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

com/locate/mine

Overview of flotation as a wastewater treatment technique
J. Rubio
a

a,*

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

b

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 effluents 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 flotation is showing a great potential due to the high throughput of modern equipment, low sludge generation and the high efficiency 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 flotation 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 emulsified oil wastes are discussed. Ó 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, off 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 fluids 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 difficult especially when the oil is emulsified, 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, flotation collectors and modifiers (activators or depressing agents, pH regulators); • separation of various wasted plastics; • radioactive control in aqueous effluents and soils.

0892-6875/02/$ - see front matter Ó 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

/ Minerals Engineering 15 (2002) 139–155 1. Parekh and Miller. such as: 1997. • The solids content present in the pulp system. However. resins and rubber. the minimum solubility for cupric hydroxide occurs at a pH value around 9. flotation is also practiced in other fields (Kitchener. Matis. silver (which are also pollutants). 1992.. It is now widely accepted that medium size and large bubble diameters (300–1500 lm) are optimal for flotation of minerals (fines and coarse particles). Yet. micro-bubbles are required. Rubio et al. namely: • the formation of metal hydroxide is ineffective in dilute metal bearing effluents. civil and chemical engineers have used dissolved air flotation (DAF) for a number of years (Hooper. Cundeva and Stafilov. 1972. high shear rates must be avoided to obviate destruction of the fragile aggregates. 1945). 1985. conventional flotation devices do not generate a sufficient number of bubbles smaller than 600 lm. this method. Clarke and Wilson. the treatment by coagulation and settling of effluent flow-rates of about 2–4 m3 sÀ1 is very difficult and costly. This paper summarizes general features of flotation in environmental applications and is aimed to: • show the potential of flotation as a wastewater treatment technique and present some advances. More.. • harvesting or removal of algae. ions. This constitutes a great challenge for the modern mining industry. 1992. Main uses of micro-bubbles (<100 lm) is in applications of flotation to solid/liquid or liquid/liquid separation. • the pH of minimum solubility of hydroxides is different for the various metals present. • plastics separation and recycling. Other advantages of flotation are the selective recovery of valuable ions such as gold. • treatment of spent photography liquors. 1. 1995. 1996. macromolecules and fibers. Regarding applications of flotation in wastewater and domestic sewage treatment. seed hulls. Rubio. palladium. 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 different minerals from each other (Kitchener. and other materials from water (Matis. €gerl. Thus. 1983. Flotation processes The use of flotation has shown to have a great potential owing to the high throughput and efficiency of modern equipment now available (Zabel.5 while for cadmium hydroxide it occurs at pH around 11. especially at high solids content (4–5%. medium or macro-bubbles. 1983. Kim et al. • odor removal. • the hydroxo precipitate tends to re-dissolve. Micro-bubbles do not float dense and big particles. • protein separation. For example. where extremely small (or even colloidal) particles have to be floated. Schu • analytical chemistry. the distinguishing feature between conventional mineral flotation and flotation in waste treatment is that. the new separation schemes now available and the low sludge generation in this process. • due to kinetic and scale problems.b. from a technical point of view.3. Voronin and Dibrov. w/w). • deinking of printed paper.140 J. It is believed that a cross exchange of flotation experience in mineral flotation and in water and effluent treatment should lead to new and improved procedures for industry waste treatment. Lemlich. • separation or harvesting of micro-organisms. 1. 1985). Mavros and Matis. and. serum.4. • precipitation of metals becomes incomplete when complexing or chelating agents are present. Roe. • filtration may be difficult as a result of the precipitates fineness. presents certain limitations. • serve as a ‘‘bridge’’ providing information on flotation activities being conducted in various engineering fields as well as in the mining and metallurgical industry. via the reaction MðOHÞn OHðÀÞ ¼ Àm MðOHÞðnþmÞ . Zabel. impurities in cane sugar. 1995. 2000). and • clarification of fruit juices. 1999. Conventional treatment processes The conventional process for treating liquid effluents containing metals ions is precipitation–aggregation (coagulation/flocculation)-settling as hydroxides or insoluble salts.2. whether diluted or not. A limiting feature of bubbles is the lifting power or carrying capacity. 1999. . dependþm ing on the metal. The main differences between ‘‘conventional’’ flotation of ores and flotation applied to water treatment are the following: • The method of producing the gas bubbles in order to generate micro. • removal of sulfur dyes. • volumes of sludge formed are too large and with a high water content. • Because the species floating are usually aggregated colloids rather than dispersed ones. • present novel separation concepts and flotation devices. This is important in the clarification of effluents and introduces distinct problems not previously encountered in mineral flotation. Rubio et al. 1992). 1998a. Main applications have been in the removal of the solids. 1999).

