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IN THIS ISSUE
• Improved nickel and cobalt recovery from laterites • Concentration of iron ore flotation tailings • Solvent extraction of zirconium using triphenylphosphine oxide • Full-scale continuous centrifugal concentrator • Copper losses in smelting slag dependent on slag composition • Organic binder for the pelletization of a magnetite concentrate • Ammonia separation of Ni from spent fly ash leach liquor • Flotation of zinc oxide minerals from low-grade tailings • Design and operation of a teeter-bed hydroseparator • Reverse flotation of diaspore from aluminosilicates
of the Society for Mining, Metallurgy, and Exploration, Inc.
Volume 27, Number 3 August 2010
PUBLISHING Mining technology SINCE 1871
2009 Transactions, vol. 326
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Improved nickel and cobalt recovery from nickeliferous laterites in acidic fluoride media
Wei Luo and Jiankang Wen: General Research Institute for Nonferrous Metals, Beijing, China Dianzuo Wang and Qiming Feng: Central South University, Beijing and Changsha, China
Pellet feed production via the concentration of flotation tailings
M.G. Vieira: Samarco Mineração SA, Ouro Preto, MG, Brazil A.E.C. Peres: UFMG, Belo Horizonte, MG, Brazil
Solvent extraction of zirconium from zircon leach liquor using triphenylphosphine oxide
K. Saberyan and E. Zolfonoun: Nuclear Science and Technology Research Institute, Iran P. Vahedian-Donyaparast: Islamic Azad University, Tehran, Iran M. Noparast and A. Nemati: Tehran University, Tehran, Iran
Performance of a full-scale continuous centrifugal concentrator in reconcentrating fine hematite from tailings
Luzheng Chen, Siqing Liu and Shuming Wen: Kunming University of Science and Technology Kunming, Yunnan Province, China
Copper losses in sulfide concentrate smelting slag are dependent on slag composition
Ž. Živkovic, I. Mihajlovic and Đ. Nikolic: University of Belgrade, Bor, Serbia N. Mitevska: Mining and Metallurgy Institute, Bor, Serbia
Laboratory study of an organic binder for pelletization of a magnetite concentrate
S. L. de Moraes: Institute for Technological Research, Sao Paulo, Brazil S. K. Kawatra: Michigan Technological University, Houghton, Michigan
Ammonia separation of Ni from spent fly ash leach liquor
N.-S. Kim: University of Texas at El Paso, El Paso, Texas S.-Y. Hwang: KEN Research Center, Seokyeong University, Seoul, Republic of Korea
Flotation of zinc oxide minerals from low-grade tailings by oxine and dithizone using the Taguchi approach
A. Hajati: Iran University of Science and Technology, Arak, Iran ˘ A. Khodadadi and S. M. Koleini: Tarbiat Modares University, Tehran, Iran
Design, operation and control of a teeter-bed hydroseparator for classification
J.N. Kohmuench, E.S. Yan and M.J. Mankosa: Eriez Manufacturing, Erie, Pennsylvania G.H. Luttrell and R.C. Bratton: Virginia Tech, Blacksburg, Virginia
Volume 27, No. 3
Reverse flotation of diaspore from aluminosilicates by a new cationic organosilicon quaternary ammonium collector
Xinyang Yu, Hong Zhong and Guangyi Liu: Central South University, Changsha, China
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there is the need to win metals from the abundant low-grade nickel laterite ores.3%) under the experimental conditions of particle size d50= 25 μm.8%). Deepatana et al.% NaF) gave a markedly enhanced metal extraction rate (Ni 81. 2005. 2006).China.. Hirasawa et al. reaction temperature 90°C. X-ray diffraction (XRD). Onodera et al. Metallurgy.R. Although metal extraction from laterites is an important step in the hydrometallurgical processing of nickel and cobalt and various aspects of the dissolution behavior of laterites have been investigated in recent decades (Briceno and Osseo-Asare. Department of Mineral Processing. 1983. With the continuous depletion of high-grade nickel sulfide ores (Tang and Valix.. such as poor metal recovery (Agatzini-Leonardou and Zafiratos. 2000).. X-ray fluorescence (XRF). as they are difficult to dissolve in ordinary mineral acid solutions at atmospheric pressure. due to a number of political. Hirasawa. Nickeliferous laterites experience poor recovery. Leaching. P. and Exploration. Beijing P. Hirasawa et al. prior to February 28. China Jiankang Wen Professor. Majima et al. 1996. only a limited number of studies have reported on metal recovery from nickeliferous laterites at atmospheric pressure in acidic fluoride media (Hirasawa. National Engineering Lab of Biohydrometallurgy. Lei et al. 2004. 1987. technical. comprising about 60% of the total 130 million tons of nickel reserves (Kempthorne and Myers. Inc. Rubisov et al. Results showed that the laterites consist mainly of nickelsubstituted lizardite with cobble-like morphology and traces amounts of magnetite and phlogopite. reaction time 2 h. Mineralogy. E-mail: luoweicsu@hotmail. 2011. Whittington et al. mineralogical. as well as increase the equilibrium constant of the lizardite dissolution in acid solution dramatically. MINERALS & METALLURGICAL PROCESSING 117 Vol. Hirasawa. 2007). Fourier transform infrared (FTIR) spectroscopy and thermal analysis..com Dianzuo Wang Chinese Academy of Engineering.Improved nickel and cobalt recovery from nickeliferous laterites in acidic fluoride media Wei Luo National Engineering Lab of Biohydrometallurgy. Lloyd and Turner. 2003). Society for Mining.2wt. 1984.China Abstract Nickeliferous laterites were characterized by particle size analysis. Valix and Cheung. commercial application of nickel laterite processing methods has been minimally successful. 1975. Curlook. Copyright 2010. 1950. Pickles. 27 No. However. As fluoride ions can react with silicon in the lizardite crystal structure and form metal-fluoride complexes. 1987. 2005. This difficulty is a result of nickeliferous laterites being residual products that derive from a wide variety of rocks through intensive chemical weathering under strongly oxidizing and leaching conditions. Caron. Central South University. General Research Institute for Nonferrous Metals. P.. General Research Institute for Nonferrous Metals. 1987. Nickel/ nickel ores Introduction Nickeliferous laterites host most of the world’s terrestrial nickel resources. 1984). Paper number MMP-09-020. Lloyd and Turner. Canterford. geographical and economic reasons. liquid-to-solid ratio 3 mL g-1 and stirring at 500 rpm compared with H2SO4 alone (Ni 69. Key words: Oxide minerals. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Many studies demonstrate that most oxide minerals can be decomposed by hot concentrated hydrofluoric acid (Comba et al. Changsha. 1983. 1991. 2004.7% and Co 52. Revised manuscript accepted for publication December 2009. scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDX).. Original manuscript submitted May 2009.. 10% (v/v) H2SO4. Beijing.6% and Co 30.R. which leads to the incorporation of nickel into the crystal structure of laterites (Rueda et al. 1995. 2002). Central South University and General Research Institute for Nonferrous Metals.China Qiming Feng Professor... 3 • August 2010 ..R. the addition of minor fluoride salts (0. Beijing. 1989. 1991.
Differential scanning calorimetry (DSC) and thermogravimetric (TG) curves were obtained using a NETZSCH STA 449C thermoanalyzer heated at 10°C min-1 in an Ar atmosphere.to form fluoro complexes. August 2010 • Vol. which are soluble in acid solution as stable species.in the leachant could break the crystal lattice of laterites. 1991. with an ionization constant of 10-3. Fourier transform infrared (FTIR) spectra were measured on a Nicolet 5700 spectrophotometer with KBr discs in the transmittance mode in the range 4000-400 cm-1. 2004). Lloyd and Turner... Methods. NH4F and CaF2. Singh and Mendenhall. These conditions were: . the H+ activity in the leachant is controlled by the ionization equilibrium of HF as long as the leaching solution contains HF alone. together with sulfuric acid increase effectiveness in leaching metals from silicates (Comba et al. as well as the formation of metal-fluoride complexes. Leica Cambridge Stereoscan S-440 Scanning Electron Microscope (SEM) by M/S Leica Cambridge Ltd UK was used for EDX analysis. which are necessary to form fluoro complexes. samples were attrition-scrubbed using vibration milling for 10 min. To prepare the feed for leaching experiments. Characterization.. Particle size analysis was performed using a Mastersizer 2000 particle size analyzer. For studying the leaching behavior of laterites in acidic fluoride media. because leaching by fluoride ions together with sulfuric acid is accomplished mainly by lattice destruction by hydrogen and fluoride ions. When the temperature of the leachant reached a predetermined constant level.Sulfuric acid concentration (% v/v) Hirasawa. In this study. A low-grade nickeliferous laterite ore (from Yunnan. the leaching mechanism of complex oxide minerals in weak acid solution containing fluoride ions was examined.Reaction temperature . H2SO4+NH4F and H2SO4+CaF2 mixtures were used as leachants for leaching experiments. the representative sample was crushed primarily using a jaw crusher followed by a roller crusher to -2 mm. A large number of researchers have demonstrated that the addition of fluoride salts. Fluoride ions prove to be the most active additives for nickel and cobalt extraction from laterites. Calcined Al2O3 was used as an inert substance. These studies indicate that the dissolution rates of metal oxides were greatly enhanced by the increase of hydrogen ion activity in the leachant. Figure 1 — Effect of sulfuric acid concentration on the leaching of nickel and cobalt from laterites. 1988. Majima et al. A number of experimental conditions were evaluated in order to investigate the impact of different fluoride salts on nickel and cobalt dissolution. will achieve better efficiency compared with adding HF or H2SO4 alone (Lei et al. on nickel and cobalt dissolution was studied. 1998). the effect of different fluoride salts. 1984. 0. The chemical composition of the Figure 2 — Effect of reaction temperature on the leaching of nickel and cobalt from laterites. 1989. After drying at 105°C. H2SO4+NaF. a mineral sample of 100 g was charged into the leachant to commence the leaching experiment.3 L of the leachant was put into a 0. Hirasawa et al.5-L Teflon separatory flask immersed in an electric-heated thermostatic water bath. Chemicals used in this study were all of reagent grade and all aqueous solutions were prepared with deionized water. Therefore. The presence of both H+ and F. Solution samples were periodically withdrawn for chemical analysis of nickel and cobalt by atomic adsorption spectroscopy (AAS) using standard procedures. 27 No... In particular.Sulfuric acid concentration . Meanwhile. However. Mechanical agitation during the experiment was done using a Teflon blade. it is hypothesized that the addition of concentrated sulfuric acid and soluble fluoride salts. Singh and Mendenhall. nickel and cobalt could react with F.Liquid-to-solid ratio . the mineralogical analysis of the nickeliferous laterites and the dissolution of nickel and cobalt from laterites at atmospheric pressure in acidic fluoride solution were investigated. such as NaF. 1991. China) was used.15K (Dean. Experimental Materials. 1983. 1991. As part of oxide dissolution studies. 2004).2 at 298. thus. which are necessary for the formation of soluble fluoro complexes and react with silicon in laterites’ crystal structure. 3 118 MINERALS & METALLURGICAL PROCESSING . The X-ray diffraction (XRD) pattern was detected on a D/Max-2550 X-ray diffractometer with CuKα radiation from 10 to 85°.Reaction time and stirring speed The aqueous solutions of H2SO4 alone. hydrofluoric acid used as a leaching agent is a weak acid. 1988). Lei et al.
