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Full Terms & Conditions of access and use can be found at https://www.tandfonline.com/action/journalInformation?journalCode=lsst20 Separation Science and Technology ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lsst20 Direct hematite flotation from an iron ore tailing using an innovative biosurfactant Andreza Rafaela Morais Pereira, Ronald Rojas Hacha, Maurício Leonardo Torem, Antonio Gutierrez Merma, Flávia P.C. Silvas & Abhilash A To cite this article: Andreza Rafaela Morais Pereira, Ronald Rojas Hacha, Maurício Leonardo Torem, Antonio Gutierrez Merma, Flávia P.C. Silvas & Abhilash A (2021): Direct hematite flotation from an iron ore tailing using an innovative biosurfactant, Separation Science and Technology, DOI: 10.1080/01496395.2021.1873374 To link to this article: https://doi.org/10.1080/01496395.2021.1873374 Published online: 17 Jan 2021. 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Silvasb, and Abhilash Ac aDepartment of Chemical Engineering and Materials, Pontifical Catholic University of Rio De Janeiro Rua Marquês de São Vicente 225, Gávea, Brazil; bInstituto Tecnológico Vale, Ouro Preto, Brazil; c CSIR-National Metallurgical Laboratory, Jamshedpur, India ABSTRACT The use of a biosurfactant (BS) in mineral flotation offers numerous advantages over conventional surfactants, such as their low toxicity, high degradation kinetics, and potential for selectively treating low-grade ores. In the present study, the use of a biosurfactant obtained from Rhodococcus opacus bacteria for the flotation of hematite from iron ore tailings was evaluated. The microflotation assessments were conducted in a modified Partridge-Smith cell, and the batch flotation studies were conducted in a mechanical cell (CDC – cell). In addition, the effects of the pH, biosurfactant concentration, and depressant concentration on hematite recovery were evaluated. The results confirmed the biosurfactant adsorption onto the hematite surface, and the biosurfac- tant decreased the surface tension of the water/gas interface. The critical micelle concentration (CMC) of the biosurfactant was approximately 1 g.L−1. Hematite recovery was feasible at a pH of around 3. In microflotation tests, the iron grade and recovery reached approximately 37% and 30%, respectively. These values increased in batch flotation circuits, specifically in the cleaner stage, the iron grade reached approximately 44% and the recovery was approximately 65%. Thus, the current development proved that this particular treatment of ore tailings carries environmental and technical benefits as an appropriate alternative cleaning technology. ARTICLE HISTORY Received 7 September 2020 Accepted 4 January 2021 KEYWORDS Iron ore tailings; bioflotation; biosurfactant; Rhodococcus opacus Introduction Deposits of high-grade iron ore are being depleted by increasing mining production. Consequently, low-grade ores are being mined, generating higher volumes of iron ore tailings, which occupy large areas and can cause substantial ecological problems.[1–4] To control environ- mental damage and replace conventional reagents, so- called green flotation reagents for processing low-grade ores and ore tailings for reuse have been developed[5–8] in recent years. Bioflotation can be used as a clean option to process the above materials. In bioflotation, micro- organisms (bacteria and yeasts) and biosurfactants (extracted from microorganisms) are used in the mineral concentration process.[9–11] The biosurfac- tants are surface-active organic molecules produced by microorganisms that have hydrophilic and hydro- phobic groups. Most of them are neutral or anionic, and they range from small fatty acids to large poly- mers. They are biodegradable, less toxic than syn- thetic surfactants, stable under extreme temperature and pH conditions, and may in the future, partially or completely replace the chemical reagents currently in use.[12–15] Several works have shown the potential uses of bio- surfactants (BSs) in flotation processes.[13,16–18] Khoshdast et al.