Advantages claimed are the clarity of the treated wastewater and disadvantages are the low throughput. • as a treatment unit on floating solids in thickeners (concentrates or tailings). bubbles characteristics in different flotation devices. Table 2 shows a partial list of current commercially available flotation devices for wastewater treatment and drinking water treatment units. Pd. 2001).b). 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. Table 1 Differences between flotation in mineral processing and in wastewater treatment Parameter Feed solids content (weight/weight basis) (%) Particle size to float (lm) Bubble size distribution (lm) Bubbles rising velocity (m hÀ1 ) Number of bubbles (cmÀ3 ) Bubbles surface area (cm2 cmÀ3 ) Air hold up (%) a Froth flotation of minerals 25–40 10–150 600–2000 250–800 (approximate values) 9 Â 103 –2 Â 102 100–30 15–25 Water and wastewater treatment < 4 (DAF) 10–30 (jet/columns) 1–50 (not flocculated) and 1–5 mm flocs (with polymers)a 30–100 (DAF) 100–600 (jet/columns) 0. They grouped different flotation techniques based on physicochemical and technological points and divided them in adsorptive or adhesive. • thicker flotation concentrates (6–12% w/w). 1998a. Applications. / Minerals Engineering 15 (2002) 139–155 141 • The type of separation: solid/solid/liquid in mineral processing and solid/liquid. 1999. Why flotation? Many advantages have been reported illustrating the technical and economical potential of this process: • high selectivity to recover valuables (Au. Conventional flotation techniques. usually flotation means an extra cost. among others. Depending on performance (water quality). Voronin and Dibrov (1999) have recently published a classification of flotation processes in wastewater decontamination. process water can be adequately treated and recycled. Zouboulis et al. residuals chemicals. • as a unit process for sludge thickening. • In mineral flotation it is necessary to produce a stable froth at the free surface of the flotation cell. such as bio-oxidation lagoons for reducing the cost of aerobic digestion. • In mineral flotation. • as a solid/liquid separation process in acid mine drainage neutralization with lime. less space needs. • as an auxiliary process to bio-oxidation lagoons or sludge thickening in water reuse. ink and fibers from water (Zabel.1. devices and processes Here some recognized techniques are summarized to show their main features. the overall process is economically attractive. thicker scums and sludge than in gravity settling or skimming and.b. • low operating costs with the use of upcoming flotation devices (Da Rosa et al. at an industrial scale.7–30 (DAF) 30–1000 (jet/columns) 6 Â 108 –2 Â 106 (DAF) 2 Â 106 –9 Â 103 (jet/columns) 4000–600 (DAF) 600–100 (jet/columns) 8–14 (DAF) 20–40 (jet/columns) Aerated flocs. solid/liquid1/liquid2 or liquid/liquid in water treatment. In applications to wastewater treatment an stable foam is not required. • as a primary treatment unit ahead of secondary treatment units. from water. savings in construction costs). In environmental application. pigments. ions.. 2. to date. 1992a. 2. • as a process for removing various organics. 1992. Rubio. • high efficiency to remove contaminants: high overflow rates.J. conducting solutions with the production of gas bubbles at both electrodes. Other differences are summarized in Table 1 comparing. A number of applications are reported without mention neither the type of equipment employed nor the bubble size distribution. including petroleum. low detention periods (meaning smaller tank sizes. Electro-flotation (EF) The basis for the micro-bubbles generation is the electrolysis of diluted aqueous. have been in the area of removal of light colloidal systems such as emulsified oil from water. . etc). Rubio et al. Pt..

suspended solids from food. volatile organic compounds. form a multitude of bubbles sizing from 700–1500 lm diameter. floatable solids It is a plug flow DAF device. aluminum ions are released from the anodes. inducing coagulation. induced-air BAF.3. is utilized also in the petrochemical industry. 1992). degassing. solids. • sludge thickening and separation of biological flocs. laundry. grease. aeration system that produces very fine bubbles Positive Flotation Mechanism (PFM). algae. with 20% more dissolved organic carbon (DOC) removed by electro-coagulation for the same Al doses (Andre et al. Dispersed (induced) air flotation (IAF) Bubbles are mechanically formed by a combination of a high-speed mechanical agitator and an air injection system. Dissolved air (pressure) flotation (DAF) Bubbles are formed by a reduction in pressure of water pre-saturated with air at pressures higher than atmospheric. animal feed contaminated waters For offshore operation the treated water discharges directly into the sea For treatment of laundry. dissolved air flotation processes – ‘‘Electrostatically’’ charged micro-bubbles ZEPHYRe IAF – using very fine bubbles Ultra-Float ADAF – plug flow DAF device High capacity DAF-filter system ISF – hydraulically operated gas flotation. dissolved oils. This method. food processing waters Vehicle washing effluents. introduced at the top. sludge thickener. food processing. ice-cream effluents. and the liquid become fully intermingled and. . air and grease For fat. 2. heavy metal. enabling flotation of the flocs. and hydrogen bubbles are generated at the aluminum cathodes. 2000). for oil–water separation (oily sewage) (Zheng and Zhao. IAF column Canadian Process Technologies WesTech OR-Tec Hydroxyl Industrial Systems Aeromax Systems Thermodyne Corporation PURAC Engineering Baker–Hughes Process ZPM Dissolved Air and Nitrogen (DNF) flotation systems HF IAF – uses a baffled. electrode costs and maintenance and the voluminous sludge produced. paper mill For oil/water separations. For food or industrial processing wastes Drinking water. An electrolytic coagulation/flotation (ECF) system has been also reported using reversible polarity aluminum electrodes. are produced just down-stream of the constriction (Bratby and Marais. 2. surfactants Canadian Process Technologies Vertical oil separation cell VOSCellR – using natural gas as a separating medium. 30–100 lm in diameter. humic acid...2. electroflotation BAF Flotation piles (underwater oil/water separator) – combines secondary treatment of produced water with disposal in one vessel CAF FF – flotation of aerated flocs Engineering Specialties Hydrocal Aquaflot the emission of H2 bubbles. 1977. Bulk water passes through the reactor and is treated by the coupled coagulation/ flocculation process. Laboratory scale tests have shown that the ECF reactor performs better than conventional aluminum sulfate coagulation when treating a model colored water. Rubio et al. and clouds of bubbles. Bennett. grease. Herein. 1988). The supersaturated water is forced trough needle-valves or special orifices. clarification Developed to remove oil and grease from produced water using natural gas as a separating medium Organic recovery flotation columns for reducing organic reagent and kerosene from rich electrolytes prior to electrowinning Wastewater treatment Flotation of fat. wastewater reclamation. vacuum BAF. 1993. The technology makes use of the centrifugal force developed.142 J. The gas. and optional skim storage components BAF – air-sparged BAF. DAF was recognized as a method of separating particles in the early 20th century and since then has found many applications including: • clarification of refinery wastewater. removal of oil. 5–7 lm oocysts. / Minerals Engineering 15 (2002) 139–155 Table 2 Examples of some commercially available flotation devices for wastewater treatment Supplier company Sionex Type of cell characteristics DAF Application details Wastewater treatment to remove suspended organic solids. screen printing. well known in mineral processing. after passing through a disperser outside the impeller. • separation of solids and other in drinking water treatment plants. Lazaridis et al. municipal and industrial waste streams Dissolved air flotation processes for solids. System in a completely enclosed flotation process For treatment of petroleum.