4 52. In order to investigate the effect of leaching temperature. The diffusion of reactants and products between the solution and the surface of the particle was fast and thus did not control the leaching within the range of stirring speeds investigated.7 85. a series of experiments were carried out with the leaching temperature varied from 30 to 90°C.8 69.0 %Co leached NH4F 30. Increasing the concentration up to 10% (v/v) appears to increase nickel dissolution dramatically.sample was determined by X-ray fluorescence (XRF) on a Philips PW2424 spectrometer.4 71.1 87. Hirasawa (Hirasawa et al.7 74. 1983) examined the effects of the addition of NaF into H2SO4 leaching solution on the extraction of Ni. The results plotted in Fig.1%.6 68.02g/g ore. when the amount of NaF was higher than 0.4 NaF 30. reaction time 2 h.0 76.8 51. the leaching rate improves.0 41.8 41.3 41.6 24. 10% (v/v) H2SO4. Figure 3 — Effect of the liquid-to-solid ratio on the leaching of nickel and cobalt from laterites.% 0 0. reaction temperature 90°C.8 44. An additional increase in NaF concentration to 0. Effect of reaction temperature.0 25.2%.3 0.8 73. A leaching temperature of 90°C was used in all subsequent experiments.4 28.6 71. it was indicated that the optimal metal extraction could be obtained after 2 h. the reason for the significant drop in leach recovery of Ni and Co beyond a certain fluoride concentration may be due to the coprecipitation of Ni2+ and Co2+ with MgF2 in the residues. Experimental conditions for the investigation were those derived from previous chemical leaching results: particle size d50=25 μm.4 0.3 51.1 71.6% of the nickel and 30. Results and discussion Derivation of chemical leaching methodology Effect of sulfuric acid concentration. Effect of reaction time and stirring speed. About 69. Table 1 — Effect of fluoride salts on the leaching of nickel and cobalt from laterites.7 72.1 77. A stirring speed of 500 rpm was used in all subsequent experiments. The highest Ni extraction (94.9 43.5 73. Effect of fluoride salts on leaching laterites.5 84.8 70.5%) was attained at an NaF addition of 0. Results included in Fig. This result suggests that increasing fluoride ion concentration in the leachants is an important way to improve dissolution.7 40.6 77. %Ni leached NaF 69. After several leaching experiments.9 74.9 52. and MgO from garnierite ores.6 74. Further increase in the concentration results in less effective nickel dissolution.8 21.5 NH4F 69. 3 • August 2010 .0 77.8 73. as well as the adsorption of silicic acid formed in the leach solution.2% results in the increase in the dissolution rates of nickel and cobalt. aContent.2 42. even at NaF additions as low as 0.6 60.6 81.2 CaF2 30.2 52. Fe. acid concentration has a pronounced effect on metal extraction.3 51. The results of the liquid-tosolid ratio (varying from 1 to 3 mL g-1) on nickel and cobalt dissolution from laterites presented in Fig. 1 show that in general.4 69.7 81.6 CaF2 71.7 NaF 71. with increasing reaction temperature. A series of leaching experiments were performed to study the effect of fluoride salts on the dissolution of nickel and cobalt from laterites in dilute H2SO4 solution containing different amounts of fluoride salts.7 67. the dissolution of both nickel and cobalt decreased dramatically.1 78.1 59. An important factor to be studied is the effect of sulfuric acid concentration.1 0.5 1 5 10 a Content refers to the mass ratio of fluoride salts to sample MINERALS & METALLURGICAL PROCESSING 119 Vol.8 70..5 73. Cobalt dissolution also supports this observation.8 78.9 82.4 39.8 68.4 28.8 62.4 78.2 CaF2 69.9 65. However. Effect of liquid-to-solid ratio.4 72.6 73.9 37. From the yield of the leaching residues with the addition of different amounts of fluoride salts.0 wt. especially for cobalt.8% of the cobalt in the laterites can be leached at a liquid-to-solid ratio of 3 mL g-1.0 72. liquid to solid ratio 3 mL g-1 and stirring at 500 rpm.8 50.8 58.3 30.8 18.6 81.1 83.2 73. 3 suggest that metal dissolutions are dependent on the liquid-to-solid ratio. 27 No. although the total H2SO4 concentration in the solution is the same.1 % Residue yield NH4F 71. Results included in Table 1 indicate that the dissolution rates of nickel and cobalt increased considerably. Keeping other reaction conditions constant.8 50. 2 indicate that reaction temperature has a noticeable effect on metal extraction.4 29.7 57.1 73.2 27.2 0.2 47.7 72.
Eq. 1998). Leaching behavior of the laterites in acidic fluoride solution indeed indicated that. 1983). 1987. 4). the use of other fluoride salts results in increased rates of nickel and cobalt dissolution. 3 120 MINERALS & METALLURGICAL PROCESSING . Si(OH)4 is the predominant species in the acidic pH range.= 3MgF2(S) + 2H4SiO4(S) + H2O(I) ΔGT (kJ mol-1) -183. the presence of magnesium sulfate in the solution as well as the low pH of the solution lowers the equilibrium concentration of silicic acid (Piryutko. Hirasawa et al.3% in both cases versus 0. Moreover. while MgF2 will remain inside the residues (Majima et al. as well as the formation of metal-fluoride complexes. 1988) and its solubility product equilibrium constant (pKsp) at 25°C is 10. it is reasonable to assume that fluoride ions not only give a markedly enhanced metal extraction. Further.88kJ mol-1 and its equilibrium constant is 1025. 5)..88 -382. While the dissolution reaction occurs in acidic fluoride solution.0 1055. On the surface are highly reactive groups. a finding consistent with Hirasawa (Hirasawa. The silicic acid particles in the solution are characterized by a very large surface area and are highly dispersed in the solution.15K is -173. 2005. As in the case of the use of NaF+H2SO4 for leaching laterites. particularly over that of magnesium. even in the presence of Mg2+ cations.15K is -382. but also improve selectivity for nickel and cobalt dissolution. Fe and MgO were similar to those of NaF addition.Fe)2O5](OH)4. silicic acid is precipitated from the solution. the intermediate product hexafluorosilicic acid forms: Mg3Si2O5(OH)4(S) + 18H+ + 18F. when the leach solution is cooled. 2003) examined nickel losses in the leach residue by pressure acid leaching of arid-region laterite ore and found that cations like Ni2+ are adsorbed on amorphous silica. fluoride ions provide an additional leaching agent. the optimum varies a little from that of NaF+H2SO4 (i.. which has a strongly negative surface charge.15K T(K) 298. To investigate more precisely the effect of fluoride ions on the dissolution of nickel and cobalt. Moreover.9 1025.29 (Dean.= 3MgF2(S) + 2H4SiO4 + H2O(I) (4) H2SiF6 + 4H20 = H4SiO4 + 6HF (3) This result means that the addition of fluoride ions has a significant influence on the lizardite dissolution reaction in acid solution. possibly through lattice destruction by fluoride ions. referred to in JCPDF file The Gibbs free energy change of lizardite dissolution in sulfuric acid solution Eq. at 363. who found that the effects of CaF2 addition on the extraction of Ni.1 363. oxygen and hydrogen (Si-O-H). August 2010 • Vol.Al)3[(Si. Whittington et al.e. Laterite characterization and comparison of derived products.2% in the case of NaF+H2SO4). which takes up ions or molecules of gas or liquid. (1) at 363.1 1059. 27 No..62 -173.96kJ mol-1 and its equilibrium constant is 1055. so this reaction should be spontaneous. Therefore. This large surface area and surface energy means that colloidal silicic acid is an excellent adsorbent. 0. which is evident from the X-ray diffraction pattern (Fig.1: Mg3Si2O5(OH)4(S) + 6H+ + 6F.0.96 KT 1032. Particle size analysis of the laterites reveals that 50% of the ore contains material smaller than 25μm (Fig.= 3MgF2(S) + 2H4SiO4(S) + H2O(I) Mg3Si2O5(OH)4(S) + 6H+ = 3Mg2+ + 2H4SiO4(S) + H2O(I) Mg3Si2O5(OH)4(S) + 6H+ + 6F. is lizardite ((Mg.Table 2 — Gibbs free energy change and the equilibrium constant of the lizardite dissolution reaction in acid solution with and without fluoride ions at 298. nickel and cobalt could react with fluoride ions to form fluoride complexes.= 3MgF2(S) + 2H2SiF6 + 9H2O(I) (2) Hexafluorosilicic acid then hydrolyzes to orthosilicic acid and hydrofluoric acid: The Gibbs free energy change of the overall reaction with the precipitation of MgF2. the use of NH4F+H2SO4 and CaF2+H2SO4 also exhibit optima. however. 1976). which are soluble in Figure 4 — Particle size analysis of laterites. Mg3Si2O5(OH)4(S) + 6H+ = 3Mg2+ + 2H4SiO4(S) + H2O(I) (1) acid solution as stable species.15K and 363. besides the free hydrogen ion action.15 Based on the equilibrium constants (Baes and Mesmer. (4). some additional leaching experiments on laterites were done in NH4F+H2SO4 or CaF2+H2SO4 solution under the same conditions as in NaF+H2SO4 solution. The main mineral. Results of the chemical composition analysis included in Table 3 and the spot EDX of the laterite samples in Table 4 show that the laterites are typical of silicate laterite. silicon. as shown in Table 2.49 -341. 1959).15 Mg3Si2O5(OH)4(S) + Reaction 6H+ = 3Mg2+ + 2H4SiO4(S) + H2O(I) Mg3Si2O5(OH)4(S) + 6H+ + 6F. Whittington (Whittington and Johnson. Hence..