[14] studied the use of Rhamnolipid pro- duced by Pseudomonas aeruginosa MA01 strain as a biosurfactant, specifically as a frother in the flotation of copper ore, and the results showed that the Rhamnolipid biosurfactant presents significant froth- ability, and its surface activity was compared to those of the frothers DF-250 (propylene glycol) and MIBC (methyl isobutyl carbinol). Didyk and Sadowski[19] used biosurfactants produced by Bacillus circulans and Streptomyces sp. for the flotation of serpentinite and quartz. The results showed a decrease in surface tension, the adsorption of the biosurfactants onto the quartz and serpentinite surfaces, and, consequently, an increase in the floatability of the two minerals. Olivera[20] studied the use of the biosurfactant from Rhodococcus erythro- polis for the flotation of a quartz-hematite system. The results showed high adsorption of the biosurfactant on the hematite surface at a pH of 3, presenting a hematite recovery of approximately 99.88%. Puelles[21] studied CONTACT Maurício Leonardo Torem torem@puc-rio.br Department of Chemical Engineering and Materials, Pontifical Catholic University of Rio De Janeiro Rua Marquês de São Vicente 225, Gávea, Brazil. SEPARATION SCIENCE AND TECHNOLOGY https://doi.org/10.1080/01496395.2021.1873374 © 2021 Taylor & Francis Group, LLC http://www.tandfonline.com https://crossmark.crossref.org/dialog/?doi=10.1080/01496395.2021.1873374&domain=pdf&date_stamp=2021-01-17 hematite flotation using a biosurfactant extracted from Rhodococcus opacus. The author observed a maximum hematite floatability (approximately 95%) at a pH of 3 and high adsorption of the biosurfactant on the hematite surface. The recent trends and potential uses of micro- bial on flotation were, recently, presented by Kinnunen et al.[22] This review article presents a nice assessment of the fundamental of microbial strains, their interactions with minerals and their effects on flotation. It was found no citations of research works dealing with biosurfac- tants related to the processing of ore tailings. So, one may suggest the novelty of current work. This work addresses the use of a biosurfactant extracted from Rhodococcus opacus, which is a bacterium from a nonpathogenic lineage of Nocardioform actinomycetales. This kind of bacteria is gram-positive, unicellular, chemoorganotrophic, and highly hydrophobic.[10,23] The biosurfactants in this kind of bacteria are amphipathic and have similar prop- erties to those of well-known synthetic surfactants.[24,25] Importantly, this field is still at an early stage of devel- opment. Most of the works found in the literature have used microscale systems, known as microflotation[6,,8,,20,,21,,26] and few works have been conducted on a larger scale.[27–31] Most important, at the present there have been no reportedapplications of this kind of biosurfactant to process iron ore tailings. Therefore, the objective of this paper is to evaluate the behavior of a biosurfactant extracted from Rhodococcus opacus in the direct flotation of hematite from an iron ore tailings and to better understand the behavior of the biosurfactant on a larger scale. Materials and methods Iron ore tailings sample Iron ore tailings samples were collected from a Brazilian ore processing plant after a reverse iron ore flotation process. The sample was dried at room temperature (35°C), homogenized, and quartered. A representative sample was characterized by differ- ent techniques. The chemical composition of the samples was determined by X-ray fluorescence (XRF) fusion with lithium tetraborate in a PW1480 spectrometer (Philips), while volumetric analysis with potassium dichromate was conducted to determine the total iron content. The X-ray diffraction (XRD) data were collected with a Bruker-AXS D5005 dif- fractometer to identify the crystalline phases present in the iron ore tailings. The granulometric analysis was performed using the wet-sieving method. For zeta potential analysis and Fourier transform infrared (FTIR) spectroscopy, a pure hematite sample was obtained in Minas Gerais, Brazil. This sample was crushed, pulverized and stored in a glass bottle prior to use in the experimental tests, and the parti- cles used in both analyses were smaller than 10 µm. Microorganisms and extraction of the biosurfactant Rhodococcus opacus bacteria were obtained from the Chemical, Biological, and Agricultural Pluridisciplinary Research Center (CPQBA – UNICAMP). The microor- ganism was cultivated in yeast malt glucose (YMG) culture medium consisting of (g.L−1): 20 g glucose, 5 g peptone, 3 g malt extract and 3 g yeast extract. The bacteria were incubated for 7 days in a rotatory shaker (CIENTEC CT-712) at 150 rpm, temperature (25°C) and pH 7.2. The procedure for the ethyl alcohol extraction of the biosurfactant can be found in Puelles.