DAF development has been very rapid in the last decade and many of its earlier limitations are being solved. 2001) Year 1924 1960 1970 1990 1995 Development First generation: Pedersen cells. 4–5 lm cryptosporidium oocysts. Rubio. 1997. dissolved oils and VOCs (dissolved toxic organic chemicals). The conventional DAF unit. Rubio et al. • treatment of ultra-fine minerals (Gochin and Solari. Tessele et al. which Table 3 Main developments in dissolved air flotation (modified from Kiuru. 1988).. Da Rosa et al. • removal of organic solids. Bubbles are of the size 400–800 lm in diameter (Bennett. algae from heavily algae laden waters. Higher throughput 10–15 m hÀ1 Third generation: ‘‘Turbulent’’ DAF deep units.. humic water treatment. to develop a twophase mixture of air and water (Fig. 1999). 1996. but with micro-bubbles (Eades and Brignall. Column flotation 3.2. 1983). 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). Fig. 5–7 m hÀ1 DAF deeper with filters for the treated water. The DAF process (see Fig. 1988). • removal of algae. 3. with water recycle to the saturator.. are the following: • lower initial costs and energy use because a single pump provides the mixing and air supply. etc. • lower maintenance and longer equipment life because the unit has no high-speed moving parts to wear out. 1998a. high capacity cell > 40 m hÀ1 . 2 m hÀ1 . • removal/separation of ions. The ‘‘capture’’ of particles by bubbles occurs in an inclined zone aside of the froth (floated product) separation tank Second generation (‘‘conventional’’): cells less shallow with higher loading capacity. 1988.b. Gopalratnam et al. 1) is by far the most widely used flotation method for the treatment of industrial effluents. They resemble more the high capacity cells used in mineral processing. Advantages claimed for the nozzle units... The separation tank is shallow and very low throughput. / Minerals Engineering 15 (2002) 139–155 143 Fig. 2). Continuous nozzle flotation unit. Rubio et al. . over induced air flotation (IAF) systems. 1. It is believed that applications will rapidly expand in the waste treatment in the metallurgical and mining field (Rubio and Tessele.. 1999.1. 5–7 lm Giardia oocysts. 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. 1998. Table 3 reviews recent important developments in DAF. 2. in turn is discharged into a flotation vessel (similar to the dispersed-air conventional machines). Santander et al. Emerging flotation techniques and processes 3.J. Nozzle flotation (NF) This process uses a gas aspiration nozzle (an eductor or an exhauster) to draw air into recycled water. 1995) Column flotation is still a subject of great interest in mineral processing with a steadily growing number of research studies and industrial applications (Finch.

In wastewater treatment.. 2001). grease. etc. bubble accelerated flotation or BC. 1994). columns with internal baffles and coalescers for oil recovery (Gu and Chiang. 1990). 1995. with no moving parts. Problems with process accuracy have been recently solved and its use has been extended to wastewater treatment and recovery of solvent extraction liquors (Wyslouzil. 3. 2001). feed enters by the column top in the middle of the ‘‘concentrate’’ product.. 1992. the jet cell has low power consumption and low maintenance costs. Vacuum BAF. 4. feed slurry enters about one-third the way down from the top and descends against a rising swarm of bubbles generated by a sparger. 1994) and municipal waters (Yan and Jameson. 4) system uses the contactor–separation concept with very low detention times in the contactor (Colic et al. Applications of column flotation in the field of oil removal in production waters (Gebhardt et al. BOD. The air-sparged hydrocyclone (ASH). Yoon and Luttrell. Centrifugal flotation (CF) The separator and contactor can be an hydrocyclone or a simple cylinder.. 1994).3. 1991). New developments in column technology include external gas spargers operating with and without addition of surfactant or frothers. ‘‘bubble chamber’’ flotation device. Environmental applications of ASH flotation have been recently reported (Beeby and Nicol. 1991. 1994) and in the recovery of heavy metals precipitates (Filippov et al. Thus.. Jet flotation 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. Aeration occurs by either injecting air (or by suction). medium size bubbles having 100–1000 lm diameters are generated. More. 1999). high efficiency and moderate equipment cost (Clayton et al. 1991.. In the columns used in the mineral processing area. Clayton et al. a bubble-particle or aggregate disengagement zone (the tank proper pulp area) and a cleaning or froth forming zone (the tank proper zone). The Microcel flotation column. 1993). such as static mixers or nozzles According to Jordan and Susko (1992). 1991). 1988). The BAF. 2000) have been reported (Fig. 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 flow of the aqueous phase.. Rubinstein... 3. An advanced ASH type of flotation has been reported in applications to remove oil. Harbort et al. Rubio et al. 3. 3). Electroflotation BAF. In the presence of the surface-active reagents micro-bubbles can be obtained as in the Microcel column (Yoon et al. The bubbles (medium size) formed in this cell may have 100–600 lm in diameter (Jameson and Manlapig. Its main advantage is its high throughput. . Depending on the bubble generation system the authors report devices named as Induced Air BAF. can be classified as a centrifugal flotation unit (Ye et al. Finch and Dobby. / Minerals Engineering 15 (2002) 139–155 Fig. 1994.144 J.4. Fig. The cell consists of an aeration/contact zone (the downcomer). a centrifugal field is developed. through flow constrictions. BAF or bubble accelerated flotation (Fig.