The shoulder at 3. 2003)..631 cm-1 is attributed to the -OH bending vibration (Madejov et al.27 Mg 20. the nickeliferous laterites consist mainly of nickel-substituted lizardite revealing the cobble-like morphology as shown in Fig..9 Co 0. 2002).42 Fe 7.% O 45.4 Mn 0.45% and 10. 2003).. 8a.88 Fe 7.8 Mg 23.14 Al 0.649 cm-1 is due to the inner -OH stretching vibrations (Scholtzov et al. the band at 3.Table 3 — Chemical analysis of nickeliferous laterite sample. □-phlogopite Figure 7 — SEM image of laterites..65%.435 cm-1. 1979). The intense band at 445 cm-1 is associated with the Si-O bending mode.% O 50. From FTIR spectra (Fig. to the presence of magnesium ions in adjacent octahedral sites (Golightly and Arancibia. ●-magnetite. As is clear from the result. respectively (Tartaj et al. 27 No. respectively (Rinaudo et al.011 Ca 0. MINERALS & METALLURGICAL PROCESSING 121 Vol.6 Mn 0. the frequency value of the stretching vibration of the inner -OH group at 3.94 No.31 Ni 1. From the FTIR spectrum of laterites included in Fig. DSC analysis included in Fig.0 Al 0. 2000). 3 • August 2010 .061 Zn 0. The 618 cm-1 peak is an -OH vibration mode specifically related Figure 6 — DSC-TG curves of laterites. wt.50-1625) and the minor phases are magnetite (Fe3O4) and phlogopite (KMg3(Si3Al)O10(OH)2). The weight loss corresponding to these two processes are 2. the frequency value of the inner -OH stretching band at 3. 6 showed two endothermic peaks at about 66 and 607°C due to the release of adsorbed water and lizardite dehydroxylation. Water in laterites gives a broad band at 3. Constituent Content.649 cm-1 and its intensity are directly proportional to the percentage of nickel cations in the trioctahedral sheet replacing the magnesium cation (Scholtzov et al. Moreover.2 Cr 0.% Constituent Content. Constituent Content.649 cm-1 increased about 11 cm-1 and the intensity of this band decreased in comparison with Figure 5 — Power XRD pattern of laterites: -lizardite. The shoulder at 579 cm-1 is associated with the Mg-O bending mode out of the plane.023 S 0. corresponding to the -OH stretching vibrations and the band at 1. wt.38 Cl 0. FTIR spectroscopy is a simple and rapid technique and has been used successfully by many investigators in the study of the structure and composition of phyllosilicates.93 Si 20. wt.687 cm-1 can be assigned to the outer -OH stretching vibrations coordinated to three magnesium of the octahedral layer. The bands at 1.48 Si 18.021 Table 4 — EDX data of nickeliferous laterite sample. DSC displayed an additional exothermic peak at 807°C associated with forsterite (Mg2SiO4) recrystallization. 2003)..011 Ni 1. 7. On heating.081 and 966 cm-1 display the asymmetric stretching modes of the Si-Otand Si-Ob-Si bond.8b-8e) of solid residues leached with H2SO4 alone and the same solution containing different fluoride salts.
The experiment results were in accordance with the FTIR observations. the presence of F. These results clearly show the importance of fluoride ions together with a strong acid. including NaF. 3 122 MINERALS & METALLURGICAL PROCESSING .3% NH4F and (e) solid residues leached with H2SO4+0. a judicious choice of fluoride ion concentration is required to optimize the overall nickel and cobalt recovery and to prevent metal loss due to the coprecipitation of Ni2+ and Co2+ with MgF2 in the residues and the adsorption of silicic acid formed in the leach solution. the inner -OH stretching vibration of the laterites which means that most of the nickel has been extracted from laterites. thus indicating that the other ions in solution had no significant impact on the manner in which F.7% Ni and 52. regardless of originating salt. The relative increase in the intensity of υasSi-Ot. (d) solid residues leached with H2SO4+0.2% NaF.at 1. Furthermore. 27 No. as fluoride ions could significantly increase the equilibrium constant of the dissolution reaction in acid solution. However. for minerals containing significant amounts of silica. As much as 81.3% Co could be leached with the addition of 0.3% CaF2. (c) solid residues leached with H2SO4+0.081 cm-1 and the decrease in the intensity of υasSi-Ob-Si at 966 cm-1 also indicate that the phyllosilicate structure has been decomposed by both hydrogen ions and fluoride ions in the leachant.interacts with the system to produce enhanced nickel and cobalt dissolution. (b) solid residues leached with H2SO4. in breaking the silicate crystal lattice of laterites and improving the metal dissolution reaction in acid solution.Figure 8 — FTIR spectra of (a) laterites.% NaF under Conclusions August 2010 • Vol. NH4F and CaF2. An investigation was conducted to study the metal dissolution behavior of nickel-substituted lizardite in acidic solution containing different fluoride salts.was the same.2 wt. The presence of both hydrogen ions and fluoride ions in the leachant was found to be necessary for the improved dissolution of laterites. such as H2SO4.
“Tantalum recovery from ore concentrates by acidic dissolution and selective extraction. No. H. 25-42. 4. McGraw-Hill Professional. M. 2006.. N. “Studies on the acid leaching of garnierite ore . S. J. 19. pp...1. and Valix. pp. Curlook. Electron Spectrosc. 2003. McDonald. 8404759. 1975.4. and Johnson. C. pp. Awakura. 3.” Shigen to Sozai. 19. Eng. F.” Hydrometallurgy.. and Carnahan. pp. Madejov. T.. “Study of phase transformation of laterite ores at high temperature. P. 3 • August 2010 . No..” Hydrometallurgy.. “Calcium fluoride-sulfuric acid leaching of a manganese silicate ore. D. Charlotte. and Papangelakis. P. G. P.” Miner. 1998. 1-4. the National High Technology Research and Development Program of China (863 Program) (No. 12th. J. Mineral commodity summaries 2007: U. and Muir. 1996. “Treatment of nickeliferous laterites..3.” Proceedings of the International Conference on Environmental Degradation of Materials in Nuclear Power Systems--Water Reactors. Washington. 3. Vol. 719-28. C. T. pp.. A.” EPD Congr. H. P. 883-890.. antigorite. No. Vol. 1989. R. 2002. J. “Pressure acid leaching of arid-region nickel laterite ore... Metall. “The solubility of silicic acid in salt solutions. “Kinetics of limonite and nontronite ore leaching by fungi metabolic acids. reaction temperature 90°C. pp. G. A. Scholtzov. I... and Cheung. T.. L. Meet.. New York. “The chemical composition and infrared spectrum of nickel.P. 37-41.. No. 188. R.G. 255-271. No. “Beneficiation of a Greek serpentinic nickeliferous ore . 3-17. Mineral. M. B. 355-363. 7.. E. and Mesmer. J.” Appl. Geological Survey.. Vol.1.2006BAB02A10).” Hydrometallurgy. No. Deng for assistance with the samples. 709219. Vol. Vol. pp.” Metall.. Tartaj. “Calcium fluoride-enhanced hydrochloric acid leaching of a manganese-bearing silicate ore. Soroako. 1987. B.. Droes. An effect on inner OH group. Kempthorne.. R.. No. 1991. Trans. Piryutko. 2004. “Sulfuric acid pressure leaching of laterites . Acknowledgments This work is supported by a grant from the Major State Basic Research Development Program of China (973 Program) (No. iron and magnesium oxide in sulfuric acid. pp. A.3. Inoue. Agatzini-Leonardou. Bureau of Mines Report of Investigations RI 9372. pp. Chen for enlightening discussions and Dr. pp. Salt Lake City. and Hirato. 176-181. Y. H. Vol. Part III: Effect of process water on nickel losses in the residue. 14-18.. Casanova. Vol. R. Comba.” Hydrometallurgy. 44.” Miner. M. E. Vol. 67-90. Y. Vol..3-4. C.2007CB613602). 231.” Can.” Metall. No..” JOM.. Symp. NC. Canterford. “Particles in hydrometallurgy. 2005. Vol. Eng. K. F.the experimental conditions of particle size d50=25 μm.. A. Johnson. Valix. Australian Pat.. No. and Zafiratos. 1984. and Osseo-Asare.Part II. Dewatering behavior of unflocculated laterite acid leach residues.. Vol... Caron. and Moog. 1959.effects of sodium fluoride addition on the extraction of nickel. Vol. D. Rinaudo. D. Quart. H.. 1988... No. 1133-1138.” Toyama Kogyo Koto Senmon Gakko Kiyo. Majima.” International Laterite Nickel Symposium. T. Mar.. Janek.. R.12. Rubisov. and Mendenhall.” Can. T. “Effects of additives and roasting on the acid leaching of References garnierite ore. 2004.” US Pat. 2003. pp. Tunega. M. “Effects of additives on the sulfuric acid leaching from the garnierite ore. pp. Lloyd.. Krowinkel.. J. C.. Deepatana. B.. TMS Annu. P.. 2000.. 26B. Eng. Vol. and Carnahan. Golightly. B. G. “Leaching of low grade limonite and nontronite ores by fungi metabolic acids.. Vol. pp.. 1274-1279. Vol. Mashima. 10% (v/v) H2SO4. 91. pp.4. Proceedings of [a] Symposium held during the TMS Annual Meeting. Jr. T. Tang. H. Lei.. J. R. Process. Vol. Miner. and Jalowiecki. and Wakabayashi.. O. 7. Lange’s Handbook of Chemistry.” Int. 8.. and Arancibia. Mol.” U. H. W.. reaction time 2 h.. 14-18.. “Characterization of Venezuelan laterites by x-ray photoelectron spectroscopy.” WO. 99. No. pp. 15-19. J. A.. M. Barbaux... J.. M. J. 325-334. No.. Cerpa.. Rodriguez. pp. Baes. Vol. J.” J. Struc-Theochem. W.S. “Characterization of chrysotile. Tang. 27 No. Part II.” Can. I. No. J. R.. No. 74. 355-360. No.. No. Wiley Interscience. D. 41.S... S. United States. We thank Dr. Sci. 21.. Pickles. 1069-1078.. A. pp. 19B. 3. M.Part I: effect of water quality. Komadel. 8. Aug.3-4. J. G.. MINERALS & METALLURGICAL PROCESSING 123 Vol. I. 2007. 17. 256-263. pp. Lei. J. Briceno.. L.2007AA060903) and Key Projects in the National Science & Technology Pillar Program during the Eleventh Five-Year Plan Period (No..universal kinetics of nickel dissolution for limonites and limonitic/saprolitic blends. Mater. 1. pp. J. Mineral. J. Singh. Whittington. 31-46.. and Imaizumi.1. M. Hirasawa. D. Trans. C. 2005. Gastaldi.and iron-substituted serpentine from a nickeliferous laterite profile. A. Herbert. Hirasawa. “Improvement to the acid pressure leaching of nickel laterite ores. and Belluso. L.. 1979. A. K. No. A. 267-275. No. 2003. Vol. 1-8. pp.. 2004. and Turi Nagy.6.. 15.. “Theoretical study of cation substitution in trioctahedral sheet of phyllosilicates.. 620. 1. 255-260.V. New York.. pp..” Russian Chemical Bulletin. 607-612.. M.” J. and Serna. Whittington. pp. 2000.. and Valix. Colloid Interface Sci. “Microwave drying of nickeliferous limonitic laterite ores. 82. Mendialdua. C. No. Indonesia.” J. pp.” Nippon Kogyo Kaishi. “FTIR analyses of water in MX-80 bentonite compacted from high salinary salt solution systems. The Hydrolysis of Cations. Vol.. M. No. “Attempts at the beneficiation of lateritic nickel ore... 105.. Trans. No. No.. G. 6.. and lizardite by FT-Raman spectroscopy. “Recovery of metals from ores. “Pressure acid leaching of arid-region nickel laterite ore . M. 397-407. Rueda. “Fundamental and practical factors in ammonia leaching of nickel and cobalt ores. 2002. 1-3. Gengembre. H. “Dissolution of columbite and tantalite in acidic fluoride media. 1995. R. M. pp. J. E. 1-11. 1991. 1983. M. 1976. Onodera. Hirasawa. 78. and Myers.. No. UT. 1987. “Surface Instability of Serpentine in Aqueous Suspensions.. 63-68. pp. Dean. H. D. Vol. 20.1139. 135-143. pp. Vol. Vol. V.. R. R. 15.. pp. K. Proc.. V. Garcia-Gonzalez. K. and Turner. Clay Sci.. 2005. United States. pp.” Miner. 70. Y. liquid-to-solid ratio 3 mL g-1 and stirring at 500 rpm. G. P. Matsuoka. 58. 1950.. Sulfuric acid heap and agitation leaching.