[21] The crude biosurfactant concentrate was stored at 4°C for a maximum of 15 days. Zeta Potential studies The zeta potentials of the hematite before and after interaction with the biosurfactant and sodium silicate were measured in a Malvern Zetasizer Nano instru- ment. The analyzed sample is the mineral-floated fraction from the microflotation studies. In this study, the mineral (particle size −10 µm) was condi- tioned at a pH of 3 using 1000 g.t−1 of biosurfactant and 300 g.t−1 of sodium silicate (depressant). After the flotation test, the sample was dried in an oven at 50°C for 8 h and then a sample (0.1 g.L−1) was resuspended in an electrolytic solution (10−3 mol. L−1 NaCl). The measurements were carried out at pH values between 2 and 14, the desired pH was obtained using HCl and NaOH. Surface tension Surface tension measurements were performed using the DC 200 Surface Electro-Optics tensiometer by the Nöuy ring method at 21 ± 2°C. The effects of solution pH (3 to 11) and biosurfactant concentration (0 to 2.23 g.L−1) were evaluated. Fourier transform infrared (FTIR) spectroscopy Infrared spectroscopy measurements were performed on a Scientific Nicolet 6700 FTIR spectrophotometer using the KBr pellet approach. Hematite samples were analyzed before and after interaction with the biosurfac- tant, and the fraction of hematite used for these tests had 2 A. R. M. PEREIRA ET AL. a particle size smaller than 10 µm. The mineral sample is the same as that used in the zeta potential studies. The ratio of the sample to KBr was 1/200 (wt./wt.). The collection of the sample spectrum was carried out at a resolution of 4 cm−1 using 360 scans. Flotation assessments The microflotation tests of the iron ore tailings were carried out in a Partridge-Smith cell (volume of 270 mL), and the biosurfactant was used to collect the hematite and the sodium silicate was used to depress the quartz. The batch flotation studies were carried out in a mechanical cell (CDC–cell) (volume of 800 mL). The details of the operating conditions used in the micro- flotation tests and batch flotation tests are indicated in Table 1. Regarding the batch studies, the tests were initially carried out in a single stage (rougher) and then using a flotation circuit (rougher, cleaner, and scavenger). Results and discussion Iron ore characteristics The results of chemical composition showed that the iron ore tailings sample had 13.85% Fe, and the XRF analysis corroborated these results (13.80%), can be seen in Table 2. This mineral composition was expected since the sample is from an itabiritic iron ore processing. The XRD analysis showed that the crystalline phase of quartz is a major phase, and the crystalline phase of hematite is a minor phase (Fig. 1). The size fraction analysis of the iron ore tailings sample showed that approximately 93% of the material was smaller than 106. Additionally, the sample pre- sented a P80 of 85 μm, and approximately 20% of the particles were smaller than 45 µm. Zeta potential studies Electrokinetic studies are important to elucidate the surface charge at the solid–liquid interface providing a helpful understanding of the flotation performance.[32] Considering this remark, Fig. 2 shows the zeta potential of hematite before and after interacting with the biosurfactant using potassium chloride (0.001 mol.L−1) as an indifferent electrolyte. The hematite IEP (isoelectric point) was attained at a pH of around 6.2.[33] This zeta potential profile shows the flexibility of hematite to interact electrosta- tically with anionic collectors in acidic media and cationic collectors in alkaline media. After condition- ing the hematite with the biosurfactant, the zeta poten- tial curve of hematite was dislocated to the left and presented a reversal charge point at around 3.6 (RCP1), the last elucidates a probable electrostatic interaction between the biosurfactant and the hematite surface. Several works have reported the same behavior, where zeta potential profile of hematite after interacting with the biosurfactant is shifted toward acidic pH values.