and its subsequent removal by attachment to air bubbles to form a flotation ‘‘concentrate’’ (Huang and Liu. Zouboulis et al. Matis. However. 1992. 1991). Ciriello et al. Cavitation air flotation (CAF) Cavitation air flotation utilizes an aerator (rotating disc). 4. paint and tanneries to remove suspended solids.. Precipitate flotation This process is based on the formation of a precipitate of the ionic species. 1996. • ionic flotation (Scorzelli et al. 1992a. 4. 1999).2. Mummallah and Wilson. column and jet flotation (Jameson cell).3. especially in the milk industry. Save and Pangarkar. which range in size from 10 to 50 lm and provide a large amount of surface area. there is no knowledge of any fundamental work with this flotation technique. the precipitation may proceed via metal hydroxide formation or as a salt with a suitable anion (sulfide. it is believed that there may be other. 1989a. Stalidis et al. 2001. 1999. Rubio. etc. Lemlich. A number of papers have recently been published illustrating techniques employed and flotation devices. 1997. Despite the potential. not reported examples. 1962.b. 1998a..b. 1992. using a suitable reagent.. 1981).). 1982). no industrial applications are known and studies are mainly related to laboratory and pilot scale (Kommlapati et al. Schu 2000). Removal of ions The removal of ions from water. In the case of anion removal. 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. greases. tion (Nicol et al. Yet. • adsorbing particulate (colloids or aggregate) flotation (Zabel. Principal removal methods are: • precipitate flotation (Silva et al.1. McIntyre et al.. 4. CAF unit. precipitation should proceed through addition of a metal cation.b. 1993.. 1992. Lazaridis et al. who established ionic flotation in 1959. Rubio et al. These can be summarized as following: 4. Matis. 5).5. 1983). Gas aphrons flotation or colloidal gas aphrons (CGA) Sebba. 1992. oils.. CAF is utilized in the food industry. the separation of molybdenum ions (Marinkovic’. 1997. 1995. 1972. carbonate.J. Applications and advances Main industrial applications of flotation in mining and metallurgy are the recovery of solvent extraction liquors losses by DAF. 1994). / Minerals Engineering 15 (2002) 139–155 145 Fig. Pinfold. similar to those encountered in other industrial fields. 1972). Rubio and Tessele. Lemlich.. BOD (biological oxygen demand) and COD (chemical oxygen demand). • gas aphrons flotation or colloidal gas aphrons (CGA). fats. Walkowiak. 1972. 2001) and manganese ions by DAF (Krofta. is technically possible through various flotation techniques (Zabel. 5. 3. .. proposed the use of colloidal gas aphrons or micro-foams or simply micro-gas dispersions. 1993. Depending on the metal solution concentration. 1982). 1992. 1995).. This produces very small bubbles. • foam flotation (Clarke and Wilson. which draws ambient air down a shaft and injects ‘‘micro-bubbles’’ directly into the wastewater (Fig. one of the most important issues in environmental problems today. ion flota€gerl.

Here NaDTC. but. with the polymer to form stable. 1989a. Heap leach liquor. Ion flotation 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.. Rubio et al. Main stages are the following: 1. 1992a. big and hydrophobic flocs.b. crystalline. A novel gold recovery scheme based on ion flotation has been developed.5. Foam separation or foam flotation This method is similar to ion flotation but uses an excess of a surfactant or a proper frother to produce a stable foam.1% v/v isopropanol frother) and the negative effect of the high strength (>10À3 M). Essentially. colloidal. LaCl3 or FeCl3 were the coagulants and Bufloc (Buckman). Despite many studies performed at laboratory and pilot scale. containing gold cyanide is reacted with a suitable surfactant and sparged using compressed air (Galvin et al. 4. The carrier can be a mineral particle. 3. Here the surfactants perform the dual role of frother and collector. 1992. was employed as precipitant. Up coming techniques and advances 5. Aggregation-DAF Precipitation. Scorzelli et al. flocs + micro (5–150 lm) and mid-sized bubbles (200– 600 lm) ¼ flotation by DAF and/or columns (nonturbulent regimes). Main finding are the high removal obtained for a metal collector ratio of 1:2 (98% with 0. (1999). only during the last few years have applications of this method in industrial scale been reported (Zouboulis et al. 1994).. frothers and surface tension was evaluated. 1992. ions + precipitant ¼ colloidal precipitate (3–10 lm). in all cases. aggregation phenomena and DAF operating parameters. Galvin et al. Here the substances removed may be ionic or molecular. colloidal precipitate + flocculant ¼ flocs ($1–3 mm).4. employing particles as carrier-sorbing (absorbing and/or adsorbing) material for the metal ion. Almost complete removal (> 98%) of the metal ions from solution was reported using DAF. a polymeric resin. studied the removal of Cd ions using sodium dodecylsulfate as collector and the effect of ionic strength (NaCl and Na2 SO4 ). 1983). 1992).146 J.1. The use of microorganisms as sorbing materials (biosorption or bio- . Adsorbing colloid flotation This method involves the removal of the metal ion by adsorption on a precipitate (coagula) acting as a carrier. This resembles oxide flotation activation by metal ions... activated coal or a by-product. 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 float readily. Process efficiency depended on the system solution and interfacial chemistry. 1998) using DAF. facilitating the adsorption of the colligend species onto the surface of an air bubble. 5. 2. Then. Sodium oleate is also added to enhance hydrophobicity and process kinetics.b). In some cases. Nicol et al. Hundreds of parpers have been reported on foam/flotation or fractionation at laboratory and pilot scale and some industrial applications are believed to exist. As and Se ions from processing streams of gold cyanidation circuits (Tessele et al. The interesting feature is that this plant uses a ‘‘rougher’’ stage to remove first the suspended solids and calcium ions (as calcium oleate) and then the Mo ions in a ‘‘cleaner’’ stage at pH about 5. the flocculant. 1994). sodium dithiocarbamate.. thereby providing an interface for ion pairing to selectively collect the gold complex.. This method has been successful in separating the molybdenum ions from Cu–Mo concentrate filtrates and meeting Chilean emission standards. 5. 4. 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. coagulation is used to enhance particle size and finally. The main carriers used have been ferric or aluminum hydroxides collected with the help of sodium oleate or lauryl sulphate (Stalidis et al. or cellular in nature. The surfac- tant adsorbs at the surface of the rising air bubbles. anion or organic by readily floatable particles. / Minerals Engineering 15 (2002) 139–155 4. A recent DAF process to remove molybdenum ions in Chile employs this principle with the FeðOHÞ3 as the molybdenum carrier and sodium oleate as collector has been reported. Adsorbing (or sorbing) particulate flotation-APF or simply carrier flotation-CF The basis of the adsorptive (or sorbing) particulate (or carrier) flotation is the uptake of cation. sulfide depression by anions or adsorption of collectors or frothers.6.. they must selectively attach to the air– liquid interfaces (of foams or of bubbles) (Clarke and Wilson. The loaded carrier is then floated. Nicol et al. usually assisted with a suitable ‘‘collector’’ surfactant. APF is a variant of the adsorbing colloid flotation process. coagulation and flocculation have been utilized in stages first to destabilize highly soluble ions to form colloidal particles or precipitates. a ligand-activator for the flotation of the metal ion followed by a suitable surfactant has been necessary (Walkowiak.2. This technique has been reported to remove Hg.