5% Fe and represent 78% of the weight and 75% of the total iron content of the combined flotation tailings. illustrating the points where flotation tailings are generated: mechanical (Wemco. 2 and 3. MG. Revised manuscript accepted for publication October 2009. The reground product (minimum 87. 160 m3.16 m3 or 500 ft3. in the state of Espirito Santo.). Original manuscript submitted May 2009. hydrocyclones of 38. Cleaner stages were not achievable with the resulting concentrates. and Exploration. 10. Copyright 2010. Inc. Department of Materials and Materials Engineering. and then the concentrate is pumped via a 396 km pipeline to the pelletizing facilities. Magnetic concentration.7 % blast furnace concentrate). 2011. Minais Gerais. operated in a closed circuit.E. The concentration of iron minerals contained in flotation tailings will maximize the production and minimize the flow of tailings disposed to the environment. operates an iron ore mine and the Germano concentrator in the Iron Quadrangle. prior to February 28. Flotation. Oliveira.0% using a representative sample of Samarco´s mechanical flotation tailings. magnetic concentration using a SLon high-gradient magnetic separator. 3 124 MINERALS & METALLURGICAL PROCESSING . 4 units) and column circuits.0% Fe and presented an F80 = 116 µm and a d50 = 63 µm. Ouro Preto. Vieira Research engineer.Pellet feed production via the concentration of flotation tailings M. reverse flotation or direct flotation. Brazil This investigation addressed the possibility of producing pellet feed at a silica content of ≤ 1. where the particle size is reduced from 44 % +105 µm to 10 % +105 µm. Figure 1 shows a simplified Germano’s concentrator flowsheet. The concentrate from the mechanical cell circuit feeds the regrinding mills #4. improving the sustainability of the operation. Brazil A.).0% and high specular hematite content. This significant participation in the tailings stream was the reason for the selection of the mechanical cells circuit tailings for the present investigation. The methods using the magnetic concentrator SLon. 2008) using magnetic concentration and/or reverse flotation. the most successful method consisted of using wet high-intensity magnetic separators (WHIMS) as a rougher stage and reverse flotation as a cleaner stage.2 % -44 µm) feeds the concentrate thickeners. 10 and 4 in. Iron/iron ores feeds the desliming (three stages. This sample contained 11. August 2010 • Vol. 5 and 6 operated in an open circuit and the reground product feeds the tank cell circuit. Rocha.C. Specular hematite is the most abundant mineralogical phase in the fraction -37 µm. where final silica specification is achieved (1. Key words: Pellet feed.5 mm feeds the pre-primary and primary grinding. ABSTRACT Introduction Samarco. reverse flotation and direct flotation did not present results meeting the target of the study: iron content in the concentrate (rougher stage) greater than 34% or iron recovery greater than 80%. 14 cells per line). 14. 27 No. Society for Mining. The column flotation concentrate is classified in hydrocyclones of 25. MG. Brazil. in average. A brief description of the flowsheet follows: the ROM containing 46 % iron and particle size -12.G. 2006.4 cm (10 in. The concentrate from the tank cells feeds the column flotation circuit. UFMG. In contrast. The pellet feed fines produced in the concentrators (24 million metric tons per year) are transported via a 396-km pipeline to the Ponta Ubu pelletizing plant. The blast furnace and direct reduction pellets are exported worldwide.0 % direct reduction concentrate and 1. The mechanical flotation tailings present. Magnetic concentration in a wet high-intensity magnetic separator (WHIMS) machines is a traditional iron ore ben- Paper number MMP-09-019. a joint venture between Vale (50%) and BHP (50%). Using this route. Metallurgy. Peres Associate professor. The purpose of the present investigation was to recover iron oxides from a stream that is currently emptied into a tailings pond. 25. Belo Horizonte. The overflow (-10 µm) feeds an iron fines recovery plant and the underflow feeds the mechanical flotation circuit.4 and 10 cm) (15. it was possible to produce a pellet feed with a silica grade of 1. 2003. 4 lines. The technological tests used one of four methods: magnetic concentration using a wet high-intensity magnetic separator. The product from this circuit Literature review The concentration of iron minerals from flotation tailings was investigated by Brazilian researchers (Santos. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Samarco Mineração SA. The higher silica content was verified in the coarser fractions and the higher iron content in the fraction -37 µm. tank cell (Outotec. where the overflow feeds the concentrate thickeners and the underflow feeds the mills #1.
feeding a rotating circular matrix (carousel) at two opposite points located under the action of a high-intensity magnetic field provided by permanent magnets. such as reduced capacity for fines. According to Hearn and Dobbins (2007).000-kg sample was generated. Materials and methods Sampling and sample preparation. it is possible to produce cleaner concentrates from feed consisting of particles greater than 100 µm. The diamagnetic quartz particles flow past the matrix. most results from laboratory investigations indicated that iron oxide flotation with anionic collectors (fatty acids) and amphoteric collectors (sarcosinates and sulfosuccinamates) yields concentrates with high silica contents. SLon was developed in China and the first industrial application occurred in 1988. Characterization of the sample. the matrix pulsates vertically. Nevertheless. The iron feed grade was 15.60%) recoveries.79%) at enhanced weight (+ 3. dewatered.(1) Mechanical flotation tailing (2) Tank cell flotation tailing (3) Column flotation tailing (1) (1) (2) (1) (3) (1) Figure 1 – Germano´s concentrator simplified flowsheet. iii. eficiation technique used in Brazil at Vale since 1972 (Jones separators). titration and loss on ignition. Vieira and Peres (2007) point out the major challenges in this system: coarse quartz particles do not respond well to the amine collecting action and fine iron oxide particles do not respond well to the starch depressant action. while the paramagnetic hematite particles stick to the matrix and are washed down when the segment is free of the magnetic field action. In addition to the horizontal movement. The increased iron recovery was attributed to the SLon pulsating mechanism. After this time a 10. concentration of marginal ores aiming at reducing the waste/ore ratio. Sodium silicate was not an effective quartz depressant in this system (Araujo et al. homogenized in a conical pile and stored in 200-L drums. Slon1500 yielded higher iron contents in the concentrate (+ 3. ii.78%. Quartz is floated with etheramines partially neutralized with acetic acid and iron minerals are depressed with nonmodified MINERALS & METALLURGICAL PROCESSING starches. matrix obstruction and nonmagnetic particle entrapment. Quartz reverse cationic flotation is the most widely used itabirite concentration method for pellet feed production. Matrix obstruction was a more severe problem in the case of WHIMS. installed in parallel at Qidashan Mineral’s concentrator. 27 No. The SLon magnetic separator was specifically designed to make up for deficiencies of wet high-intensity magnetic separators. Zeng and Dahe (2003) compared the performances of WHIMS-2000 and SLon-1500.. The fact that the matrix is always clean results in enhanced iron recovery.57%) and metallurgical (+13. The motivation for developing this technology was to concentrate Chinese ores with iron grades of < 30%. concentration of low grade ores. The size distribution of the fraction -297 µm +37 µm was determined by Tyler sieves and the size distribution of the fraction -37 μm was done by a laser diffraction particle size Vol. preventing obstruction and entrapment. The splitting for technological tests was done using a riffle sampler. 3 • August 2010 125 . Quantitative chemical analyses of the head sample and fractions from -297 µm +37 µm and -37 µm were performed using ICP-OES. The anionic direct flotation of iron oxides is potentially attractive regarding: i. resulting in a lower iron grade in the concentrate. The flotation tailings sample was formed by increments collected over 20 days in the four lines of mechanical flotation. iron recovery from material deposited in tailings ponds. The pulp flows vertically. 2006).