[20,21] This can be explained by the higher con- tent of anionic functional groups than nonionic or cationic groups. The Rhodococci genus generally pro- duces trehalose lipid biosurfactants, which can be structurally diverse and often occur as complex Table 1. Experimental conditions for the microflotation tests and batch flotation tests. Conditions Microflotation Batch Flotation pH 3, 5, 7, 9, and 11 3 Concentration of BS 1000–8000 g. t−1 1000–8000 g.t−1 Concentration of SS 0–1200 g.t−1 0–1200 g.t−1 Sample mass 5 g 132.66 g (30% solids by mass) Agitation 300 rpm 800 rpm Volume 270 mL 800 mL Airflow rate 25 mL.min−1 Natural injection Ore conditioning time with the depressant 5 min. 5 min. Ore conditioning time with the collector 5 min. 5 min. Flotation time 5 min. 5 min. Table 2. Chemical analyses of the iron ore tailings sample through XRF. Sample Composition Fe (%) SiO2 (%) Al2 O3 (%) P (%) TiO2 (%) CaO (%) MgO (%) PF (%) Tailings sample 13.85 79.60 0.24 0.011reagent widely used in the mineral industry as a dispersant and as a quartz depressant. In the case of quartz depression, the depres- sant mechanism is believed to involve micelles of hydrated silica acid, [39] which adsorb onto the mineral surface. However, these silicate species can also be adsorbed onto iron oxide surfaces, which limits their separation efficiency.[40–42] This effect can be observed in the zeta potential profile of the hematite in the pre- sence of the depressant (Fig. 2). The zeta potential curve dislocated to the left and a second reversal charge point was observed at pH of around 4.2 (RCP2). This point indicates that the silicate interacted with the hematite surface, and this interaction was more relevant in an acidic medium. Under acidic conditions, silicic acid (Si(OH)4) and SiO2 are the predominant species; such species can adsorb on the hematite surface and are responsible for the characteristic depression of sodium silicate.[41,43–45] Therefore, if sodium silicate adsorbs on the hematite surface, then the biosurfactant will not be adsorbed, and as a consequence, the hematite would be depressed. Surface tension studies Figure 3.a presents the effect of the biosurfactant con- centration on the surface tension of the air/water inter- face at 21°C and pH 3, as determined by the Nöuy ring method. The surface tension decreased with increasing biosurfactant concentration, achieving a value of 36 mN. m−1 at a biosurfactant concentration of 1 g.L−1. The surface tension remained relatively constant when the concentration of biosurfactant was further increased, so this point was considered the critical micelle concentra- tion (CMC). Most biosurfactants extracted from the Rhodococcus genus reported a reduction in surface and interfacial tension relative to those achieved with syn- thetic surfactants at the same concentrations. This simi- larity may be attributed to the presence of substances that produce trehalose-containing glycolipids.[21,34,46] Other works have reported similar behavior, such as Puelles, [21] who studied the effect of the concentration of biosurfactant from Rhodococcus opacus on surface tension. The author observed a decrease in surface ten- sion from 72 mN.m−1 to 50.5 mN.m−1, and the CMC was found at a biosurfactant concentration of approxi- mately 92 g.mL−1. Rufino et al.[15] studied the effect of the biosurfactant produced by Candida lipolytica UCP 0988 on surface tension. The authors observed a reduction in the surface tension (from 70 mN.m−1 to 25 mN.m−1) with increasing biosurfactant concentra- tions. Didyk and Sadowsky[19] studied the biosurfactants produced by Bacillus circulans and Streptomyces sp. These biosurfactants were used for the biomodification of serpentinite and quartz surfaces. The biosurfactant 1 2 3 4 5 6 7 8 9 10 11 12 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 Ze ta P ot en tia l ( m V ) pH Hematite Hematite + Biosurfactant Hematite + Sodium silicate RCP 1 RCP 2 IEP Figure 2. Zeta potential curves of hematite before and after interacting with biosurfactant and sodium silicate. Particle size: −10 µm, [KCl]: 0.001 mol.L−1. 4 A. R. M. PEREIRA ET AL. produced by Bacillus circulans decreased the surface tension from 72 to 28.6 mN.m−1, and the biosurfactant obtained from Streptomyces sp. decreased the surface tension by up to 29.3 mN.m−1. Figure 3.b presents the effect of the pH on the surface tension of the water-biosurfactant solution. This evalua- tion was carried out at 21°C and a biosurfactant con- centration of 0.16 g.L−1. Low values of surface tension were observed under acidic and neutral conditions and reached values of approximately 35 mN.m−1. Higher pH values resulted in higher surface tension in the solution, reaching a maximum of 47 mN.m−1. The low surface tension values observed under acidic and neutral condi- tions may indicate that the biosurfactant has excellent surface-active properties. Under these conditions, it is likely that active species of the biosurfactant is more soluble, which contributes to the decrease in surface tension. Other causes, such as temperature, viscosity, electrolytes and time, can also interfere with surface tension measurements.