Recently. Zn and Ni from diluted solutions by APF was studied at laboratory and pilot scale (F eris. (1993) Zouboulis et al. no collector or froth is required but a thick and stable float layer is formed. 1993) Zouboulis et al. flow rates. / Minerals Engineering 15 (2002) 139–155 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. Results showed that best separation was obtained when optimizing medium pH. by pumping the flow fluid through a venturi or needle valve. 2001). Crþ6 ions Author(s) F eris (2001) Rubio and Tessele (1997) Tessele et al. A very important feature only reported for DAF. 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. (1997) F eris et al. the minimum saturation pressure required for DAF to occur was found to be 3 atm. Thus. They conclude that the precipitate flotation effectiveness in columns is related to floc stability under turbulence created by the swarming of rising bubbles. Conventional DAF flotation was studied as a function of saturation pressure in the absence and presence of surfactants in the saturator. air is drawn into the pipe and bubbles are produced.. This behavior was found to occur in both batch and pilot DAF operation tests and almost complete recovery of the precipitates was attained. Thus. (2001) 147 sorptive flotation) has been proposed and may be another alternative (Zouboulis et al. (1998) Zouboulis et al. (2000) studied the interactions between superficial feed and gas velocities and recycling pulp flow rate on bubble size distribution and its effect on Mo-precipitate flotation. Best results (> 95% removal) showed that the residual ions concentration is below the standards limits dictated by the local legislation. This explains the fact that in DAF. Zn Ni. part of the dissolved air in water. 2001). (1993) Duyvesteyn and Doyle (1995) Zouboulis et al. (1993) Zouboulis et al. Cu. (1992a. Table 4 summarizes main reported studies in this subject.4. apart from particles/bubbles collisions and adhesion. 1992) with feed entering by the cell top (to improved solid/liquid separation) was studied to float loaded (with metal ions) FeðOHÞ3 precipitates as a function of pH (Souza and Rubio.3. Without surfactants. which make separation easier. Cu. As Cu Pb Ni Cu Cd Dye (Rodamine B) Oil Emulsified oil Chromate. More. The sorbing used was a coal washing tailing material from a coal industry from south of Brazil and the flotation process applied was DAF. 5. was rio de Tecnologia Mineral e studied at the Laborato Ambiental (F eris and Rubio. Se Cu. . bubble entrapment into flocs or coagula and aggregate entrainment by the rising bubbles are mechanisms. etc. by lowering the air/water surface tension in the saturator. This mechanism is independent on surface hydrophobicity and allows flotation of hydrophilic particles. But. The removal of Cu. However. Zn Hg. 5. Since the saturation stage accounts for about 50% of the total operating energy costs and considering the low cost involved in the surfactant. The size of the bubbles can be modulated with addition of a surfactant. addition of sodium oleate (as ‘‘collector’’) and operating parameters. which does not convert into bubbles in the nozzle. remains in solution and ‘‘nucleate’’ at the particle surface (Solari and Gochin. 1999). (1999) Santander and Rubio (1998) Santander and Rubio (1998) Lazaridis et al. in DAF. among others conditioning. Dissolved air flotation DAF of iron hydroxide precipitates at working pressures lower than 3 atm.J. DAF was possible at a saturation pressure of 2 atm. The column employs water treated recycling procedure to generate bubbles.b. concerns with the mechanisms of bubble/particle (aggregates) interactions other than the common adhesion through hydrophobic forces (Fig. unpublished results). using modified flotation units to improve the collection of fragile coagula. this option appears to have a great potential. Filippov et al. Results show high clarification effluents are obtained in DAF. 6). Column flotation to remove ions A modified Microcel column (Yoon et al. 1992).. a major disadvantage is that rapid air bubble levitation speed is not attainable and hydraulic loadings are low (this is dictated by the Henry’s law) reducing and limiting process capacity. As. Rubio et al.

