining elds as well as inindustry. in the and metallurgical It is believed that a cross ex- change of otation experience in mineral otation and water and euent treatment should lead toinnew and improved procedures for industry waste treatment.

nm

must be avoided to obviate destruction of the fragile aggregates. This is important in the clarication of efuents and introduces distinct problems not previously encountered in mineral otation. The solids content present in the pulp system, whether diluted or not. A limiting feature of bubbles is the lifting power or carrying capacity. Microbubbles do not oat dense and big particles, especially at high solids content (45%, w/w).

J. Rubio et al. / Minerals Engineering 15 (2002) 139155

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 mineral The type processing of separation: and solid/solid/liquid in solid/liquid1/liquid2or liquid/liquid solid/liquid, in water treatment. stable In mineral otation itsurface is necessary produce a froth at theto free of the to otation cell. In applications wastewater treatment an stable foam is not required. In mineral otation, the overall process is economically attractive. In environmental application, usually otation means an extra cost. Other dierences are summarized in Table 1 comparing, among others, bubbles characteristics in dierent otation devices. Flotation technology can be incorporated in mining and industrial wastewater-treatment schemes in the following ways: as a unit process (ancillary or main process) to remove contaminants which are not separated by other means. Depending on performance (water quality), process water can be adequately treated and recycled; as a treatment unit on oating solids in thickeners (concentrates or tailings); as an auxiliary process to bio-oxidation lagoons or sludge thickening in water reuse; as a process for removing various organics, residuals chemicals, including petroleum, from water; as a solid/liquid separation process in acid mine drainage neutralization with lime; as a primary treatment unit ahead of secondary treatment units, such as bio-oxidation lagoons for reducing the cost of aerobic digestion; as a unit process for sludge thickening. Why otation? Many advantages have been reported illustrating the technical and economical potential of this process: high selectivity to recover valuables (Au, Pt, Pd, etc); high eciency to remove contaminants: high overow rates, low detention periods (meaning smaller

tank sizes, costs); less thicker space scums needs,and savings in construction sludge than in gravity settling or skimming and; low operating costs(Da withRosa the use of upcoming otation devices et al., 1999; Rubio, 1998a,b, 2001); thicker otation concentrates (612% w/w). Table 2shows a partial list of current commercially available otation devices for wastewater treatment and drinking water treatment units. Voronin and Dibrov (1999) have recently published a classication of otation processes in wastewater decontamination. They grouped dierent otation techniques based on physicochemical and technological points and divided them in adsorptive or adhesive. A number of applications are reported without mention neither the type of equipment employed nor the bubble size distribution. 2. Conventional otation techniques, devices and processes recognized techniques are summarized to Here show some their main features. 2.1. Electro-otation (EF) The basis for the diluted micro-bubbles generation is the electrolysis of aqueous, conducting solutions with the production of gas bubbles at both electrodes. Applications, to date, at an industrial scale, have been such in the area of removal ofwater, light colloidal systems as emulsied oil from ions, pigments, ink and bers from water (Zabel, 1992; Zouboulis et al., 1992a,b). Advantages claimed are the clarity of the treated wastewater and disadvantages are the low throughput,

Table 1 Dierences between otation in mineral processing and in wastewater treatment

106 9

103 (jet/columns)

Parameter Feed solids content (weight/weight basis) (%) Particle size to oat (lm) Bubble size distribution (lm) Bubbles rising velocity (m h ) Number of bubbles (cm 3 ) Bubbles surface area (cm2 cm 3 ) Air hold up (%)
a 1

Froth otation of minerals 2540 10150 6002000 250800 (approximate values) 9 103 2 102

Water and wastewater treatment < 4 (DAF) 1030 (jet/columns) 150 (not occulated) and 15 mm ocs (with polymers)a 30100 (DAF) 100600 (jet/columns) 0.730 (DAF) 301000 (jet/columns) 6 108 2 106 (DAF) 4000600 (DAF) 600100 (jet/columns) 814 (DAF) 2040 (jet/columns)

10030 1525

Aerated ocs.