[47] According to Christova and Stoineva, [38] the biosurfactants from the genus Rhodococcus can powerfully lower the surface tension of the water from 72 mN.m−1 to 19 mN.m−1 due to the surfactant properties of the trehalose lipids. Thus, this kind of bioreagent is suitable for use in flotation pro- cesses in which the biosurfactant interacts at the solid– liquid interface, resulting in modification of the mineral surface.[19] Fourier transform infrared (FTIR) spectroscopy Infrared spectroscopy has been widely applied to confirm the adsorption of chemical modifiers onto mineral surfaces since it can be used to identify the main functional groups present.[48–50] Fig. 4 shows the FTIR spectrum of the biosurfactant extracted from Rhodococcus opacus. The presence of some functional groups characteristic of conventional sur- factants can be observed, which indicates the poten- tial of this material as a biosurfactant. The absorption band at 3346.34 cm−1 may indicate the presence of hydroxyl groups (O-OH) and amine groups (NH).[18,48,51] The absorption region near 1629.52 cm−1 corresponds to alkene (C = C) and ketone groups.[21] The absorption region between 1500 cm−1 and 1300 cm−1 corresponds to the stretch- ing of the CH2 and CH3 groups.[18] The absorption 0,0 0,5 1,0 1,5 2,0 2,5 30 40 50 60 70 S ur fa ce te ns io n (m N /m ) Biosurfactant concentration (g/L) 2 3 4 5 6 7 8 9 10 11 12 30 32 34 36 38 40 42 44 46 48 50 52 54 ) m/ N m( noisnet ecafruS pH a) b) Figure 3. Effect of the biosurfactant concentration (a) and pH (b) on the surface tension. 4000 3500 3000 2500 2000 1500 1000 500 0 1 2 3 4 3.5 2.5 1.5 0.5 71 6. 22 94 0. 30 99 5. 24 10 40 .5 7 11 44 .9 2 14 05 .7 2 16 29 .5 2 29 31 .3 7 23 60 .9 333 46 .3 4 37 05 .1 9 46 5. 99 54 5. 42 10 84 .5 6 16 31 .9 2 34 26 .2 9 A bs or ba nc e Wavenumber (cm-1) Biosurfactant Hematite Hematite+Biosurfactant Figure 4. FTIR spectrum of the biosurfactant extracted from Rhodococcus opacus and hematite before and after interacting with the biosurfactant. SEPARATION SCIENCE AND TECHNOLOGY 5 band at 1040.57 cm−1 corresponds to the vibrations of the alkane functional groups.[21] The alkane, alkene, alcohol, and ketone groups may indicate the presence of mycolic acids, which are produced by Rhodococci [52] and could be responsible for the mineral hydrophobicity. Figure 4, also presents the FTIR spectra of the hematite surface before and after interacting with the biosurfactant. Absorption bands at 465.99 cm−1 and 545.42 cm−1 correspond to the stretching vibra- tions of the Fe-O group of the hematite. The spectra after interactions show different bands. The band at 3426.29 cm−1 indicates the presence of hydroxyl groups (O-OH) and amine groups.[18,48,51] The absorption peak at 1084.56 cm−1 corresponds to the asymmetric stretching of the phosphate groups (PO2) present in the phospholipids and nucleic acids.[18,48] The absorption band at 1632.92 cm−1 indicates the presence of alkene (C = C), carbonyl (C = O), and C = N groups.[18] Thus, the observed FTIR spectra indicate the pre- sence of certain functional groups characteristic of bio- surfactants on the hematite surface after the hematite- biosurfactant interactions. This would be indicative of biosurfactant adsorption and thus modification of the mineral surface properties. Puelles[21] reported similar absorption bands for the spectrum of hematite after interaction with a biosurfactant from Rhodococcus opacus. Microflotation studies Effect of the pH on microflotation One of the most important variable in flotation pro- cesses is the pH of solution, particularly, it can dee-ply influence the activation of the functional groups on the biosurfactant and the surface properties of the mineral.