. flotation can reduce organic losses and reduce potential environmental problems. . Bubble-particle mechanisms in DAF: (a) particle–bubble collision and adhesion. 5. DAF employs microbubbles (30–100 lm). 5. The flotation separation of very fine oil droplets (2–30 lm) is even more complicated and usually requires fine bubbles. Here the flotation devices are used in the discharge aqueous streams from the solvent extraction–electrowinning (SX–EW) plant to recover the organic liquor lost by entrainment into the aqueous phase. 1995). type and concentration of destabilizing agents for o/w emulsions and the type of flotation technique to be employed (Bennett. Most of the research studies on the separation of oil from water have addressed the effect of oil concentration. In the mining–metallurgical industry. this process is inefficient when treating high volume effluents and high flow-rates. Rubio et al. Thus. 1988). with highly emulsified feeds having up to 603 mg lÀ1 of oil. emulsified or in solution in water in concentrations up to 1000 ppm. / Minerals Engineering 15 (2002) 139–155 Fig. 1983). the presence of emulsified oil in water droplets around 50 lm in size causes problems in phase separation by conventional techniques (oil/water gravity separation. 1988). quiescent hydrodynamic conditions in the cell separation zone or emulsion breakers prior to flotation (Gopalratnam et al. (c) micro-bubble entrapment in aggregates. the removal was almost constant at or greater than 80% regardless of the initial oil content. Strickland. It is believed that this type of flotation cell has a great potential for oil or organic solvent removal at high throughput values (>600 m dÀ1 ). 1993). Results show that this cell is more accurate than the conventional cell yielding high oil removal values and treated water with low oil levels. Belhateche. because retention times are higher (20–60 min). 6. column flotation with CGA (prereagentized gas bubbles) and conventional columns are now being utilized in solvent extraction plants (Readett and Clayton. residual oily wastewaters commonly discharged are waters containing flotation chemicals and solvent extraction reagents. enters a cylinder obligating the coalesced or flocculated oilbubbles aggregates units to leave the separation tank by the froth layer. Oil in water may be dispersed. especially when. which makes the process very slow. DAF). The process has low retention times. the slurry abandoning the downcomer. have been used extensively in the removal of stable oily emulsions (Bennett. In particular. 1988. Separation of oils and organic compounds by flotation The flotation of organic bearing waters such as oil spills on water. oily sewage or oil-in-water emulsions has been used in various fields for a number of decades but is not commonly used in the mining and/or metallurgy industries. treating high flow-rates. Thus. Conversely. 7).6. Modified jet flotation cell A modified jet flotation cell has been studied in our laboratory (Fig. normally <5 min.148 J. 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. IAF and DAF. and quiescent regimes.. surface waters contaminated with free wasted oil and process waters containing oil spills (Pushkarev et al. 1980. However.5. IAF utilizes bubbles between 40–1000 lm in size and turbulent hydrodynamic conditions. This is due to collection and adhesion factors. (d) bubbles entrainment by aggregates. The Jameson cell. (b) bubble formation at particle surface.

Brazil. 1997. high separation efficiency and low water split. Rubio et al. Universidade Federal do Rio Grande do Sul.J. Feed oil concentration ¼ 152 mg lÀ1 . 9. are Fig. The FF-flocculation-flotation process 5. The LTM-centrifugal flotation device. 5. Main characteristics are the very low residence time (high throughput). However. Effect of flocculant concentration on oil centrifugal flotation performance ð33:3 l minÀ1 Þ. 1998). 8. which rapidly ‘‘float’’. The device will be A new turbulent on-line flocculation system assisted with air bubbles has been developed at LTM yielding aerated flocs (flocs with entrained and entrapped bubbles). / Minerals Engineering 15 (2002) 139–155 149 Fig. . Modified jet flotation pilot unit (Santander and Rubio. 8) has been rio de recently performed on a pilot scale in the Laborato Tecnologia Mineral e Ambiental (LTM). 7. These flocs.7. Fig. 9) depends mainly on the degree of flocculation and on the vortex finder clearance. in the very near future placed on offshore platforms in Brazil. the flotation efficiency (Fig. Centrifugal flotation cell The separation of flocculated (coalesced) oil emulsions in a centrifugal flotation machine (Fig.8.

. 6. Alga cells such as Microcystis sp. formed only in the presence of high molecular weight polymers and bubbles and under high shearing in the flocculator (Fig. The ‘‘multibubble’’ flotation column Recently. These authors named this column flotation device a ‘‘multibubble column’’. 11 shows some details of this flotation device. Using this modified microbubble column they reported better results as compared to DAF alone. while nonionic or anionic polymers are not. Cationic polymer flocculants are found to be effective. Alga removal by flotation is becoming a Schu good alternative to other treatment methods in tropical countries. that occur commonly in wastewater maturation ponds are usually very small in size (3–7 lm) and to induce efficient alga cell–air bubble contact. Miscellaneous separations 6. Fig.1. In such environments. €gerl. the algae grow at a great rate causing problems in all water reservoirs. The aerated flocs are large units (some millimeters in diameter) having an extremely low density (Rubio.150 J. proliferation of algae in maturation ponds often results in values exceeding EPA license limits for suspended solids and elevated pH values. Furthermore. Microcystis. (2001) reported data on the removal of colloidal ferric hydroxide by flotation in a column with bubbles generated in an static mixer (medium-sized bubbles) and micro-bubbles generated as in DAF..g. Also. The air excess air leaves the flotation tank (a centrifuge) by the top and the flocs float after very short residence times (within seconds). for many years. 10). 10. F eris et al. FF-flocculation-flotation device. 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. 1989. Different types of algae appear to share common surface characteristics.9. aggregates of greater than 10 lm in size are required. but of algae and other micro-organisms (Smith. 2000). 2001). Gains reported were a better air-to-solids ratio (higher bubble surface flux). Micro-organisms It has been demonstrated. The jet flotation process for alga removal reported by Yan and Jameson (2001) appears to be an interesting application of flotation for the treatment of algae bearing municipal waters. improved process kinetics and improved process throughput. Rubio et al. that bacteria can be readily concentrated by froth or foam flotation and since that time a number of investigators have confirmed not only the flotation of bacteria. / Minerals Engineering 15 (2002) 139–155 Fig. Anabaena). 5. discharge of algae (especially blue-green algae) laden effluents can also cause possible release of their associated toxins to surface and ground waters. The same flocculant was found to be effective in flocculating very different types and forms of alga cells (e.