86 3.96 0. The tests involved four technological options for the rougher stage: 1.09 0.44 93.68 0. Figure 3 shows the main mineralogical phases present in the tailings sample from the mechanical flotation. respectively.01 95. representing about 51 % by weight.59 98. direct flotation. F80 and the slimes content (fraction < 10 µm) were.10 83.08 The cleaner stage was performed only if 74 36.42 3.19 0.27 0.analyzer (Mastersizer Micro).014 0.00 11.13 reverse flotation. 44 18. The iron content in the -37 μm single fraction is 44. the collector being oleic acid saponified 210 93. If this condition was not achieved.12 the route was discarded.001 0.09 sodium silicate. August 2010 • Vol. 27 No. 37 15.25 7. Results and discussion Figure 3 – Mineralogical phases distribution.15 0. 105 63.69 %. µm passing Direct flotation was performed at pH = 297 98.22 0.014 0.01 83.68 0.22 with caustic soda solution at 5:1 w/w acid : NaOH ratio. a consequence of the difference in grindability between the harder quartz particles and the softer iron oxides.98 4.74 0.13 0. 63 µm.13 The cleaner stage was performed using -37 0.06 83. The depressant used was 149 75.33 Size distribution and chemical analyses by size range.22 97. magnetic concentration using a SLon high-gradient magnetic separator (OUTOTEC).13 0.001 0.68 0. reverse flotation.26 3. Mineralogical analyses were performed by the counting grains method.47 94. 116 µm and 2. mine and 25% dietheramine. 2.001 0. There is a high silica distribution in the coarse fractions and a higher iron distribution in the fine fractions. respectively. decyl ether amine and gelatinized manioc starch.06 92.001 0.60 95. magnetic concentration using a wet high-intensity magnetic separator (Minimag / GAUSTEC). It is noted that quartz is the most abundant mineral phase.44 2. Flotation pH was set at 10. using a reflected light optical microscope.35 0. Technological tests. % Fe % SiO2 % Al2O3 % P% LOI % and figures.82 0.37 0.001 0. both dosed at 1% w/v solution. The collector and depressant used in the cationic reverse flotation were.007 0.18 0. The most representative iron mineralogical phases are specular hematite and martite.21 0.10 80%.13 and a pilot flotation column.43 5. 3 126 MINERALS & METALLURGICAL PROCESSING . at an iron recovery level > 53 26.10 the iron content of the rougher concentrate was > 34%. The manioc starch depressant was gelatinized with caustic soda solution at 5:1 w/w starch : NaOH ratio. Table 1 shows the chemical analyses of cumulative retained fractions.41 1.001 0. 4.65 0. Figure 2 presents the sample size distribution.73 0. The phosphorus is concentrated predominantly in the -37 μm fraction and alumina and LOI in fractions above 210 μm. The amine was a blend of 75% monoetheraFigure 2 – Sample size distribution. The reagent dosages used in Table 1 – Size distribution and chemical analyses of cumulative retained fractions.27 0.014 0. 3.43 0.02 %.5.45 0. The values of d50.90 94. Analyzed sample 11. the experiments are presented in the tables Aperture Cum.005 0.08 0. with the flotation tests done in a bench scale mechanical machine Calculated sample 11.
35 – 10. the iron content does not increase significantly (except at a 200 g/t starch dosage).70 SiO2 % 1. 3 • August 2010 .026 0. the greater the percentage of quartz and the lower the percentage of specular hematite.68 Iron % 46.16 Weight recovery % 20. The variables tested were: magnetic field intensity.38 1. solids percentage in the feed and carousel speed.77 67. thus. a pressure of 2. MINERALS & METALLURGICAL PROCESSING 127 Vol. average).36 – 28. Increased starch dosage provided higher iron recoveries and higher iron content in the concentrate and the results for the starch dosages 150 and 200 g/t were similar. at an iron recovery > 80 %.23 -44µm % 85. The change of stroke from 0 to 15 mm was not significant. the larger the particle size. Specular hematite is the most abundant mineral phase in the -37 µm fraction.79 86. Figure 5 shows concentrate iron recovery and iron content curves as a function of increased amine dosage and starch dosage. followed by liberated quartz (24 % by weight) and martite (22 % by weight).65 – 2. Figure 4 shows the iron recovery and iron content curves versus magnetic field intensity. The percentage of nonliberated quartz is around 2 % by weight and the quartz liberation degree is 96 %.07 P% 0. washing pressure.5 rpm rotation and 200 Hz pulse rate. Flow Feed Concentrate Tailings Fe % 9.02 Table 3 – Minimag’s concentrate flotation tests. at 49 % by weight. With 100 g/t amine and 600 g/t starch it was possible to achieve a pellet feed within the 1.56 23.82 Iron recovery % 82.69 32. It can be observed that above 100 g/t amine. 27 No. Reverse flotation. Amine starch g/t 80 / 600 100 / 600 Concentrate Fe % 67. Figure 5 – Iron content and recovery curves versus starch and amine dosage.000 G. Table 3 shows the results of two flotation tests (bench scale) performed on a concentrate obtained by the Minimag. The best results were achieved using a field of 12. solids percentage of 35 % and rotation of 4 rpm.44 855 831 with 29 % and 14 % by weight.02 45. Table 2 summarizes the results of tests of high-intensity magnetic concentration using Minimag. Magnetic concentration using a SLon.Table 2 – Compilation of 12 preconcentration tests using Minimag (Fe% minimum to maximum. The best results were achieved using 2. In general.026 Al2O3 % 0. respectively.35 24.0 % silica specification.38 – 38. indicating that higher starch dosages do not affect significantly the concentrate Figure 4 – Curves of iron recovery and iron content obtained with the flotation tailings concentration using SLon.23 0.57 – 88. None of the tests yielded 34 % iron in the concentrate. Magnetic concentration using WHIMS (Minimag).43 BSA cm2/g Recovery Weight % 24. Technological tests.47 86. The percentage -44 μm was also satisfactory.5 kfg/cm2. cleaner tests were not performed.52 1.
.. Figure 6 shows the curves of iron recovery and iron content depending on the oleic acid and sodium silicate dosages. Vol.. and size range in the flotation of quartz.Figure 6 . A. 107 pp. thesis. The WHIMS concentrate was submitted to reverse flota- Araujo. 2008. 3 128 MINERALS & METALLURGICAL PROCESSING . 20.” Minerals Engineering.. M. 2007. “The latest application of SLon vertical ring and pulsating high-gradient magnetic separator.. I. PPGEM UFOP. reverse flotation and direct flotation.. P. but decreased the iron recovery. Viana. Zeng.. Due to the oleic acid low selectivity. Study on the production of iron ore concentrates from Germano´s pond tailings. W. M.C. (in Portuguese) Vieira. Increasing the sodium silicate dosage increased the iron content of the concentrate. tion cleaning stages yielding 1. thesis. “The effect of amine type. pH.E.R. V.Sc. p.. 2006. M. (in Portuguese) Santos. (in Portuguese) Rocha.J. WHIMS. thesis. Hearn.. 27 No. 2005. Oliveira. The iron recovery curves are consistent. P. Acknowledgments The authors are grateful to Samarco.E. increasing with higher oleic acid dosage. SLon magnetic separator: a new approach for recovering and concentrating iron ore fines.C. A. Fapemig and CNPq for financial support. 8 pp. Routes for recovery of iron oxides fines contained in the Conceição´s concentrator slimes thickener underflow. Study on the economic recovery of slimes from an iron ore concentrator via reverse cationic flotation. Increasing the oleic acid dosage decreased the concentrate iron content.” Minerals Engineering.S. Direct flotation. and Dahe. the collected quartz particles contaminate the concentrate. August 2010 • Vol. pp. M. iron grade and recovery.C.M.” Minerals Engineering.M. and Dobbins.Iron content and recovery curves versus oleic acid and sodium silicate dosages. A. S. pp. and Peres. 2007. Vol. 16. WHIMS was the only one to meet the target of an iron content greater than 34% and iron recovery greater than 80%.Sc.. 219-224. 2003. 121 pp. 18. References Conclusions Among the four methods selected for the production of rougher concentrates from iron ore flotation tailings. 219-224. SLon high-gradient magnetic separator. Vol. “Reagents in iron ores flotation.. 113 pp. L. 2003.Sc. also indicating a low selectivity.B. 1008-1013. A. CPGEM UFMG. Montreal Energy & Mines..0% silica grade in the pellet feed product.N. CPGEM UFMG. and Peres.