[18] Fig. 5 presents the effect of pH on iron recovery and grade using 4000 g.t−1 of biosurfactant in the absence of a depressant (sodium silicate). Up to pH 5, increasing the pH reduced the iron recovery but improved the iron grade; higher pH values nega- tively affected the iron recovery and grade. The iron recovery close to pH 2 was approximately 35%. This result could be attributed to the different organic substances, such as polysaccharides, fatty acids, phos- pholipids and amino acids, present in the biosurfac- tants that can be activated in this pH range contributing to the adsorption of the biosurfactant on the hematite surface. Puelles[21] and Olivera[20] studied hematite floatabil- ity using biosurfactants from Rhodococcus opacus and Rhodococcus erythropolis in Hallimond tubes, respec- tively. The authors observed that the highest floatability occurred at approximately pH 3. The authors explained that in an acidic medium, electrostatic attraction occurs between the mineral surface and the biosurfactant that contains anionic groups, resulting in the maximum adsorption and, therefore, the maximum recovery of hematite. Effect of the biosurfactant concentration on microflotation Figure 6 presents the effect of the biosurfactant concen- tration on the iron recovery and grade at pH 3 in the absence of sodium silicate. Increasing the biosurfactant concentration negatively affected the iron grade but favored recovery, presenting maximum grade (approxi- mately 37%) and recovery values at a biosurfactant con- centration of 6000 g.t−1; lower values were observed with higher concentrations. This result is in agreement with the surface tension studies, which showed a CMC of approximately 1 g.L−1. Previous microflotation experiments showed that the biosurfactants extracted from Rhodococcus erythropolis and Rhodococcus opacus act as hematite collectors. For example, Merma et al.[17] showed that the highest hema- tite floatability was achieved at pH 3, achieving 98% hematite recovery using a biosurfactant concentration of 50 mg.L−1. Puelles[21] achieved 95% hematite recovery at pH 3 using a biosurfactant concentration of 75 mg.L−1. Effect of the depressant concentration Figure 7 shows the effect of the sodium silicate concen- tration on the iron recovery and grade using 4000 g.t−1 of biosurfactant and at pH 3. Increasing the depressant concentration negatively affected the Fe recovery and slightly favored the iron grade. 0 5 10 15 20 25 30 35 40 45 50 55 60 Ir on g ra de ( % ) pH Fe recovery (%) Fe (%) 1 2 3 4 5 6 7 8 9 10 11 12 0 10 20 30 40 50 60 Ir on r ec ov er y (% ) Figure 5. Effect of pH on iron recovery and grade in Partridge- Smith cell in the presence of 4000 g.t−1 biosurfactant. 6 A. R. M. PEREIRA ET AL. According to the study of sodium silicates in aqueous solution by Yang et al., [43] when the concentration of silicate in solution increases, the distribution of silicate species becomes more complex, as dimers, trimers, oligo- mers, and colloidal SiO2 are formed under acidic condi- tions. Distribution diagrams presented by Wang et al.[53] and Zhang et al.[54] showed that Si(OH)4 and SiO2 are the predominant species in the acidic pH region. Silva et al.[55] observed colloidal silicate at low to moderate pH levels. Lopes et al.[56] explained that colloidal silicate can be responsible for depression through electrostatic forces and that silicate anions can adsorb onto negatively charged surfaces by chemisorption. Therefore, the hematite depres- sion under acidic conditions can be attributed to the silicate species, and the formation of these species impairs hematite recovery. Batch flotation studies Effect of the biosurfactant concentration on the flotation According to our results, different behaviors are obtained in microflotation and batch flotation, which could be attributed to different factors. According to Kim et al., [57] physical factors (e.g., shear force and the percentage of solids) are different at the two scales and can affect recovery, which explains the difference. Figure 8 shows the effect of the biosurfactant concentration on the iron recovery and grade at pH 3 in the absence of a depressant (sodium silicate). Within the range of 1000 and 4000 g.t−1, the biosurfactant concentration did not affect the iron grade, and concentrations above this range negatively affected the iron grade. The metallurgical recovery was improved when the biosurfactant concentration was increased from 1000 to 2000 g.t−1, and concentrations above this negatively affected the recovery. The decrease in recovery and grade was produced by the increase of the biosurfactant concentration to values around its CMC. Compared with anionic chemical collectors, the biosurfactant pre- sents behavior similar to AERO 825 (sulfonate), which achieved an iron grade of 57.90% at a concentration of 1200 g.t−1 under acidic conditions.