can be removed from water by DAF flotation after precipitation and flocculation (Schneider et al. tannic acid. Most of the studies are based on ink removal using surfactants and calcium bearing salts. showing and discussing a variety of approaches used to optimize the characteristics of such flotation systems. 6..J. which include sodium lignin sulfonate. process selectivity is a difficult task.. no systematic investigations on removal of these substances from soil by flotation have been reported.5. 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. Soil washing Flotation is being studied for removal of toxic and relatively non-volatile hydrophobic compounds such as heavy oil. 6. The effects of the basic parameters of the process have been investigated and compared with soil washing. 1996).2. plastics vary in their hydrophobicities and their critical surface tensions have been explored using surface-active reagents. However. 6. The ‘‘multibubble’’ flotation column. which are primarily . polycarbonates. Thus. and Aerosol OT (Shibata et al. Rubio et al. or PCB from contaminated soils. 1995). 6. Proteins Various other non-fatty organic materials. their floatabilities can be modulated by use of suitable depressants. and the advantages of flotation demonstrated (Ososkov and Kebbekus. Most of the commonly used plastics. PAH. Soluble protein removed by this process from aqueous waste streams from soybean plants can potentially be used as supplemental animal feed. in paper deinking for paper recycling.4. such as polyvinyl chloride. for a number of years. polyacetal. 1997). / Minerals Engineering 15 (2002) 139–155 151 Fig. Deinking Flotation has been used. The basis for protein separation by flotation is the aggregation of the macromolecules with inorganic salts and/or polymers and flotation with micro-bubbles. Some limited reports in the literature point out that a significant fraction of toxic hydrophobic organics may be removed from contaminated soil by flotation. 11. Plastics Modern industrial and home use of plastics has created an environmental need to recycle waste plastics of a number of different types. such as soluble proteins derived from soybean processing.3. Thus. and polypropylene ether are naturally hydrophobic and are readily floated without addition of a flotation collector. Hydrophobic non-volatile organic compounds are poorly adsorbed by soil particles. However. Finch and Hardie (1999) have reviewed the main flotation machines and techniques employed in this area.

the bulk of material to dispose of in a waste repository is much reduced. Removal of radioactive nuclides from soils Flotation of radioactive nuclides from contaminated soils and coral sand by both conventional-induced air flotation and column flotation has been studied and evaluated (Misra et al. Fig. / Minerals Engineering 15 (2002) 139–155 hydrophilic. or adTable 5 Averaged hydraulic loading values reported for some flotation devices operating in mineral processing (Ã) and wastewater treatment Equipment DAF IAF (induced air) Column cell Jameson (jet) cell ASH (Miller cyclone) FF-flocculation flotation BAC Hydraulic loading (m hÀ1 ) 7–40 36–430Ã 50–360Ã 70–350Ã 500–720Ã 140–2160 (oil removal) 1. Thus.. Rubio et al. These contaminants are mainly trapped in the soil pore space. complexed. • The nature of pollutants. Misra et al. DAF ¼ Dissolved air flotation. but a low-grade concentrate. volatile. EF ¼ Electroflotation. but is still a low-level radioactive material. Soil organic matter or hydrophobic impurities in soil matrix adsorb some of hydrophobic pollutants. Flotation techniques/devices operating with ‘‘micro-bubbles’’. 12. inorganic-organic or mixtures. However. Some of these factors are the following: • The wastewater flow-rate (m3 hÀ1 . m3 sÀ1 or m3 dayÀ1 ) and the equipment throughput. Their concentration in effluents and in standard emissions. whether in the form of coagula. Trapped compounds can be transported to the surface of soil/water slurry by bubbles during flotation. Table 5 shows examples of some reported values for flotation hydraulic loading Theses values are related to the bubble size distribution generated in the different flotation devices (see Figs. CAF ¼ Cavitation air flotation. 12 and 13). whether free. flotation may remove only part of the adsorbed pollutants. GA ¼ Gas aphrons. 6. Flotation techniques/devices operating with ‘‘medium sized’’ (200–800 lm) and ‘‘macrobubbles’’ (IAF > 800 lm). • The nature of aggregates to be removed.152 J. . 1995. capacity and the techniques to be employed. In such separations it is desired to produce a very clean material (non-float) and a concentrate that contains most of the radionuclides. Final remarks Since the flotation depends on multiple interconnected factors.5–500 7. sublate (metal-collector complexes). 1996).. The goal is high recover. many considerations should be taken into account when selecting a flotation device and its Fig. Experimental studies will define the best way to remove the pollutants. flocs. 13.6. precipitates.