Solvent extraction. Key words: Zirconium. Inc. Saberyan Professor. AbdelRehim. Copyright 2010. Zircon. is concentrated with other heavy resistant minerals in placer deposits. University of Tehran. The trioctylamine reagent is less effective for mutual separation of elements when they are present as Paper number MMP-09-003.5 . Department of Inorganic Chemistry. 2000). The method involved extracting zirconium from a hydrochloric acid solution with TOA in benzene. Tehran. MINERALS & METALLURGICAL PROCESSING 129 Vol. as a heavy mineral very resistant to chemical decomposition and erosion. 2002 a. 1994. and Exploration. Abdel-Rehim.. Original manuscript submitted January 2009. 1971). Zirconium has also been recovered quantitatively from 0. Organophosphorus compounds. Solvent extraction studies of Zr (IV) from chloride solutions by TOPO have indicated that the species are extracted into the organic phase as disolvates (Sato. but extractions in nitric and hydrochloric acids (as media) were negligible.5 M) and determined with inductively coupled plasma atomic emission spectrometry. Thiocyanate. Nuclear Fuel Cycle Research School. principally in river and beach sands. 1983). 1975). Revised manuscript accepted for publication October 2009. prior to February 28. zirconium has been extracted quantitatively from 0. 2006. Iran M. The resulting extracted metal ion has been stripped with sulfuric acid (0. Zolfonoun A. A literature survey in this subject reveals that trioctylamine (TOA) has been used to extract zirconium (Rajmane and Sargar. 1999. namely TBP and D2EHPA. NSTRI. Vahedian-Donyaparast Graduate student. Department of Mining Engineering.org P.Solvent extraction of zirconium from zircon leach liquor using triphenylphosphine oxide K. E-mail: ksaberyan@nrcam. Tehran University. Nuclear Science and Technology Research Institute (NSTRI). magnetite. Tehran. diorites and gneisses. such as illmenite.. Das and Lahiri. due to its excellent corrosion resistance and low neutron cross-section. Zirconium is used in the nuclear industry. Nemati Chemical engineer. In this method. Levitt and Freund (1956) have studied the extraction of Zr (IV) from hydrochloric acid solutions by TBP and suggested that ZrCl4. Doyle and Duyvesteyn. Iran Professor. 27 No. 1974 a.b. Department of Mining Engineering. 1990. Several methods have been used for the industrial processing of zircon to extract zirconium and produce zirconium dioxide and tetrachloride (Bidaye and Venkatachalan. 3 • August 2010 . Metallurgy. Kutyrev et al. 2005. USA and Egypt. have been extensively employed in the solvent extraction studies of Zr (IV). This method has been applied successfully to achieve 95% recovery of zirconium from zircon concentrate. in which the extraction efficiency was subjected to the length of amine chain (Sato and Watanabe. particularly in syenitic and granitic pegmatites and granites. Faculty of Chemistry. Triphenylphosphine oxide. Tehran. It has been reported that higher reagent concentrations are required (Seidl et al. Zircon occurs as a common mineral in pegmatites. 2000). Hesarak. Large commercial detrital deposits are found in Australia.b.3 using 0. Noparast Professor. Science and Research Branch. Welham. Habashi. Tehran. 1982). Iran. Stanley and Lafond. Madagascar. Poonak. Islamic Azad University. Chatterjee and Basu. 1999. Zircon is commonly associated with other heavy minerals. 2011. Society for Mining. The extraction behavior of Zr (IV) from aged chloride solutions by di-(2-ethyl hexyl) phosphoric acid (D2EHPA) has been investigated by Biswas and Hayat (2002). monazite and rutile (Abdel-Rehim.01 M triphenylphosphine oxide dissolved in toluene as an extractant. Ceylon.005 M sodium salicylate solution at pH 2. Iran Abstract A technique is described for the solvent extraction of zirconium. Iran E. Nuclear Fuel Cycle Research School. South Africa. India.2S is the extracting species. Salicylate Introduction Zircon is the most important commercial source of zirconium and its compounds and alloys. 1982. Brazil. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Tehran.2 M potassium thiocyanate solution.
Following separation. Organic and aqueous phases were separated by a separatory funnel.Table 1 — The effect of hydrochloric and nitric acid on zirconium extraction. Reagents. which was about twice that required to attain apparent equilibrium. Extraction of zirconium from hydrochloric acid solution with di-n-octylamine in benzene has also been investigated under different conditions (Nekovar et al. extraction is decreased.6 7. An aliquot of solution (20 ml) containing zirconium (10 μg mL-1) and sodium salicylate (0. In this study. It is therefore felt worthwhile to evolve an entirely new procedure. tetraphenylalkylenediphosphine dioxides (Turanov et al.1 congeneric pairs in aqueous solutions. The extraction of zirconium decreased markedly with increasing sulfate ion concentration in the aqueous phase. Zilberman et al.5 M sulfuric acid.4 40. However. A solution of Alamine 336 in an appropriate diluent has been used to extract zirconium from 1 M sulfuric acid and 4 M malonic acid media (Kutyrev et al. Moreover.3 HCl 2.1 3 5 Table 2 — Effect of adding complexing agents into the aqueous phase. A Metrohm model 744 digital pH-meter. the solvent extractions of the tetravalent metal ions zirconium (IV).005 M) was adjusted to pH 2. 1996) from sulfuric acid solutions have been investigated systematically. The results are shown in Fig. di-o-tolylphosphoric acid (Biswas and Habib.4 Extraction. zirconium was then stripped from the organic phase by 20 mL of 0.1 M hydrochloric acid. Figure 1 — The effect of the pH of the aqueous phase containing salicylate anion on extraction efficiency. 2000). Effect of pH of the aqueous phase.5 3. 1994). Zirconium extraction. the extraction was found to be incomplete. into the aqueous phase was studied.5 with dilute hydrochloric acid and sodium hydroxide. Preliminary experiments on zirconium extraction with this extractant have shown that zirconium extraction efficiencies in nitric and hydrochloric acids (as media) without adding complexing agents are negligible. thiocyanate and salicylate.8H2O (from Merck) in 100 ml of 0.. equipped with a combined glass-calomel electrode. from Merck Company. 1997). one which facilitates the extraction and separation of zirconium (IV) from associated elements with a minimum amount of manipulation. about 7% in 5 M hydrochloric acid media. The extractant triphenylphosphine oxide was obtained from Fluka. 2000). 2008).2 5. such as acetate. hafnium (IV) and thorium (IV) have been investigated using a recently synthesized naphthol-derivative Schiff base (HAPMN) (Saberyan et al.. whereas at a lower pH. in many instances the available methods are found to be inadequate for effective extraction.01 M) pH=1 Acetate Thiocyanate Salicylate 7. Cyanex 302 and Cyanex 301 (Wang and Li. dibutyl hydrogen phosphate (Fedorov et al. All other reagents were pro-analysis grade. 27 No. hafnium stripping has not yet been studied in any literature review. Results and discussion Effect of hydrochloric and nitric acids. was employed for the pH adjustments.. and the maximum extraction has been achieved. although the addition of some hydrogen peroxide to sulfuric acid can improve stripping efficiency. of 100 µg mL-1 were prepared by dissolving appropriate amounts of ZrOCl2. 1990). Even though extensive work has been performed on the extraction and separation of zirconium (IV). tri-isoamyl phosphate (TAP) (Hasan and Rupainwar. % pH=2 18.. Some other phosphorus-containing extractants have been reported for the extraction of zirconium from acid media.5 and higher.2 22. The organic phase was prepared by dissolving triphenylphosphine oxide (0. Complexing agents (0. Reddy and Kumar (2004) and Taghizadeh et al.5 60.2 97. (2007) have shown that sulfuric acid is the proper reagent for zirconium stripping from loaded Cyanex 272. these methods suffer mainly from being multistage extractions and from emulsion formation. 2000). the effect of aqueous phase pH containing salicylate ion on zirconium extraction was examined..05 M) in toluene. 1985).3 4. The results are shown in Table 1. 2000. (1993).3 pH=3 37. Effect of addition of complexing agents. The results are summarized in Table 2. such as tritolyl phosphate (TTP) (Curtui and Soran. Batch contacts with phase ratio O/A=1 were performed at 25 °C using a mechanical shaker..6 85. as well.4 Concentration (M) 0. Extraction procedure.7 16. Selective stripping of zirconium has never been reported. The determination of zirconium was performed on a Varian model Liberty 150 AX inductively coupled plasma optical emission spectrometer (ICP–OES). the extraction of zirconium by triphenylphosphine oxide is maximized by using salicylate as a complexing agent. The present research attempts to determine the solvent extraction behavior of Zr (IV) using triphenylphosphine oxide (TPPO) in toluene. probably due to the reaction of salicylate anions with H+ ions preventing the formation of a neutral complex 130 MINERALS & METALLURGICAL PROCESSING Experimental Apparatus. 3 . The zirconium stock solutions August 2010 • Vol. The metal concentrations in the aqueous phase and stripped phase were determined by ICP-OES. However. The behavior of a third phase formation in solvent extraction of zirconium by TBP has also been studied by Kim et al. As the results indicate. % HNO3 1. 2000). 1 and show that the maximum extraction efficiency can be achieved at a pH over 2. The effect of the addition of various complexing agents. Solvent extractions of zirconium with Cyanex 272 (Kent and Corinne. The contact time was 30 min.