[58] According to the literature, the biosurfactant is anionic, [38] and based on electrophoretic studies, the IEP of hematite is approxi- mately 6.2. Therefore, the hematite surface is positively charged, and the biosurfactant is anionic, allowing the formation of electrostatic interactions and enabling hematite recovery. 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 0 5 10 15 20 25 30 35 40 45 50 55 60 Ir on g ra de (% ) Silicate concentration (g/t) Fe recovery (%) Fe (%) 0 10 20 30 40 50 60 Ir on r ec ov er y (% ) Figure 7. Effect of the sodium silicate concentration on the iron recovery and grade in Partridge-Smith cell in the presence of 4000 g.t−1 biosurfactant at pH 3. 0 1000 2000 3000 4000 5000 6000 7000 8000 0 5 10 15 20 25 30 35 40 45 50 55 60 Ir on g ra de ( % ) Biosurfactant concentration (g/t) Fe recovery (%) Fe (%) 0 10 20 30 40 50 60 Ir on r ec ov er y (% ) Figure 8. Effect of the biosurfactant concentration on the iron recovery and grade at pH 3 in a CDC mechanical cell, single-stage (rougher). 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 0 5 10 15 20 25 30 35 40 45 50 55 60 Ir o n g ra d e (% ) Biosurfactant concentration (g/t) Fe recovery (%) Fe (%) 0 10 20 30 40 50 60 Ir o n r ec o ve ry ( % ) Figure 6. Effect of the biosurfactant concentration on the iron recovery and grade in Partridge-Smith cell at pH 3. SEPARATION SCIENCE AND TECHNOLOGY 7 Effect of the depressant concentration on the flotation Figure 9 shows the effect of the sodium silicate concen- tration on the iron recovery and grade at a biosurfactant concentration of 4000 g.t−1 and at pH 3. The silicate concentration had minimal influence on the iron grade, and the recovery increased slightly with increasing depressant concentration. The interaction of silicate with hematite can explain the low recovery and grade; under acidic conditions, the silicate species can interact with quartz and hematite at the same time. These interac- tions prevent interactions between the biosurfactant and the hematite surface, preventing the surface from becoming fully hydrophobic, which is reflected with low Fe recovery and grade. Lopes and Lima[58] studied hematite flotation on a batch scale using 1200 g.t−1 AERO 825 and 2100 g.t−1 sodium silicate, and a similar iron grade of 57.90% was achieved under acidic conditions. Flotation circuit assessments A flotation circuit evaluation was conceived in order to increase the iron grade of the concentrate, preliminary tests involving a flotation circuit were performed. In industrial flotation processes, different steps (circuits) are developed to achieve both high recovery and grade. Most of the time, the concentrate grade from a single flotation step is not high enough, requiring additional flotationstages. The flotation circuit tests were per- formed in three steps: rougher, cleaner, and scavenger. The tests were performed at pH 3 with and without the silicate (depressant of gangue); the operational condi- tions are presented in Table 3. RG=rougher; SCV=scavenger; CL=cleaner; BS=biosurfactant; SS=sodium silicate; Conc.=con- centrate; Tail.=Tailings According to the obtained results, the tests in the absence of the depressant presented better performance than was observed for the tests in the presence of silicate. In previous studies of batch flotation and microflotation, sodium silicate also depressed hematite, consequently decreasing hematite recovery.[20,55,59,60] The low perfor- mance in the presence of the depressant can be linked to the operating conditions, especially the acid medium. Under these conditions, different silicate species (colloi- dal silicate and silicate anion) interact with quartz and with hematite, which is discussed above. Higher 0 1000 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 Ir on g ra de (% ) Silicate concentration (g/t) Fe recovery (%) Fe (%) 0 10 20 30 40 50 60 70 80 90 Ir on r ec ov er y (% ) Figure 9. Effect of the sodium silicate concentration on the iron recovery and grade in the presence of 4000 g.t−1 biosurfactant at pH 3 in a CDC mechanical cell, single-stage (rougher). Table 3. Conditions