Table 2 Examples of some commercially available otation devices for wastewater treatment Supplier company Sionex Canadian Process Technologies using Canadian Process Technologies WesTech OR-Tec Hydroxyl Industrial Systems dissolved Type of cell characteristics DAF Vertical oil separation cell VOSCell natural gas as a separating medium. IAF column Dissolved Air and Nitrogen (DNF) otation systems HF IAF uses a baed, aeration system that produces very ne bubbles Positive Flotation Mechanism (PFM); air otation processes Electrostatically charged micro-bubbles ZEPHYRe IAF using very ne bubbles Ultra-Float ADAF plug ow DAF device High capacity DAF-lter system ISF assing, hydraulically operated gas otation, degand optional skim storage components BAF air-sparged BAF, induced-air vacuum BAF, electrootation BAF BAF, Flotation piles (underwater oil/water combines secondary treatment of produced water with disposal in one vessel CAF FF otation of aerated ocs
R

Application details Wastewater treatment to oils, remove suspended organic solids, algae, 57 lm oocysts, volatiledissolved organic compounds, humic acid, clarication Developed to remove oil and grease from produced water using natural gas as a separating medium Organic recovery otationand columns for from reducing organic prior reagent kerosene rich electrolytes to electrowinning Wastewater treatment Flotation of fat, grease, suspended solids from food, municipal industrial waste streams Dissolved air and otation processes for solids, air and grease

Aeromax Systems Thermodyne Corporation PURAC Engineering BakerHughes Process ZPM Engineering Specialties separator) Hydrocal Aquaot

For fat, grease, oatable solids It is a plug ow DAF device. For food or industrial processing wastes Drinking water, sludge thickener, ice-cream euents, paper mill For oil/water separations. System in a completely enclosed otation process For treatment of petroleum, heavy metal, laundry, food contaminated processing, screen printing, animal feed waters For oshore operation the treated water discharges directly into the sea

For treatment of laundry, food processing waters Vehicle washing euents, removal of oil, solids, surfactants

the emission of H2the bubbles, electrode costs and maintenance and voluminous sludge produced. An electrolytic coagulation/otation (ECF) system has been also reported using reversibleions polarity aluminum electrodes. Herein, aluminum are released from the anodes, inducing coagulation, and hydrogen bubbles are generated at the Bulk aluminum cathodes, enabling otation of the ocs. water passes through the reactor and process. is treated by the coupled coagulation/ occulation Laboratory scale tests have shown that the aluminum ECF reactor performs better than conventional sulfate coagulation when treating organic a model colored (DOC) water, with 20% more dissolved carbon removed by electro-coagulation for the same Al doses (Andre et al., 2000). 2.2. Dispersed (induced) air otation (IAF) Bubbles are mechanically formed by aand combination of a high-speed mechanical agitator air injection system. The technology makes use an of the centrifugal force developed. The gas, introduced at the top, and the liquid become fully intermingled and, after passing

through a disperser outside the impeller, form lm a multitude of method, bubbles sizing from 7001500 diameter. This wellin known in mineral processing, is utilized also the petrochemical industry, oilwater separation (oily sewage) (Zheng and Zhao, for 1993; Bennett, 1988). 2.3. Dissolved air (pressure) otation (DAF) Bubbles are formed with by aair reduction in pressure of water pre-saturated at pressures higher than atmospheric. Theor supersaturated water is clouds forced trough needle-valves special orices, and of bubbles, 30100 in diameter, are produced just down-stream of thelm constriction Lazaridis et al., 1992). (Bratby and Marais, 1977; DAF was recognized as a method of since separating particles in the early 20th century and then has found many applications including: clarication of renery wastewater, wastewater recla- mation, separation solids and other in drinking water treat- mentof plants; sludge thickening and separation of biological ocs;

Fig. 1. The conventional DAF unit, with water recycle to the saturator.

removal/separation of ions; treatment of ultra-ne minerals (Gochin and Solari, 1983); removal of organic solids, dissolved oils and VOCs (dissolved toxic organic chemicals); removal of algae, 57 lm Giardia oocysts, 45 lm cryptosporidium oocysts, humic water treatment, algae from heavily algae laden waters, etc. The DAF process (see Fig. 1) is by far the most widely used otation method for the treatment of industrial euents. It is believed that applications will rapidly expand in the waste treatment in the metallurgical and mining eld (Rubio and Tessele, 1997; Tessele et al., 1998; Rubio et al., 1996; Rubio, 1998a,b; Santander et al., 1999; Da Rosa et al., 1999). DAF development has been very rapid in the last decade and many of its earlier limitations are being solved. Table 3 reviews recent important developments in DAF. 3. Emerging otation techniques and processes 3.1. Nozzle otation (NF) This process uses a gas aspiration (an eductor or an exhauster) to draw air nozzle into recycled water, which
Table 3 Main developments in dissolved air otation (modied from Kiuru, 2001) Year 1924 Development

Fig. 2. Continuous nozzle otation unit.

in turn is discharged into a otation vessel (similar to the dispersed-air conventional machines), to2). develop a twophase mixture of air and water (Fig. Bubbles are of the size 400800 l m in diameter (Bennett, 1988; Gopalratnam et al., induced 1988). Advantages claimed for the nozzle units, over air otation (IAF) systems, are the following: lower initial costs and energy use because a single pump provides the mixing and air supply; lower maintenance and longer equipment life because the unit has no high-speed moving parts to wear out. Applications reported have been exclusively in the petrochemical industry for the separation of o/w emulsions and treatment of oily metal-laden wastewater (Gopalratnam et al., 1988). 3.2. Column otation Column otation is still a subject of great growing interest in mineral processing with a steadily number of (Finch, research studies and industrial applications

First generation: Pedersen cells. separation tank is shallow and very low product) throughput, 2 m h 1tank . The capture of particles by bubbles occurs inThe an inclined zone aside of the froth (oated separation

1960 1970 1990 and 1995

Second generation (conventional): cells less shallow with higher loading capacity, 57 m h 1 DAF deeper with lters for the treated water. Higher throughput 1015 m h 1 Third generation: Turbulent DAF deep units, high capacity cell > 40 m h . The capture zone is now deep horizontal Fourth generation: co-current type of cell with the capture occurring in the same tank (Cocco-DAF). They resemble more the high capacity cells used in mineral processing, but with micro-bubbles (Eades and Brignall, 1995)

Fig. 3. The Microcel otation column.

1995; Rubinstein, Finch and Dobby, 1990). Infeed the columns usedabout in 1994; the mineral processing area, slurry enters one-third the way down from the top and descends against a rising swarm of bubbles generated by athe sparger. In top wastewater treatment, feed enters by column in the middle of the concentrate product. New developments in column technology include external gas spargers operating and without addi-internal tion of surfactant or with frothers, columns with baes and coalescers for oil recovery (Gu and Chiang, 1999). In the presence of obtained the surface-active reagents micro-bubbles can be as in and the Microcel col- Apumn plications (Yoon etof al., 1992; otation Yoon Luttrell, 1994). column in the eld of oil removal in production waters (Gebhardt et al., 1994) and in recovery of heavy metals precipitates (Filippov etthe al., 2000) have been reported (Fig. 3). 3.3. Centrifugal otation (CF) The separator and contactor can Thus, be an hydrocyclone a simple cylinder. a centrifugal eldor is developed. Aeration occursow by either injecting air (or by suction), through constrictions, such as static mixers or nozzles According Jordan1001000 and Susko (1992), medium size bubblestohaving lm diameters are generated. The air-sparged hydrocyclone (ASH), can be classied as a centrifugal otation unit (Ye et air al., 1988). It consists of an aeration system whereby is sparged through a jacketed porous tube and is sheared into numerous bubbles bywall thephase. highvelocity swirl ow small of of the aqueous Environmental applications ASH otation have been recently reported (Beeby and Nicol, 1993).

Fig. 4. Theotation BAF, bubble accelerated otation or BC, bubble chamber device.

An advanced ASH type of otation has BOD, been reported in to remove oil, grease, etc. BAF orapplications bubble accelerated otation (Fig. 4) system uses the contactorseparation concept with very low detention times in the contactor (Colic et the al., 2001). Depending on the bubble generation system authors devices named Induced Air BAF, Vacuum report BAF, Electrootation as BAF. 3.4. Jet otation This cell appears to have and a great for solid/ liquid separations for potential liquid/liquid separations as well as in mineral processing (Jameson and Manlapig, 1991). Its main advantage is its high throughput, high et al.,eciency and moderate equipment cost (Clayton 1991; Harbort et al., 1994). More, consumption with no moving parts, the jet cell has low The power low maintenance costs. cell consists of and an aeration/contact zone (the downcomer), a(the bubbleparticle or aggregate disengagement zone tank proper pulp area) and a cleaning or froth (medium forming zone (the tank proper zone). The bubbles size) formed in this cell may have 100600 l m in diameter (Jameson and Manlapig, 1991; Clayton et al., 1991). Problems with process accuracy have to been recently solved and its recovery use has been extended wastewater treatment and of solvent extraction liquors (Wyslouzil, 1994) and municipal waters (Yan and Jameson, 2001).

Fig. 5. CAF unit.

3.5. Cavitation air otation (CAF) Cavitation air otation utilizes an a aerator (rotating disc), which draws ambient air down shaft and injects micro-bubbles directly into the wastewater 5). However, work there is knowledge of (Fig. any fundamental with thisno otation technique. is utilized in the food industry, especially in the CAF milk industry, paint and tanneries to remove suspended solids, fats, BOD (biological demand) and oils, CODgreases, (chemical oxygen demand).oxygen 4. Applications and advances Main and industrial applications of otation in mining metallurgy are recovery of and solvent extraction liquors losses by the DAF, column jet otation (Jameson cell), the separation of molybdenum ions (Marinkovic, 2001) and manganese ions by DAF (Krofta, 1991). it is believed that there may be other, not Yet, reported examples, similar to those encountered in other industrial elds. A number of papers have recently been published illustrating techniques employed and otation devices. These can be summarized as following: 4.1. Removal of ions Theimportant removal of ions water, one of the most issues infrom environmental problems today, is technically possible through various otation techniques (Zabel, Matis, 1992; 1995). Lazaridis et al., 1992; Rubio, 1998a,b; Principal removal methods are: precipitate otation (Silva et al., 1993; Stalidis et al., 1989a,b; Lemlich, 1972; Pinfold, 1972; Mummallah and Wilson, 1981); gas aphrons otation or colloidal gas aphrons (CGA);

foam otation (Clarke and Wilson, 1983); ion otation (Nicol et al., 1992; Walkowiak, 1992; Schugerl, 2000); adsorbing particulate (colloids or aggregate) otation (Zabel, 1992; Matis, 1995; Rubio and Tessele, 1997; Zouboulis et al., 1992a,b, 1993, 1997, 2001; McIntyre et al., 1982). ionic otation (Scorzelli et al., 1999). 4.2. Precipitate otation This process is the formation of a precipitate its of subsequent the based ionic on species, using a suitable reagent, and removal by attachment to air bubbles form a otation concentrate (Huang and Liu, to 1999; Lemlich, 1972). Depending on the metal solution concentration, the precipitation may proceed via metal hydroxide formation or as a salt with a suitable anion (sulde, carbonate, etc.). In the case of anion removal, precipitation should cation. proceed through addition of a metal 4.3. Gas aphrons otation or colloidal gas aphrons (CGA) Sebba, who established ionic in micro1959, proposed the use of colloidal gas otation aphrons They or foams or simply micro-gas dispersions. are dispersions of gases in which liquids introduces formed with use of a venturi generator a the gas to a circulating surfactant solution in a region of high velocity and low pressure (Sebba, 1962; Ciriello et al., 1982). This produces very bubbles, which range of in size from 10 toDespite 50 lm small and a large surface area. the provide potential, no amount industrial applications are known and studies are mainly related to laboratory and pilot scale (Kommlapati et al., 1996; Save and Pangarkar, 1994).

4.4. Foam separation or foam otation This method similar to ion otation but uses an excess of a is surfactant asubstances proper frother to produce a stable foam. Here or the removed may be ionic or molecular, colloidal, crystalline, or cellular in nature, but, in all cases, they must selectively attach to the air liquid interfaces (of foams or of bubbles) (Clarke and Wilson, 1983). Some authors denote the accurately separation as foam fractionation since this term describes the removal of the surface active carrier compounds in solution in a foam column. Hundreds of parpers have been reported on foam/otation or fractionation at laboratory and pilot industrial applications are believed toscale exist.and some 4.5. Adsorbing colloid otation This method on involves the removal of the metal ion by adsorption a precipitate acting as a carrier. The loaded carrier is (coagula) then surfactant. oated, usually assisted with a suitable collector The main carriers used have been ferric or aluminum hydroxides collected with the help of sodium oleate or lauryl sulphate (Stalidis et al., 1989a,b). A recent DAF process to remove ions in Chile employs this principle with molybdenum the FeOH3 as the molybdenum carrier and sodium as collector has been reported. This method oleate has been successful in separating the molybdenum ions from CuMo concentrate ltrates and meeting Chilean emission standards. The interesting is that this plant uses a rougher stage feature to remove rst the suspended solids oleate) and then the and Mo calcium ions in aions (as calcium cleaner at pH hydrophobicity about 5. Sodium is also addedstage to enhance andoleate process kinetics. 4.6. Ion otation This method involves the removal of ions (colligend orasurface inactive by species transport to froth as counter-ion to a species) surfactant of opposite charge. Here the surfactants perform the dual role of of the frother andspecies collector, facilitating the adsorption colligend onto the surface of an airotation bubble. In some cases, a ion ligand-activator the of the metal followed byfor a suitable surfactant has been necessary (Walkowiak, 1992; Nicol et al., 1992; Galvin et al., 1994). Despite many studies performed at years laboratory and pilot scale, only during the last few have applications of this method in industrial scale been reported (Zouboulis et al., 1992a,b; Nicol et al., 1992). A novel gold recovery scheme based on ion otation has been developed. Heap leach liquor, containing gold cyanide is reacted with a suitable surfactant and sparged et al., 1994). The surfac- using compressed air (Galvin

tant adsorbs at providing the surface the rising air bubbles, thereby an of interface for ion pairing to selectively collect the gold complex. Scorzelli et al. (1999), studied the removal of Cd ions using sodium dodecyl- (NaCl sulfateand as Na collector and the eect of ionic tension strength 2 SO 4 ), frothers and surface was evaluated. Main nding are the removal obtained for a metal ratio of high 1:2(98% with 0.1% v/v isopropanolcollector frother) and the negative eect of the high strength (>10 3 M). 5. Up coming techniques and advances 5.1. Aggregation-DAF Precipitation, coagulation and occulation have been utilized in stages rst to destabilize highly soluble ions to form colloidal particles or precipitates. Then, coagulation is used to enhance particle size and nally, with ocs. the polymer to formhas stable, big and hydrophobic This technique been reported to remove Hg, As and Se ions from processing streams of gold cyanidation cir- NaDTC, cuits (Tessele et al., 1998) usingwas DAF. Here sodium dithiocarbamate, employed as precipitant, LaCl 3 or FeCl were the coagulants and Buoc (Buck3 man), the occulant. Almost complete removal (> 98%) of the metal ions from solution was reported using DAF. Process and eciency depended on the system solution interfacial chemistry, aggregation phenomena and DAF operating parameters. Main stages are the following: 1. ions + precipitant colloidal precipitate (310 lm), 2. colloidal precipitate + occulant ocs ( 13 mm), 3. ocs + micro (5150 lm) and mid-sized bubbles (200 600 lm) otation by DAF and/or columns (nonturbulent regimes). 5.2. Adsorbing (or sorbing) particulate otation-APF or simply carrier otation-CF The basis otation of the adsorptive (or sorbing) particulate (or carrier) is the uptake of particles. cation, anion or organic by readily oatable This resembles oxide otation activation by metal ions, sulde depression by anions or adsorption of collectors or frothers. tially, APF isemploying a variant of the adsorbing colloidEssenotation process, particles as carrier-sorbing (absorbing and/or adsorbing) material for the metal ion. The key to the process is the selection of a good sorbing carrier having a high surface area and a high reactivity with the pollutant to be removed and it should oat readily. The carrier can be a or mineral particle, The a polymeric resin, activated a by-product. use of microorganismscoal as sorbing materials (biosorption or bio-

Table 4 Main reported studies of APF Adsorbing material Coal jigging tailings Zeolites Zeolites Pyrite Red mud Dolomite Fly ash Exchange resin Hydroxyapatite Activated coal Coal jigging tailings Barite Clay (hydrotalcite) Contaminants Ni, Cu, Zn Ni, Cu, Zn Hg, As, Se Cu, As Cu Pb Ni Cu Cd Dye (Rodamine B) Oil Emulsied oil 6 Chromate, Cr ions Author(s) F eris (2001) Rubio and Tessele (1997) Tessele et al. (1998) Zouboulis et al. (1992a,b, 1993) Zouboulis et al. (1993) Zouboulis et al. (1993) Zouboulis et al. (1993) Duyvesteyn and Doyle (1995) Zouboulis et al. (1997) F eris et al. (1999) Santander and Rubio (1998) Santander and Rubio (1998) Lazaridis et al. (2001)

sorptive otation) has been proposed may be an- other alternative (Zouboulis et al., and 2001). The removal of Cu, Zn and Ni from diluted solutions by APF was studied at laboratory and pilot scale (F eris, 2001). The sorbing used was a coal washing tailing material from a coal industry from south of Brazil and the otation process applied was DAF. Best results (> 95% removal) showed that the residual ions concentration is below the standards limits dictated by the local legislation. Table 4 summarizes main reported studies in this subject. 5.3. Column otation to remove ions A modied Microcel column et improved al., 1992) with feed entering by the cell (Yoon topto(to solid/liquid separation) studied oat loaded (with metal ions) FeOHwas 3 precipitates as a function of pH (Souza and Rubio, unpublished results). The column employs water treated recycling procedure to generate bubbles. Thus, by valve, pumping the ow uid through a venturi or needle airThe is drawn into the pipe and bubbles are produced. size of the bubbles can be modulated with addition of a surfactant. Results showed that medium best separation was obtained when optimizing pH, of sodium oleate (asothcollector) andaddition operating parameters, among ers conditioning, ow rates, etc. Recently, Filippov et al. (2000) studied the interactions between supercial feed and gas velocities and recycling pulp ow rate on bubble size distribution and its eect on Mo-precipitate otation. They conclude that the precipitate otation eectiveness in columns is related to oc stability under turbulence created by the swarming of rising bubbles. 5.4. Dissolved air otation DAF of iron lower hydroxide at working pressures thanprecipitates 3 atm, using modied otation

units to improve the Laborato collection of coagula, was studied at the rio fragile de Tecnologia Mineral e Ambiental (F eris and Rubio, 1999). Conventional DAF otation was studied as a function of saturationin pressure in the absence and presence of surfactants the saturator. Without surfactants, the minimum saturation pressure required for DAF to occur was found to be 3 atm. But, by lowering the air/wateratsurface tension in the DAF was possible a saturation pressure of saturator, 2atm. This behavior was operation found to occur inand both almost batch and pilot DAF tests complete re- covery of the precipitates attained. Results are explained of was the minimum energy which has bubbles to in be terms transferred to the liquid phase to form by a cavity phenomenon. Since the saturation stage accounts for about 50% of the total operating energy costs and considering low cost involved in potential. the surfactant, this option the appears to have a great A very important feature only reported for DAF, concerns with the mechanisms of bubble/particle (aggregates) interactions other than the common adhesion through hydrophobic forces (Fig. 6). Thus, apart from particles/bubbles collisions and adhesion, in DAF, part of the dissolved air in water, which does not convert into bubbles in the nozzle, remains in solution and nucleate at the particle surface (Solari and Gochin, 1992). This mechanism is independent on surface hydrophobicity and allows otation of hydrophilic particles. More, bubble entrapment into ocs or coagula and aggregate entrainment by the rising bubbles are mechanisms, which make separation easier. This explains the fact that in DAF, no collector or froth is required but a thick and stable oat layer is formed. Results show high clarication euents are obtained in DAF. However, a major disadvantage is that rapid air bubble levitation speed is not attainable and hydraulic loadings are low (this is

dictated by the limiting process capacity.

Henrys

law)

reducing

and

Fig. 6. Bubble-particle mechanisms in DAF: (a) particlebubble collision and adhesion; (b) bubble formation at particle surface; (c) microbubble entrapment in aggregates; (d) bubbles entrainment by aggregates.

5.5. Separation of oils and organic compounds by otation The otation of organic bearing watersemulsions such as oil spills on used water, oily sewage or oil-in-water has been in various elds for in a number of decades but is not commonly used the mining and/or metallurgy industries. Most of the research studies on the separation of oil from water have addressed the eect of oil concentration, type concentration of destabilizing agents technique for and o/w emulsions and the type of otation to be employed (Bennett, 1988). In the miningmetallurgical industry, residual oily wastewaters commonly discharged waters containing otation chemicals and solventare extraction reagents, surface waters contaminated with free wasted oil and process waters containing oil spills (Pushkarev et al., 1983). Oil in water may be dispersed, emulsied or in solution in water in concentrations up to 1000 ppm. In particular, the presence of emulsied oil in water droplets around 50 lm in size causes problems in phase separation by conventional techniques (oil/water gravity separation, DAF). The otation separation of very ne oil droplets (230 lm) is even more complicated and usually requires ne bubbles, quiescent hydrodynamic conditions in the cell separation zone or emulsion breakers prior to otation (Gopalratnam et al., 1988). This is due to collection and adhesion factors, which makes the process very slow, especially when, treating high owrates. IAF and DAF, have been used extensively in the removal of stable oily emulsions (Bennett, 1988; Strick-

land, 1980; Belhateche, 1995). IAF utilizes bubbles between 401000 lm in size and turbulent hydrodynamic conditions. The process has low retention times,

normally <5 (30100 min. Conversely, DAF employs microbubbles lm),times and quiescent regimes. However, because retention are higher (2060 min), this process is inecient when treating high volume euents and high ow-rates. The Jameson cell, column otation with CGA (prereagentized gas being bubbles) and conventional columns are now utilized in solvent extraction plants (Readett and Clayton, 1993). Here the otation devices are used in the discharge aqueous streams from the solvent extractionelectrowinning (SXEW) plant to recover the organic liquor lost by entrainment into the aqueous phase. and Thus, otation can environreduce organic losses reduce potential mental problems. 5.6. Modied jet otation cell A laboratory modied jet otation cell has been in our (Fig. 7), to for account for a studied better oil droplet coalescence and the decrease in the amount of short circuit observed in the conventional (Jameson typeenters cell). Thus, the slurry abandoning the downcomer, a cylinder obligating the coalesced or occulated oilbubbles aggregates units to leave the separation tank by the froth layer. Results show that cell this cell is more accurate than the conventional yielding high oil re- moval values and treated water with low oil levels. Thus, with 1 highly emulsied feeds having up to 603 mg l of oil, the removal was almost constant at or greater than 80% regardless of the oilcell content. It is believed this of initial otation has at a great potential that for oil or type organic solvent removal high 1 throughput values (>600 m d ).

Fig. 9. Eect of occulant concentration on oil centrifugal otation1 performance 33:3 l min 1 . Feed oil concentration 152mg l .

in the very Main near future placed onare oshore platforms in Brazil. characteristics the separation very low residence time low (high throughput), high eciency and water split. However, the otation eciency (Fig. 9) depends mainly on the degree of occulation and on the vortex nder clearance.
Fig. 7. Modied jet otation pilot unit (Santander and Rubio, 1997, 1998).

5.8. The FF-occulation-otation process A new turbulent on-line occulation system assisted with air bubbles has been developed at LTM yielding aerated ocs (ocs with entrained and entrapped bubbles). These ocs, which rapidly oat, are

5.7. Centrifugal otation cell The separation of occulated (coalesced) oil emulsions in a centrifugal otation machine (Fig. 8) has been recently performed on a pilot scale in the Laborato rio de Tecnologia Mineral e Ambiental (LTM), Universidade Federal do Rio Grande do Sul, Brazil. The device will be

Fig. 8. The LTM-centrifugal otation device.

Fig. 10. FF-occulation-otation device.

formed only in the of high molecular weight polymers and presence bubbles and under high shearing in the the occulator (Fig. 10). The air by excess air leaves otation tank (a centrifuge) the top and the ocs oat after very short residence times (within millimeters seconds). The aerated ocs are large units (some in diameter) having an extremely low density (Rubio, 2001). 5.9. The multibubble otation column Recently, F colloidal eris et al. (2001) reported data on the removal of ferric hydroxide by otation in a column with bubbles generated in an static mixer (medium-sized bubbles) and micro-bubbles generated as in DAF. These authors named this column otation device a multibubble column. Using this modied microbubble column they reported better results as compared to DAF alone. Gains reported were a better air-to-solids ratio (higher bubble surface ux), improved process kinetics and improved process throughput. Fig. 11 shows some details of this otation device. 6. Miscellaneous separations 6.1. Micro-organisms It has been for many years, that bacteria can demonstrated, be readily concentrated by froth or foam

otation and since that not time number of investigators have conrmed only a the otation of bacteria, but of algae and othermicro-organisms (Smith, 1989; gerl, a Schu 2000). removal by otation is becoming good Alga alternative to other treatment methods in tropical countries. In such environments, the algae grow at a great rate causing problems in all water reservoirs. Furthermore, proliferation of algae in maturation ponds often results in solids values exceeding EPA license limits for suspended and elevated pH values. Also, discharge of algae (especially blue-green algae) laden ef- uents can also cause release of their associated toxins to surfacepossible and ground waters. The jet otation process for alga removal reported by Yan and Jameson (2001) appears to be the an interesting application of municipal otation for treatment of algae bearing waters. Alga cells such as Microcystis sp. that occur commonly in wastewater ponds are usuallyalga very small in size contact, (37 maturation lm)aggregates and to induce ecient cellair bubble of greater than 10 l m in size areto required. Cationic polymer occulants are found be not. eective, while nonionic or anionic polymers are Dierent types of algae appear to share common surface characteristics. The same occulant was found to be eective in occulating dierent types and of Cell alga cells (e.g., very Microcystis , Anabaena ). forms Jameson technology was shown to be capable of simultaneously removing algae and phosphorus enabling thealternative continued use of maturation and provides an to costly upgrades ponds of existing wastewater treatment plants.

Fig. 11. The multibubble otation column.

6.2. Proteins Various other non-fatty organic materials, such as soluble proteins derived from soybean processing, can beitation removed from water by DAF otation after precipand occulation (Schneider et al., 1995). Soluble protein removed by soybean this process from aqueous waste streams from plants can potentially be used as supplemental animal feed. basis for protein separation ecules by otation is The the aggregation of the macromolwith inorganic salts and/or polymers and otation with microbubbles. Problems arise when proteins contain associated de-foaming agents or short dispersing molecules that modify the surface properties of protein enhancing their hydrophilic character aggregates and reducing bubble-particle adhesion. 6.3. Plastics Modern industrial and home use plastics has created environmental need to of recycle waste plastics of an a used number of dierent types. Most of the commonly plastics, such as polyvinyl chloride, polycarbonates, polyacetal, and polypropylene ether are naturally hydrophobic and are readily oated without addition a otation collector. Thus, process selectivity is hydrophobicities a of dicult task. However, plastics vary in their and their critical surface tensions have been explored using surface-active reagents. Thus, their oatabilities can be modulated by use of suitable depressants, which

include sodium lignin sulfonate, tannic acid, and Aero- sol OT (Shibata et al., 1996). 6.4. Deinking Flotation has been used, for a number of of years, in paper deinking for paper recycling. Most the studies are based on ink removal using surfactants and calcium bearingthe salts. Finch and machines Hardie (1999) have reviewed main otation and techniques employed in of thisaparea, showing and discussing a variety proaches to optimize the characteristics of such used otation systems. 6.5. Soil washing Flotation is non-volatile being studied for removal of toxic and relatively hydrophobic compounds such as heavy oil, PAH, orbasic PCB parameters from contaminated soils. The eects of the ofwith the process have been and compared soil washing, andinvestigated the and advantages otation demonstrated (Ososkov Kebbekus, of 1997). Some limited reports intoxic the literature point organics out that a signicant fraction of hydrophobic may be Howremoved from contaminated soil on by otation. ever, no systematic investigations removal of these substances from soil by otation have been reported. Hydrophobic non-volatile organic compounds are poorly adsorbed by soil particles, which are primarily

hydrophilic. These contaminants are mainly trapped in the ported soil pore space. Trapped compounds can by be transto otation. the surface of organic soil/water slurry bubbles during Soil matter or hydrophobic impurities in soil matrix adsorb some of hydrophobic However, otation may remove only part pollutants. of the adsorbed pollutants. 6.6. Removal of radioactive nuclides from soils Flotation of radioactive nuclides from contaminated soils and coral sand bycolumn both conventional-induced air otation and otation has been studied and evaluated (Misra al., 1995; Misra et al., In such separations it et is desired to produce a 1996). very clean material (non-oat) and a concentrate that contains most of the radionuclides, but is still a low-level radioactive material. The goalthe is high butto a dispose low-grade concentrate. Thus, bulk recover, of material of in a waste repository is much reduced. 7. Final remarks Since nected the factors, otation depends on multiple interconmany considerations should be taken device and into its account when selecting a otation

capacity and the techniques to be employed. Some of these factors are the following: 1 1 1 The wastewater ow-rate (m3 h , m3 s Table or 3 m day ) and the equipment throughput. 5 shows examples of some reported values for otation loading Thesesgenerated values are related to hydraulic the bubble distribution in the dierent otation size devices (see Figs. 12and 13). complexed, The nature of pollutants, whether free, volatile, inorganic-organic Their concentration in euents and or in mixtures. standard emissions. ExperimenThe nature of aggregates to be removed. tal studies will dene the bestform way of to remove the pollutants, whether in the coagula, precipitates, complexes), or ad- ocs, sublate (metal-collector
Table 5 Averaged hydraulic loading values reported for some otation devices operating in mineral processing ( ) and wastewater treatment Equipment DAF IAF (induced air) Column cell Jameson (jet) cell ASH (Miller cyclone) FF-occulation otation BAC Hydraulic loading (m h ) 740 36430 50360 70350 500720 1402160 (oil removal) 1.5500
1

Fig. 12. Flotation techniques/devices operating with micro-bubbles. EF Electrootation; GA Gas aphrons; CAF Cavitation air otation; DAF Dissolved air otation.

Fig. 13. Flotation techniques/devices operating with medium sized (200800 lm) and macrobubbles (IAF > 800 lm).

sorbed on coagula a carrier.withstand Flocs andshear particulate carriers and not and with may be separated in(cenotation devicesjet). operating high turbulence trifugal, DAF is more amenable for separation of coagula or precipitates. Nevertheless, DAF of aer- ated ocs is also a good and fast alternative. condiThe need for collectors, optimal pH, redox tions, residence time, air-to-solids ratio, air hold up, bubble surface ux, lifting power of bubbles, eect of temperature, density, viscosity, surface tension (frothability), interfacial properties of aggregates (charge, hydrophobicity). cleaner Flow-sheet design. Whether a rougherscheme is needed: destiny of the oated product and the process water (possible reuse?), ltration characteristics, drying, economics of the process. Figs. 12and 13 show approximate bubble size ranges, which have reported in various otation devices and been techniques. 8. Conclusions Flotation especially is ever increasingly in waste treatment, in the used mining and metallurgical industry. Furthermore, the introduction of new, superior, otation devices should lead to new and better contaminated applications wafor ters remediation of mineral industry and solids. A cross fertilization of otation experience in mineral otation and in wastewater treatment should lead to new and improved procedures in the mineral and metallurgical industry, the chemical and petroleum treatment. industries and domestic wastewater Acknowledgements Authors thank the students and colleagues responsible for theall friendly atmosphere at LTMUniversidade Federal do Rio Grande dothe Sul and to all institutions supporting research in Brazil. References
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