1995. Dobby.D. 1999. 2000. From air-sparged hydrocyclone to bubble accelerated flotation: mineral industry technology sets stage for development of new wastewater treatment flotation.. 1983. 32–51. 2001. Joussemet. F eris. Flocs and particulate carriers and not coagula withstand shear and may be separated in flotation devices operating with high turbulence (centrifugal. 1999.. A cross fertilization of flotation experience in mineral flotation and in wastewater treatment should lead to new and improved procedures in the mineral and metallurgical industry.K.A.).A. Load and froth flotation of a chelating ion-exchange resin. F. 1977. J. 1995.. especially in the mining and metallurgical industry. S. DAF is more amenable for separation of coagula or precipitates. the chemical and petroleum industries and domestic wastewater treatment.... Proceedings of Global Symposium on Recycling. G.. Ciriello. Kelsall. Separation Science and Technology 17. I.. J. In: Proceedings of the 1994 Summer National Meeting... Minerals Engineering 12 (5). New York. Column Flotation. surface tension (frothability). Removal of heavy metals from aqueous solutions using microlgae dispersions. Nicol. F. Brandon.T. M. Solid/Liquid Separation Equipment Scale-Up. air hold up. Morse. G. Foam Flotation: Theory and Applications (Ed. Matherly. 2123–2132. J. pp.V. Engel. M.).J. J. J.A. Clayton. 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... D.. Water Science and Technology 8. Marcel Dekker. Nevertheless. Hardie. Filippov. (Eds. F eris. Counter-current dissolved air flotation/filtration. first ed Pergamon Press. An example of innovation from the waste management industry: deinking flotation cells..F. CO. Carty. Cundeva. 8. 84–92. 11. Ions and Minerals.J.. The removal of oil from wastewater by air flotation: A review. Schneider.. R. K.. 1983. Bubble spargers in column flotation. flotation devices should lead to new and better applications for remediation of mineral industry contaminated waters and solids. C52–58. R.. Miller. Hager.J.. Deluise. Peters. viscosity. Rodrigues. CRC Critical Review in Environmental Control 18 (3). 173–178.. Belhateche. J. Rubio. Environmental Progress 7. 61–65. M. pp. Aproveitamento de subprodutos do beneficiamento de carv~ ao mineral na remoc ao de poluentes por sorc ao-flotac ao ß~ ß~ ß~ FAD. Choose appropriate wastewater treatment technologies. K. 1079–1086. Galvin. (Ed. 141– 145. Upland Press. R. M. L..A. Gochin.L.. 1993. Wastewater treatment by non-conventional flotation. 1982. 12 and 13 show approximate bubble size ranges.. 467–475. W.. Nicol. 37–51. N. vol. J. In: Purchas. Solari. 587–602. L.. D. paper No.. S.. Column flotation: a selected review-part IV: novel flotation devices. density. S.. Da Rosa. Transactions of the Institute of Mining and Metallurgy.A. pp. residence time. Dissolved air flotation (DAF) performance at low saturation pressures.. Chemical Industries. UEF Conference. T. EPSRC.. (Ed. Journal of Serbian Chemical Society 62 (6). 1999. 432 pp.. Filtration and Separation 36 (9). R.. 29b.. D. Gebhardt. 1994. San Sebastian/Spain. 2000.D. Brazil (in portuguese). J. R. Bratby. 2000. Furthermore.J..J. lifting power of bubbles. Rio de Janeiro. The simultaneous removal of oil and heavy metals from industrial wastewaters by joint precipitation and air flotation. C. 14–17 August.E. • The need for collectors. Mankosa. F eris.. Minerals Engineering 8 (6). 155–168. DAF of aerated flocs is also a good and fast alternative. 189–253. redox conditions. 512–519. C. Rubio. air-to-solids ratio.).. (Eds. Optimizing dissolved air flotation design and saturation. 1995.. Graham. A. In: Proceeding of 19th Congresso Brasileiro de Engenharia Sanit aria e Ambiental.J. G. in press. Dias de Souza. 123–129... bubble surface flux. UFRGS.V.S. T.. 1990.A. Remoc ao de corantes em ß~ efluentes do tingimento de  agatas por flotac ao de part ıculas ß~ adsorventes. G. J. International Journal of Mineral Processing 42. effect of temperature. L. L. Wilson. 145–152. Colic. S. Rubio et al....W. the introduction of new. Rodrigues. Separation Processes: Heavy Metals..A.A.H. 2001.. Bennett. Minerals Engineering 4.G. 925– 933. Manlapig.. J. Figs. Filtration and Separation 30 (2). Marais. 523–530. J. D.. economics of the process.T.... Houot. G. In: Gaballah. Tahoe City. 75–98. In: Proceedings of the Froth Flotation/Dissolved Air Flotation: Bridging The Gap.. Finch. J.. L. G. hydrophobicity). E.. 1999. Sect.H. R. Chemical Engineering Progress 91 (8). 1988. F eris.. 2001. Stafilov. Conclusions Flotation is ever increasingly used in waste treatment. Denver.. Bennett. Whether a ‘‘rougher-cleaner’’ scheme is needed: destiny of the floated product and the process water (possible reuse?). Morse.P.O. Waste Treatment and Clean Technology – REWAS ’99. jet). References Andre. Water Science and Technology 31.E. TMS.F. Precipitate flotation of lead and zinc and their determination by atomic absorption spectrometry. interfacial properties of aggregates (charge. Barnett. AIChE... C. The development and application of the Jameson cell.. Flotation. Hubred. Finch. filtration characteristics. Eades. Jameson. 1994. drying. G. L.R. S. pp. Porto Alegre. M. The potential for reagent recycle in the ion flotation of gold cyanide-a pilot scale field trial. R. 1997. Oxford. W. Solozabal.W. Ph.).. C. Duyvesteyn.J. .D. Removal of oil produced water by Microcele column flotation. which have been reported in various flotation devices and techniques. optimal pH. superior. Rubio. TMS – Inasmet.K. Clarke. J. Gopalratnam. Rubio. 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