of Flotation circuit in a CDC mechanical cell (pH 3). Conditions Step Mass Recovery (%) Fe Recovery (%) Content (%) RG SCV CL Si Fe BS (g.t−1) SS (g.t−1) BS (g.t−1) SS (g.t−1) BS (g.t−1) SS (g.t−1) Test 1 4000 0 2000 0 4000 0 SCV Conc. 5.76 18.11 17.63 43.56 SCV Tail. 79.04 26.77 43.60 4.69 CL Conc. 9.43 44.11 3.45 64.78 CL Tail. 4.74 7.80 31.51 22.78 Test 2 2000 0 1000 0 3000 0 SCV Conc. 5.04 18.27 13.16 50.26 SCV Tail. 84.88 43.81 41.96 7.15 CL Conc. 5.11 25.01 1.36 67.91 CL Tail. 3.94 8.58 26.59 30.16 Test 3 4000 600 2000 900 4000 300 SCV Conc. 5.41 15.01 21.06 38.42 SCV Tail. 84.22 31.24 43.30 5.14 CL Conc. 4.97 20.59 8.38 57.41 CL Tail. 3.86 5.73 33.00 20.55 Test 4 2000 600 1000 900 3000 300 SCV Conc. 3.11 8.13 22.56 36.19 SCV Tail. 91.44 47.19 41.96 7.15 CL Conc. 1.48 6.22 7.78 58.30 CL Tail. 3.01 4.85 31.81 22.34 8 A. R. M. PEREIRA ET AL. performance was obtained in test 1; in the scavenger stage, the iron recovery and grade were approximately 18% and 43.50%, respectively, and in the cleaner stage, the iron recovery and grade were approximately 44% and 65%, respectively. Conclusions The zeta potential studies showed that the IEP of hematite occurred at pH around 6.2. After condition- ing with biosurfactant and in the presence of sodium silicate, two reversal charge points were detected at pH of around 3.6 and 4.2, respectively. This charge reversal may suggest electrostatic interactions of the reagents onto the hematite surface. FTIR spectro- scopy indicated that after interacting with hematite, absorption bands belonging to the functional groups of the biosurfactant were presented onto the hematite surface. The surface tension results showed the reduction of the air/water surface tension after the addition of BS. The critical micelle concentration was approximately 36 mN.m−1 with a biosurfactant con- centration of approximately 1 g.L−1. Microflotation and batch flotation tests showed that acidic media, specifically pH 3, was a satisfactory condition for the recovery of hematite from the tailings. Under acidic conditions, the pre- sence of silicate provoked a drop in the efficiency of the process. This can be attributed to the presence of silicate species (colloidal silicate or silicate anion) that can also interact with the hematite surface. In microflotation, the highest iron recovery and grade were near 29% and approximately 37%, respectively. Flotation circuit results presented higher iron recov- ery and grades of approximately 44% and 65%, respectively. These results were obtained in the absence of the depressant. Therefore, the present research work shows bioflotation as a fruitful alter- native cleaning technology using the biosurfactant extracted from Rhodococcus opacus termed as a “green” collector for the recovery of hematite from iron ore tailings. Acknowledgements The authors acknowledge Vale Institute of Technology – ITV, CNPq (National Council for Scientific and Technological Development); CAPES (Coordination for the Improvement of Higher-Level Personnel), FAPERJ (Rio de Janeiro State Research Foundation), Pontifical Catholic University of Rio de Janeiro, and Technological Characterization Laboratory (LCT) – Department of Mining Engineering and Petroleum – USP for the financial and technological support. Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References [1] Praes, P. E.; de Albuquerque, R. O.; Luz, A. F. O. 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R.; Pereira, R. D.; Lima, R. M. F. Influence of Sodium Silicate on Floatability and Charge of Hematite and Quartz with Sodium Oleate. Latin Am. Appl. Res. 2013, 43, 189–191. SEPARATION SCIENCE AND TECHNOLOGY 11 Abstract Introduction Materials and methods Iron ore tailings sample Microorganisms and extraction of the biosurfactant Zeta Potential studies Surface tension Fourier transform infrared (FTIR) spectroscopy Flotation assessments Results and discussion Iron ore characteristics Zeta potential studies Surface tension studies Fourier transform infrared (FTIR) spectroscopy Microflotation studies Effect of the pH on microflotation Effect of the biosurfactant concentration on microflotation Effect of the depressant concentration Batch flotation studies Effect of the biosurfactant concentration on the flotation Effect of the depressant concentration on the flotation Flotation circuit assessments Conclusions Acknowledgements Declaration of interests References