Zr (IV) has been extracted with different concentrations of triphenylphosphine oxide in toluene (10-3-10-1 M) and the results are shown in Fig. The studied system has been implemented to determine the zirconium in zircon concentrate. The loading capacity of 0. Figure 4 — The effect of triphenylphosphine oxide (TPPO) concentration on extraction efficiency. However. Choice of stripping agents. Then the residue was leached with 5 M hydrochloric acid at an S/L ratio of 1/5 g.01 M TPPO in toluene has been determined by contacting the organic phase repeatedly with the same volume of aqueous phase containing 10 – 2000 μg mL-1 of Zr(IV) and 0. respectively. Effect of metal loading.3%) and n-hexane (92. 3 • August 2010 131 .05 M of salicylate.) (1) has been extracted quantitatively in the concentration range of 10 – 500 μg mL-1. aluminum (III) and iron (III) (10 and 100 μg mL-1 each) have been studied under the optimum conditions for zirconium extraction.) + Sal2-(aq.01. 5. 2. An aliquot (2 mL) of this solution was diluted to the proper volume and extracted for zirconium by this technique. (1954). the optimum concentration of extractant selected is 10-2 M triphenylphosphine oxide in toluene.Figure 2 — The effect of sodium salicylate concentration on extraction efficiency.) → ZrO(Sal)(aq. The sodium salicylate concentration required for quantitative extraction of Zr (IV) is found to be 5×10-3 M. Vol. In this step. is higher than other metal ions. 27 No. The mass was then mixed with 100 mL water for about five hours and filtered through medium-speed filter paper.mL-1 and 90 °C for about one hour (leaching recovery 97%). It is possible to quantitatively extract higher concentrations of zirconium (IV) using a larger volume and a higher concentration of TPPO. for the extraction of zirconium was investigated. The suitability of several diluents.005 M salicylate and 0. Therefore. Zirconium (IV) Application Figure 3 — Plot of log (D) (distribution ratio) versus log sodium salicylate concentration. MINERALS & METALLURGICAL PROCESSING Figure 5 — The effect of Zr (IV) concentration on extraction efficiency.05 M solution triphenylphosphine oxide in toluene (97%). 20 g of zircon concentrate was mixed with NaOH (50%) at a phase ratio of 1/1 g. 4.5. nTPPO(org. The results are shown in Fig. benzene (95. the extraction of Zr (IV) is incomplete with xylene (93.) ZrO (Sal)(aq.mL-1 in a nickel crucible and heated at 600 °C for about four hours.05 and 0. The extraction was found to be almost total with 0. different stripping agents have been tested to strip the zirconium from the organic phase and the obtained results are represented in Table 3. ionpair with zirconium (IV). Effect of sodium salicylate concentration. benzene and n-hexane. The results are shown in Fig. the sodium salicylate concentration has been varied from 5×10-4 to 5×10-2 M at pH 2. Zircon concentrate (procured from China) was treated as described in Gilbert (1954) and Beyer et al. The mechanism for such reaction can be represented as follows: ZrO2+(aq. In order to obtain a quantitative extraction of Zr (IV). The extraction of Hf (IV). phase ratio O/A = 1 and contact time 30 min. The extraction behaviors of hafnium (IV). 3. Comparison of extraction efficiency of Zr (IV) with other associated metal ions. The lowest extraction belongs to Ti (IV). such as toluene. Effect of TPPO concentration. It was found that 0.) + nTPPO(org. In Fig. The sodium salicylate and TPPO concentrations were 0. titanium (IV). a log–log plot of the distribution ratio versus log [salicylate] (at fixed pH and triphenylphosphine oxide concentration) gave a slope of 1.5 M sulfuric acid back-extracts zirconium (IV) quantitatively from the organic phase. xylene.29.2%).1%).) → ZrO(Sal) . The results are summarized in Table 4 and show that the extraction efficiency of zirconium in the presence of other metal ions is nearly constant. because of chemical similarities with Zr (IV). Quantitative extraction has been achieved from 10-2 M triphenylphosphine oxide solution. The result shows that about 95% of zirconium was recovered (2) The effect of diluents.
” U. 9 –17..” Use of Di(n-butyl) and Di(iso-butyl) dithiophosphoric acids as complexing agents in the TLC separation of some d and f transition metal ions.1M 94.43 90. 11 (in Czech). Abdel-Rehim. S.C.mL-1) 10 100 10 100 10 100 10 100 Foreign ions Hf (IV) Fe (III) Al (III) Ti (IV) from leach liquor.5 69. Abdel-Rehim. I. N. Abdel-Rehim. and Habib. and Chebotnikova. 391. K. D. and Wilhelm H. 3. “Extraction of TPE.5 36.. pp.. Chatterjee. Basargin.08 2. Ghasemzadeh. pp. 1975. “Solvent extraction of zirconium with Tributylphosphate..K. 149– 158.2.. No. S.” Bulletin of the Korean Chemical Society.K. Indian Journal of Chemistry. No..223–234.M..Y. Kukharev. August 2010 • Vol.M. No. “Solvent extraction separation of zirconium (IV) from succinate media with N-n-octylaniline.” American Chemical Society. R.. and Hayat. 2004..29A. 439-446.7. A. F. Quebec. Vol.” Minerals Engineering. 378.” Radiochemistry (Moscow).9 32. pp. Beyer G.76.. Metallurgical. New York. Issue 4.” Analytical Science. Vol.. 372-376. 1996.. Bidaye.4. 169.42. 1999. B. D.. Issue 4.. 2002. Akhmatov. A..127. and Salavati-Niasari.. Karandashev. David (Ed. H. Vol. A. and zirconium from nitric acid solutions with tetraphenylalkylenediphosphine dioxides. Shmidt. p.. “Aqueous processing of minerals.. 1994.. Curtui. “Extraction of uranium.42. San Diego.N.. In’kova.. pp.. pp. 2000.06 Zr Extraction. and Goletskii. 2002. 78. and Mo from Nitric Acid Solutions with Zirconium Salt of Di(butyl) Hydrogen Phosphate. S. Shamsipur. Vol.. 1983. 20. % 76. “Extraction of metal ions with a primary amine. “Studies on chlorination of zircon.R. and Rupainwar... 1990.. pp.63 93....” Radiochemistry (Moscow).. 67.. and Freund..S. Fedorov.S. 1. B. and Yarkevich. 5091 pp. J. pp. No. Bangladesh Chemical Society. The advantages of this method are: • The method is simple. EP. G. Thermal Analysis. Synthesis of ceramic composite of zirconium and aluminum oxides. Vol. No.G. D. REE. pp..R.243 Welham.M. Mater.. and Petroleum Engineers. K. Vol. 94-98. “Extraction of zirconium (IV) from hydrochloric acid solution with tri-isoamyl phosphate (TAP). “Desilication of zircon with aluminum fluoride in presence of graphite. C. “The extraction of zirconium (IV) from hydrochloric acid solutions by high-molecular-weight amines. 56. Biswas. Reddy.A. P. Zilberman. S. Hasan. 2005.. M. 54. M.M. 1971.Table 3 — The effect of stripping agents on stripping efficiency.” Proceedings of Solvent Extraction Symposium. J.” Report Investment U. pp.” Hydrometallurgy. Doyle. Nukleon. and Oh.. USA. O. 158. Sainte-Foy. pp. Stanley. scandium. and Sargar. hafnium and thorium with a new tetradentate naphthol-derivative schiff base. “Caustic treatment of zircon sand. A. Vol.” American Institute of Mining. Vol. N. Vol.N. Lab.1 69. 78 pp.M.K.” Radiochemistry.. 3 132 MINERALS & METALLURGICAL PROCESSING . Lee. A. B.. “A new technique for extracting zirconium from Egyptian zircon concentrate. Zolfonoun.. “Value adding solvent Extraction.71 Concentration (μg.. A. pp.. pp..” Proceedings of 4th International Conference of Thermal Analysis. S. “Beneficiation of low grade zircon concentrates. Vol. Lee. and Lahiri. thorium. 20. Atomic Energy Commission Report ISC. 2002a. pp. 173– 193. European Patent Appl.” Metals and Materials.N.. A. and References Goletskii.6 10. 1. “Solvent extraction of zirconium (IV) from chloride media by D2EHPA in kerosene”. W. (Diagn. Hydrometallurgy. 1993. Yu.R. Stripping.. pp. 2.” International Journal of Mineral Processing. pp. Turanov.5M 98. 1275– 1283. Wang..C.9 51. • The method needs no pre-equilibration and is free from interference resulting from commonly associated elements. Tejenecky.. 71. Ashrafizadeh..C. 1997.” Radioanalytical and Nuclear Chemistry.... 1974a. 523– 539. pp. A. “Selective zirconium stripping of a loaded Cyanex 272 using Taguchi orthogonal array design. Shmidt.V. July 1–6. A. Fidler. 2006. A Textbook of Hydrometallurgy.8 64. Bureau of Mines.9 Sulfuric acid Nitric acid Hydrochloric acid Stripping agents Table 4 — Comparison of extraction efficiency of Zr (IV) with other associated metal ions Extraction.8 17. R. “Liquid-liquid extraction of trace level zirconium and hafnium with trioctylamine.3.” Radioanalytical and Nuclear Chemistry. 1990.23 88... Nekovar. T. Vol. 63. Kim.. Vol. Vol. Kutyrev. 2000. pp. Vol. pp.5 2. Y. 1. and Corinne. Vol..D. 181. 223. “An innovative method for processing Egyptian monazite. Vol. Vol. pp. “Caustic soda fusion of zirconium ores. pp. Das. selective and rapid.” Serbian Chemical Society.L. Vol. 2000.6 0. A. pp. Akhmatov. 2000..16 95. 1401-1403.. B. and Li D. 1954. “(ZrSiO4) dissolution by ambient temperature processing Australia. K. J.” Acta Chemistry Hungary. 235 Kent. 99–102. 29.. 2000. 437 pp. A. “Industrial minerals and rocks. 30. and Ghannadi Maragheh. A.99 –102.M.M. S.J. Institution of Engineers India.V..” ISEC’96. M... Vol. M.. Kharitonov.V.. 1954. • Using this method to extract zirconium (IV) from associated elements of zircon leach liquor led to 95% zirconium recovery. REE. Y. R.M. Levitt.82 96. F. 1985. M. and Lafond. 1974b. M..9 41.% 96. % 2M 88.6 0. N.K.” Analytica Chimica Acta. F... West D. M. 1. 234– 243. A. H. 154448 A2 11 Sep.” Metallurgical and Materials Transactions. H. 46– 54.. Zilberman. 153– 158 pp Sato. 378. 157. 1956. Taghizadeh. Chernysheva. pp. pp. and Basu. T. Saberyan.. 2008. E. No..Y.N. Vol.2 9. Fedorov.42. N..R. 1982. Metallurgie Extractive Quebec. J.. Conclusions A technique has been developed to extract the zirconium from zircon leach liquor. M. O. A..R.” Studia Universitatis Babes-Bolyai Chemia 45.A. M.8 28..). Distributed by Laval University Bookstore.H. Vol. E. 1071-1075. Abdel-Rehim.6 83.M. and Soran L. Gilbert H. Vol. S. pp.. “Extraction of Zr (IV) from aqueous acid solutions of tri-alkylphosphine. 2nd ed. 17. Vol. N. In: Hui.. 2002b.W.35 89. pp. S. Vol.. No. pp.” IMM Processing.N. 2000. 18 pp.. “Recovery of TPE. Safronova. 56. and Venkatachalan.M.205– 213. Proceedings of 9th International Conference on Composites Engineering. 1982. 501–506. 45.. “Liquid-liquid distribution of the tetravalent zirconium. D. H... 27 No. Ind. Habashi. N.” Journal of Indian Institute of Chemical Engineers. B 30.58 96.9 1M 98.A. 1–2. Vol. and Duyvesteyn. Inc. M. pp. Saberyan. A. Abdel-Rehim.H. and Watanbe. G. Hanguk Chawon Konghak Hoechi.M. and Kumar. 1999.S. A. Schroetterova.A. pp. 6 87.E. Seidl. “Liquid–liquid extraction of tetravalent zirconium from acidic chloride solution using Cyanex 272.35. and Mrnka.). Z.. Biswas.1545– 1549.. Sato. V. 2007. and Mo from high-level raffinate with zirconium salt of Di(butyl)hydrogen phosphate. The final concentration of zirconium in the leach liquor was 500 μg mL-1 and the amount of zirconium recovered by the proposed method was 475 μg mL-1.. 1994.. Rajmane.
2003). Society for Mining. flotation always presents a relatively high energy cost.. feed percent solids and the reciprocation and spacing of water sprays). this concentrator provides a potential way to achieve continuous concentration and obtain a high-grade concentrate from tailings. Kunming University of Science and Technology. due to its high operating expenses and complexity compared with physical separation methods. Yunnan Province. Moreover. 1999) and to the increasing demand for high-grade materials in the iron and steel industries on the other (Arol and Aydogan. 2008) and the concentration of magnetite in a flotation column (Zhang Haijun et al.40 % Paper number MMP-09-031.Performance of a full-scale continuous centrifugal concentrator in reconcentrating fine hematite from tailings Luzheng Chen. Key words: Gravity separation. 2007. Faculty of Land Resource Engineering. due to limitations in the scale-up design and the fluctuations of feed material characteristics. For example. Iron/ iron ores Introduction Currently. Copyright 2010. as well as having a high reagent consumption and causing environmental pollution. feed volume flow rate. 3 • August 2010 . centrifugal acceleration. However. Original manuscript submitted July 2009. It should be noted that numerous pilot-scale trials to clean various magnetite minerals using magnetic aggregation techniques have been conducted during the past decade in China. 2004. The results indicate that among the variables considered in the study (water spray pressure. 2004). prior to February 28. simple operation and flexibility are needed. reverse flotation is widely used to obtain a high-grade concentrate in iron ore processing flowsheets. Revised manuscript accepted for publication November 2009. China Abstract The study aimed to evaluate the separation performance of a full-scale continuous centrifugal concentrator in the reconcentration of fine hematite from high-gradient magnetic separation (HGMS) concentrate in a tailings recovery plant. Jin Wenjie et al. Siqing Liu and Shuming Wen Associate professors and professor. 2011. Although performance of the full-scale concentrator is slightly inferior to pilot-scale trials. 2008). (2000) achieved an improved concentrate product assaying 53. and to investigate the usefulness of the technology in industrial applications. In addition. Hematite. the removal of hematite from silica (Mowla et al. where low capacity and cost. Pavlovic and Brandao. There is increasing interest in using physical separation devices to clean tailings material and obtain high-grade iron concentrates.. the change in centrifugal acceleration affects the recovery the most and continuous concentration can be achieved only when the water spray has a sufficient pressure. in such applications as the concentration of hematite from quartz (dos Santos and Oliveira. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. the reciprocation and spacing of the water sprays have a significant influence on the concentrate grade. flotation may not be preferred. and Exploration. Metallurgy. Tailings. Inc. The effect of changing the operating variables on concentrate grade and recovery was studied. This interest is due to increasing energy and reagent costs and stringent environmental restrictions on the one hand (Burt. Yu Yongfu. respectively. MINERALS & METALLURGICAL PROCESSING 133 Vol. 27 No. Kunming.
. This outcome is due to the fact that the strong capturing effect of the magnetic force upon magnetic particles results in the high recovery of partially liberated magnetic particles. instead.Figure 1 — Schematic demonstration of a continuous centrifugal concentration. 2005) and Falcon concentrators are used for fine coal cleaning (Honaker et al. Knelson concentrators are widely applied in the gold industry (Coulter and Subasinghe. 2 = drum. it cannot be used to treat weakly magnetic minerals. in which particles separate depending on differences in density and the characteristics of the flowing film (Ergün and Ersayin. 2009). notably in reconcentrating fine hematite from HGMS concentrate. 1) and flow out of the drum. resulting in deterioration of the concentrate grade. 58 62% Fe or higher. It was reported by Chen Luzheng et al. 8 = drum driver. e. W = water inlet.. Further theoretical analysis and pilot-scale trials have demonstrated the effectiveness of this concentrator. due to being subjected to the stronger centrifugal force. even negligible (Liu Yang et al. but generally it does not produce a high-grade marketable concentrate. as the sprays flush down the settled bed through the whole depth of the film. 4 = guard. While traveling over the drum. concentrate mass compared with that of precious minerals. similar to the cutting of rocklike material with a moving water jet (Momber and Kovacevic.. The reciprocation of the sprays is much lower than the axial velocity of the flowing film. 7 = reciprocating mechanism. they are in the upper moving layers of the film and flow quickly out of the drum. Light minerals (hollow circle in Fig. This magnetic separator usually achieves a 1 . thereby deteriorating the quality of magnetic concentrate. to investigate using the technology to reconcentrate fine hematite from an HGMS concentrator in industrial applications. because the concentration of iron minerals always involves a tremendous Brief introduction to continuous centrifugal concentration. The August 2010 • Vol. The purpose of this paper is to evaluate the separation performance of the concentrator. 2002. slurry is evenly fed onto the inner surface of the drum. C = concentrate. the main focus being the grade and recovery of the concentrate product and the response of the concentrator to changes in feed and operating conditions. Continuous concentration is achieved using reciprocating water sprays to remove the settled bed. 2008) that a continuous centrifugal concentrator was able to obtain a high-grade concentrate by reconcentrating HGMS concentrate from a refractory fine hematite ore and tailings. but a lower radial settling velocity. but not many centrifugal concentrators are reported to be effective in concentrating iron minerals. the axial velocity of the flowing film increases due to the drum’s angle of inclination. Majumder et al.. Therefore. 3 = feed device. 2001). 2006).89 % Fe using a magnetic separation column. exceeding this grade. a full-scale continuous centrifugal concentrator was installed in a tailings recovery plant at the Hainan Iron and Steel Company in southernmost China in 2007. Although magnetic aggregation is used to obtain highgrade magnetite concentrate. 1997). quality improvement becomes increasingly difficult. due to being subjected to a weaker centrifugal force. As the drum rotates. As illustrated in Fig. 1) obtain a higher axial acceleration over the drum. 27 No. High-gradient magnetic separation (HGMS) is now widely used to preconcentrate weakly magnetic minerals (Xiong Dahe. 1996). heavy and light minerals stratify and leave it in separated layers. 6 = water sprays. Some of the lighter minerals will inevitably be flushed down into the concentrate.4% grade improvement when used to clean relatively high-grade magnetite concentrates. these materials travel through the sprays in spiral curves via the spacings between the sprays (as schematically presented in Fig. 1997).1. (2007. 5 = concentrate collector. Centrifugal concentration provides a means to reconcentrate weakly magnetic minerals and produces a high-grade concentrate. Fe by cleaning a magnetite concentrate assaying 46. 3 134 MINERALS & METALLURGICAL PROCESSING . so that the light minerals in the film escape being flushed into the concentrate. F = feed. such as hematite. thus. Figure 2 — Full-scale continuous centrifugal concentrator: 1 = support frame. A magnetic gravity concentrator using the technique was also reported effective in obtaining a high-grade magnetite concentrate (Yuan Zhitao et al.g. T = tailings. Heavy minerals (solid circle in Fig. such as gold. The concentrator achieves separation due to the centrifugal acceleration of a thin flowing film.. 1) in the film settle down into the drum and form a settled bed.
epidote. 2 consists of a conical drum made of polyester alkyd with a wearable layer in the inner surface and a unique reciprocating mechanism.54 % region. due to the limitations in precision and the slight elasticity of the polyester alkyd material of the drum.5°.or two-inclination configuration of 3 . Feed volume flow rates were measured using a sample can and a chronometer. tremolite.60 mm/s and water spray pressure is 0 .45 × 0. instead of the single.76% of the material is respectively less than 74 μm and 37 μm. and light particles are driven outward to become tailings. 1600 × 900 mm. i.60% (-74 μm). the spacing of water sprays is designed to be adjustable from 50 to 100 mm. The reciprocating mechanism of the concentrator was connected to a nearby clean water pipe via a high-pressure water tube. 3 • August 2010 . In the upper chamber of the drum is installed a concentrate collector below the reciprocating water sprays. the continuous concentrator has an decreasing three-inclination drum configuration of 10°. causing the settled bed of heavy particles on the drum surface to be flushed down into the concentrate collector. This full-scale continuous concentrator is modeled on the pilot-scale concentrator (Chen Luzheng et al. due to centrifugal force. Normally..5° in a conventional concentrator. quantity of these lost minerals. muscovite.97 % and 68 .. However. compared with other centrifugal separators.45 m3. water spray reciprocation is 20 .Figure 3 — Experimental setup of full-scale continuous centrifugal concentration: 1 = full-scale continuous centrifugal concentrator. In addition. the feed material enters the rotating drum as a slurry through a feeding device. As shown in Fig. 6 = sample can. can be minimized by optimizing the reciprocating sprays.60 g (g is gravity acceleration). 2008) and the conventional intermittent centrifugal concentrator. Description of feed.56% Fe. instead of a vertical one as characteristic of the Knelson and Falcon concentrators. