Minerals Engineering 15 (2002) 139155 www.elsevier.

com/locate/mine

Overview of otation as a wastewater treatment technique

J. Rubio
a

a,*

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

Departamento de Engenharia de Minas-PPGEM, Laborato rio 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 the most serious environmental issues faced by the minerals and metallurgy industries. Main pollutants are residual reagents, powders, chemicals, metal ions, oils, organic and some may be valuable (Au, Pt, Ag). The use of otation is showing a great potential due to the high throughput of modern equipment, low sludge generation and the high eciency of the separation schemes already available. 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 in environmental applications is fully discussed. Examples of promising emerging techniques and devices are reported and some recent advances in the treatment of heavy metal containing waters and emulsied oil wastes are discussed. 2002 Elsevier Science Ltd. All 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 widespread throughout the world and can become contaminated by various pollutants. These substances include powders, chemicals, metal ions, oils, organic and others, sometimes rendering the water useless for recycling as process water, often dangerous 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 Barreto, 1996; Warhurst (Smith, 1996; Villas Bo and Bridge, 1996). Sometimes, due to their chemical complexity and/or volume, these process waters cannot be treated economically even in cases where they contain valuable materials. Further, 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 dicult especially when the oil is emulsied, and worse when the mean droplet size is small or if the emulsions are chemically stabilized (Beeby and Nicol, 1993). Smith (1996) showed in detail characteristics of liquid and solid wastes from mineral processing plants. Various techniques and technologies available were discussed and the quality and quantity of typical pollutants were listed. Thus, current and future technologies will eventually have to deal with 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 matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 8 9 2 - 6 8 7 5 ( 0 1 ) 0 0 2 1 6 - 3

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1.2. Conventional treatment processes The conventional process for treating liquid euents containing metals ions is precipitationaggregation (coagulation/occulation)-settling as hydroxides or insoluble salts. However, this method, from a technical point of view, presents certain limitations, namely: the formation of metal hydroxide is ineective in dilute metal bearing euents; the hydroxo precipitate tends to re-dissolve, dependm ing on the metal, via the reaction MOHn OH m MOHnm ; 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 s1 is very dicult and costly. This constitutes a great challenge for the modern mining industry. 1.3. Flotation processes The use of otation has shown to have a great potential owing 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 otation are the selective recovery of valuable ions such as gold, palladium, silver (which are also pollutants), the new separation schemes now available and the low sludge generation in this process. This paper summarizes general features of otation in environmental applications and is aimed to: show the potential of otation as a wastewater treatment technique and present some advances; present novel separation concepts and otation devices; serve as a bridge providing information on otation activities being conducted in various engineering elds as well as in the mining and metallurgical industry. It is believed that a cross exchange of otation experience in mineral otation and in water and euent treatment should lead to new and improved procedures for industry waste treatment.

1.4. Flotation process in wastewater treatment Flotation had its beginning in mineral (ore) processing and as such has been used for a long time in solid/ solid separation applications using stable froths to selectively separate dierent minerals from each other (Kitchener, 1985). Regarding applications of otation in wastewater and domestic sewage treatment, civil and chemical engineers have used dissolved air otation (DAF) for a number of years (Hooper, 1945). Main applications have 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, gerl, 2000), such as: 1997; Kim et al., 1999; Schu 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, micro-bubbles are required. Because the species oating are usually aggregated colloids rather than dispersed ones, high shear rates 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. Micro-bubbles do not oat dense and big particles, especially at high solids content (45%, w/w).

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The type of separation: solid/solid/liquid in mineral processing and solid/liquid, solid/liquid1/liquid2 or liquid/liquid in water treatment. In mineral otation it is necessary to produce a stable froth at the free surface of the otation cell. In applications to 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, less space needs, savings in construction costs); thicker scums and sludge than in gravity settling or skimming and; low operating costs with the use of upcoming otation devices (Da Rosa et al., 1999; Rubio, 1998a,b, 2001); thicker otation concentrates (612% w/w). Table 2 shows 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 Here some recognized techniques are summarized to show their main features. 2.1. Electro-otation (EF) The basis for the micro-bubbles generation is the electrolysis of diluted aqueous, conducting solutions with the production of gas bubbles at both electrodes. Applications, to date, at an industrial scale, have been in the area of removal of light colloidal systems such as emulsied oil from water, 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 Parameter Feed solids content (weight/weight basis) (%) Particle size to oat (lm) Bubble size distribution (lm) Bubbles rising velocity (m h1 ) Number of bubbles (cm3 ) Bubbles surface area (cm2 cm3 ) Air hold up (%)
a

Froth otation of minerals 2540 10150 6002000 250800 (approximate values) 9 103 2 102 10030 1525

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) 2 106 9 103 (jet/columns) 4000600 (DAF) 600100 (jet/columns) 814 (DAF) 2040 (jet/columns)

Aerated ocs.

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Table 2 Examples of some commercially available otation devices for wastewater treatment Supplier company Sionex Type of cell characteristics DAF Application details Wastewater treatment to remove suspended organic solids, dissolved oils, algae, 57 lm oocysts, volatile organic compounds, humic acid, clarication Developed to remove oil and grease from produced water using natural gas as a separating medium Organic recovery otation columns for reducing organic reagent and kerosene from rich electrolytes prior to electrowinning Wastewater treatment Flotation of fat, grease, suspended solids from food, municipal and industrial waste streams Dissolved air otation processes for solids, air and grease 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 processing, screen printing, animal feed contaminated 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

Canadian Process Technologies

Vertical oil separation cell VOSCellR using natural gas as a separating medium. IAF column

Canadian Process Technologies

WesTech OR-Tec Hydroxyl Industrial Systems

Aeromax Systems Thermodyne Corporation PURAC Engineering BakerHughes Process ZPM

Dissolved Air and Nitrogen (DNF) otation systems HF IAF uses a baed, aeration system that produces very ne bubbles Positive Flotation Mechanism (PFM); dissolved 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 hydraulically operated gas otation, degassing, and optional skim storage components BAF air-sparged BAF, induced-air BAF, vacuum BAF, electrootation BAF Flotation piles (underwater oil/water separator) combines secondary treatment of produced water with disposal in one vessel CAF FF otation of aerated ocs

Engineering Specialties

Hydrocal Aquaot

the emission of H2 bubbles, electrode costs and maintenance and the voluminous sludge produced. An electrolytic coagulation/otation (ECF) system has been also reported using reversible polarity aluminum electrodes. Herein, aluminum ions are released from the anodes, inducing coagulation, and hydrogen bubbles are generated at the aluminum cathodes, enabling otation of the ocs. Bulk water passes through the reactor and is treated by the coupled coagulation/ occulation process. Laboratory scale tests have shown that the ECF reactor performs better than conventional aluminum sulfate coagulation when treating a model colored water, with 20% more dissolved organic carbon (DOC) 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 a combination of a high-speed mechanical agitator and an air injection system. The technology makes use 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 a multitude of bubbles sizing from 7001500 lm diameter. This method, well known in mineral processing, is utilized also in the petrochemical industry, for oilwater separation (oily sewage) (Zheng and Zhao, 1993; Bennett, 1988). 2.3. Dissolved air (pressure) otation (DAF) Bubbles are formed by a reduction in pressure of water pre-saturated with air at pressures higher than atmospheric. The supersaturated water is forced trough needle-valves or special orices, and clouds of bubbles, 30100 lm in diameter, are produced just down-stream of the constriction (Bratby and Marais, 1977; Lazaridis et al., 1992). DAF was recognized as a method of separating particles in the early 20th century and since then has found many applications including: clarication of renery wastewater, wastewater reclamation, separation of solids and other in drinking water treatment plants; sludge thickening and separation of biological ocs;

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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.

Fig. 2. Continuous nozzle otation unit.

in turn is discharged into a otation vessel (similar to the dispersed-air conventional machines), to develop a twophase mixture of air and water (Fig. 2). Bubbles are of the size 400800 lm in diameter (Bennett, 1988; Gopalratnam et al., 1988). Advantages claimed for the nozzle units, over induced 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

3. Emerging otation techniques and processes 3.1. Nozzle otation (NF) This process uses a gas aspiration nozzle (an eductor or an exhauster) to draw air into recycled water, which
Table 3 Main developments in dissolved air otation (modied from Kiuru, 2001) Year 1924 1960 1970 1990 1995 Development First generation: Pedersen cells. The separation tank is shallow and very low throughput, 2 m h1 . The capture of particles by bubbles occurs in an inclined zone aside of the froth (oated product) separation tank Second generation (conventional): cells less shallow with higher loading capacity, 57 m h1 DAF deeper with lters for the treated water. Higher throughput 1015 m h1 Third generation: Turbulent DAF deep units, high capacity cell > 40 m h1 . The capture zone is now deep and 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)

Column otation is still a subject of great interest in mineral processing with a steadily growing number of research studies and industrial applications (Finch,

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Fig. 3. The Microcel otation column.

1995; Rubinstein, 1994; Finch and Dobby, 1990). In the columns used in the mineral processing area, feed slurry enters about one-third the way down from the top and descends against a rising swarm of bubbles generated by a sparger. In wastewater treatment, feed enters by the column top in the middle of the concentrate product. New developments in column technology include external gas spargers operating with and without addition of surfactant or frothers, columns with internal baes and coalescers for oil recovery (Gu and Chiang, 1999). In the presence of the surface-active reagents micro-bubbles can be obtained as in the Microcel column (Yoon et al., 1992; Yoon and Luttrell, 1994). Applications of column otation in the eld of oil removal in production waters (Gebhardt et al., 1994) and in the recovery of heavy metals precipitates (Filippov et al., 2000) have been reported (Fig. 3). 3.3. Centrifugal otation (CF) The separator and contactor can be an hydrocyclone or a simple cylinder. Thus, a centrifugal eld is developed. Aeration occurs by either injecting air (or by suction), through ow constrictions, such as static mixers or nozzles According to Jordan and Susko (1992), medium size bubbles having 1001000 lm diameters are generated. The air-sparged hydrocyclone (ASH), can be classied as a centrifugal otation unit (Ye et al., 1988). It consists of an aeration system whereby air is sparged through a jacketed porous tube wall and is sheared into numerous small bubbles by the high-velocity swirl ow of the aqueous phase. Environmental applications of ASH otation have been recently reported (Beeby and Nicol, 1993).

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

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

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Fig. 5. CAF unit.

3.5. Cavitation air otation (CAF) Cavitation air otation utilizes an aerator (rotating disc), which draws ambient air down a shaft and injects micro-bubbles directly into the wastewater (Fig. 5). However, there is no knowledge of any fundamental work with this otation technique. CAF is utilized in the food industry, especially in the milk industry, paint and tanneries to remove suspended solids, fats, oils, greases, BOD (biological oxygen demand) and COD (chemical oxygen demand).

foam otation (Clarke and Wilson, 1983); ion otagerl, tion (Nicol et al., 1992; Walkowiak, 1992; Schu 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 based on the formation of a precipitate of the ionic species, using a suitable reagent, and its subsequent removal by attachment to air bubbles to form a otation concentrate (Huang and Liu, 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 proceed through addition of a metal cation. 4.3. Gas aphrons otation or colloidal gas aphrons (CGA) Sebba, who established ionic otation in 1959, proposed the use of colloidal gas aphrons or micro-foams or simply micro-gas dispersions. They are dispersions of gases in liquids formed with the use of a venturi generator which introduces a gas to a circulating surfactant solution in a region of high velocity and low pressure (Sebba, 1962; Ciriello et al., 1982). This produces very small bubbles, which range in size from 10 to 50 lm and provide a large amount of surface area. Despite the potential, no industrial applications are known and studies are mainly related to laboratory and pilot scale (Kommlapati et al., 1996; Save and Pangarkar, 1994).

4. Applications and advances Main industrial applications of otation in mining and metallurgy are the recovery of solvent extraction liquors losses by DAF, column and jet otation (Jameson cell), the separation of molybdenum ions (Marinkovic, 2001) and manganese ions by DAF (Krofta, 1991). Yet, it is believed that there may be other, not 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 The removal of ions from water, one of the most important issues in environmental problems today, is technically possible through various otation techniques (Zabel, 1992; Lazaridis et al., 1992; Rubio, 1998a,b; Matis, 1995). 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);

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4.4. Foam separation or foam otation This method is similar to ion otation but uses an excess of a surfactant or a proper frother to produce a stable foam. Here the substances 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 separation as foam fractionation since this term accurately 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 scale and some industrial applications are believed to exist. 4.5. Adsorbing colloid otation This method involves the removal of the metal ion by adsorption on a precipitate (coagula) acting as a carrier. The loaded carrier is then oated, usually assisted with a suitable collector surfactant. 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 molybdenum ions in Chile employs this principle with the FeOH3 as the molybdenum carrier and sodium oleate as collector has been reported. This method has been successful in separating the molybdenum ions from CuMo concentrate ltrates and meeting Chilean emission standards. The interesting feature is that this plant uses a rougher stage to remove rst the suspended solids and calcium ions (as calcium oleate) and then the Mo ions in a cleaner stage at pH about 5. Sodium oleate is also added to enhance hydrophobicity and process kinetics. 4.6. Ion otation This method involves the removal of ions (colligend or surface inactive species) by transport to froth as a counter-ion to a surfactant species of opposite charge. Here the surfactants perform the dual role of frother and collector, facilitating the adsorption of the colligend species onto the surface of an air bubble. In some cases, a ligand-activator for the otation of the metal ion followed by a suitable surfactant has been necessary (Walkowiak, 1992; Nicol et al., 1992; Galvin et al., 1994). Despite many studies performed at laboratory and pilot scale, only during the last few years 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 using compressed air (Galvin et al., 1994). The surfac-

tant adsorbs at the surface of the rising air bubbles, thereby providing an interface for ion pairing to selectively collect the gold complex. Scorzelli et al. (1999), studied the removal of Cd ions using sodium dodecylsulfate as collector and the eect of ionic strength (NaCl and Na2 SO4 ), frothers and surface tension was evaluated. Main nding are the high removal obtained for a metal collector ratio of 1:2 (98% with 0.1% v/v isopropanol frother) and the negative eect of the high strength (>103 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 the polymer to form stable, big and hydrophobic ocs. This technique has been reported to remove Hg, As and Se ions from processing streams of gold cyanidation circuits (Tessele et al., 1998) using DAF. Here NaDTC, sodium dithiocarbamate, was employed as precipitant, LaCl3 or FeCl3 were the coagulants and Buoc (Buckman), the occulant. Almost complete removal (> 98%) of the metal ions from solution was reported using DAF. Process eciency depended on the system solution and 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 of the adsorptive (or sorbing) particulate (or carrier) otation is the uptake of cation, anion or organic by readily oatable particles. This resembles oxide otation activation by metal ions, sulde depression by anions or adsorption of collectors or frothers. Essentially, APF is a variant of the adsorbing colloid otation process, employing 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 mineral particle, a polymeric resin, activated coal or a by-product. The use of microorganisms as sorbing materials (biosorption or bio-

J. Rubio et al. / Minerals Engineering 15 (2002) 139155 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 Chromate, Cr6 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)

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sorptive otation) has been proposed and may be another alternative (Zouboulis et al., 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 (Yoon et al., 1992) with feed entering by the cell top (to improved solid/liquid separation) was studied to oat loaded (with metal ions) FeOH3 precipitates as a function of pH (Souza and Rubio, unpublished results). The column employs water treated recycling procedure to generate bubbles. Thus, by pumping the ow uid through a venturi or needle valve, air is drawn into the pipe and bubbles are produced. The size of the bubbles can be modulated with addition of a surfactant. Results showed that best separation was obtained when optimizing medium pH, addition of sodium oleate (as collector) and operating parameters, among others 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 hydroxide precipitates at working pressures lower than 3 atm, using modied otation

units to improve the collection of fragile coagula, was rio de Tecnologia Mineral e studied at the Laborato Ambiental (F eris and Rubio, 1999). Conventional DAF otation was studied as a function of saturation pressure in the absence and presence of surfactants in the saturator. Without surfactants, the minimum saturation pressure required for DAF to occur was found to be 3 atm. But, by lowering the air/water surface tension in the saturator, DAF was possible at a saturation pressure of 2 atm. This behavior was found to occur in both batch and pilot DAF operation tests and almost complete recovery of the precipitates was attained. Results are explained in terms of the minimum energy which has to be transferred to the liquid phase to form bubbles by a cavity phenomenon. Since the saturation stage accounts for about 50% of the total operating energy costs and considering the low cost involved in the surfactant, this option appears to have a great potential. 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 Henrys law) reducing and limiting process capacity.

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

5.5. Separation of oils and organic compounds by otation The otation of organic bearing waters such as oil spills on water, oily sewage or oil-in-water emulsions has been used in various elds for a number of decades but is not commonly used in 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 and concentration of destabilizing agents for o/w emulsions and the type of otation technique to be employed (Bennett, 1988). In the miningmetallurgical industry, residual oily wastewaters commonly discharged are waters containing otation chemicals and solvent 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 ow-rates. IAF and DAF, have been used extensively in the removal of stable oily emulsions (Bennett, 1988; Strickland, 1980; Belhateche, 1995). IAF utilizes bubbles between 401000 lm in size and turbulent hydrodynamic conditions. The process has low retention times,

normally <5 min. Conversely, DAF employs microbubbles (30100 lm), and quiescent regimes. However, because retention times 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 bubbles) and conventional columns are now being 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. Thus, otation can reduce organic losses and reduce potential environmental problems. 5.6. Modied jet otation cell A modied jet otation cell has been studied in our laboratory (Fig. 7), to account for a better oil droplet coalescence and for the decrease in the amount of short circuit observed in the conventional (Jameson type cell). Thus, the slurry abandoning the downcomer, enters a cylinder obligating the coalesced or occulated oilbubbles aggregates units to leave the separation tank by the froth layer. Results show that this cell is more accurate than the conventional cell yielding high oil removal values and treated water with low oil levels. Thus, with highly emulsied feeds having up to 603 mg l1 of oil, the removal was almost constant at or greater than 80% regardless of the initial oil content. It is believed that this type of otation cell has a great potential for oil or organic solvent removal at high throughput values (>600 m d1 ).

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Fig. 9. Eect of occulant concentration on oil centrifugal otation performance 33:3 l min1 . Feed oil concentration 152 mg l1 .

Fig. 7. Modied jet otation pilot unit (Santander and Rubio, 1997, 1998).

in the very near future placed on oshore platforms in Brazil. Main characteristics are the very low residence time (high throughput), high separation eciency and low water split. However, the otation eciency (Fig. 9) depends mainly on the degree of occulation and on the vortex nder clearance. 5.8. The FF-occulation-otation process

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

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

Fig. 8. The LTM-centrifugal otation device.

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Fig. 10. FF-occulation-otation device.

formed only in the presence of high molecular weight polymers and bubbles and under high shearing in the occulator (Fig. 10). The air excess air leaves the otation tank (a centrifuge) by the top and the ocs oat after very short residence times (within seconds). The aerated ocs are large units (some millimeters in diameter) having an extremely low density (Rubio, 2001). 5.9. The multibubble otation column Recently, F eris et al. (2001) reported data on the removal of colloidal 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 demonstrated, for many years, that bacteria can be readily concentrated by froth or foam

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

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Fig. 11. The multibubble otation column.

6.2. Proteins Various other non-fatty organic materials, such as soluble proteins derived from soybean processing, can be removed from water by DAF otation after precipitation and occulation (Schneider et al., 1995). Soluble protein removed by this process from aqueous waste streams from soybean plants can potentially be used as supplemental animal feed. The basis for protein separation by otation is the aggregation of the macromolecules with inorganic salts and/or polymers and otation with micro-bubbles. Problems arise when proteins contain associated de-foaming agents or short dispersing molecules that modify the surface properties of protein aggregates enhancing their hydrophilic character and reducing bubble-particle adhesion. 6.3. Plastics Modern industrial and home use of plastics has created an environmental need to recycle waste plastics of a number of dierent types. Most of the commonly used plastics, such as polyvinyl chloride, polycarbonates, polyacetal, and polypropylene ether are naturally hydrophobic and are readily oated without addition of a otation collector. Thus, process selectivity is a dicult task. However, plastics vary in their hydrophobicities 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 Aerosol OT (Shibata et al., 1996). 6.4. Deinking Flotation has been used, for a number of years, in paper deinking for paper recycling. Most of the studies are based on ink removal using surfactants and calcium bearing salts. Finch and Hardie (1999) have reviewed the main otation machines and techniques employed in this area, showing and discussing a variety of approaches used to optimize the characteristics of such otation systems. 6.5. Soil washing Flotation is being studied for removal of toxic and relatively non-volatile hydrophobic compounds such as heavy oil, PAH, or PCB from contaminated soils. The eects of the basic parameters of the process have been investigated and compared with soil washing, and the advantages of otation demonstrated (Ososkov and Kebbekus, 1997). Some limited reports in the literature point out that a signicant fraction of toxic hydrophobic organics may be removed from contaminated soil by otation. However, no systematic investigations on 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

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hydrophilic. These contaminants are mainly trapped in the soil pore space. Trapped compounds can be transported to the surface of soil/water slurry by bubbles during otation. Soil organic matter or hydrophobic impurities in soil matrix adsorb some of hydrophobic pollutants. However, otation may remove only part of the adsorbed pollutants. 6.6. Removal of radioactive nuclides from soils Flotation of radioactive nuclides from contaminated soils and coral sand by both conventional-induced air otation and column otation has been studied and evaluated (Misra et al., 1995; Misra et al., 1996). In such separations it is desired to produce a very clean material (non-oat) and a concentrate that contains most of the radionuclides, but is still a low-level radioactive material. The goal is high recover, but a low-grade concentrate. Thus, the bulk of material to dispose of in a waste repository is much reduced.

capacity and the techniques to be employed. Some of these factors are the following: The wastewater ow-rate (m3 h1 , m3 s1 or m3 day1 ) and the equipment throughput. Table 5 shows examples of some reported values for otation hydraulic loading Theses values are related to the bubble size distribution generated in the dierent otation devices (see Figs. 12 and 13). The nature of pollutants, whether free, complexed, volatile, inorganic-organic or mixtures. Their concentration in euents and in standard emissions. The nature of aggregates to be removed. Experimental studies will dene the best way to remove the pollutants, whether in the form of coagula, precipitates, ocs, sublate (metal-collector complexes), or adTable 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 h1 ) 740 36430 50360 70350 500720 1402160 (oil removal) 1.5500

7. Final remarks Since the otation depends on multiple interconnected factors, many considerations should be taken into account when selecting a otation device and its

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).

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sorbed on a carrier. Flocs and particulate carriers and not coagula withstand shear and may be separated in otation devices operating with high turbulence (centrifugal, jet). DAF is more amenable for separation of coagula or precipitates. Nevertheless, DAF of aerated ocs is also a good and fast alternative. The need for collectors, optimal pH, redox conditions, 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). Flow-sheet design. Whether a rougher-cleaner scheme is needed: destiny of the oated product and the process water (possible reuse?), ltration characteristics, drying, economics of the process. Figs. 12 and 13 show approximate bubble size ranges, which have been reported in various otation devices and techniques.

8. Conclusions Flotation is ever increasingly used in waste treatment, especially in the mining and metallurgical industry. Furthermore, the introduction of new, superior, otation devices should lead to new and better applications for remediation of mineral industry contaminated waters 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 industries and domestic wastewater treatment.

Acknowledgements Authors thank all the students and colleagues responsible for the friendly atmosphere at the LTM-Universidade Federal do Rio Grande do Sul and to all institutions supporting research in Brazil. References
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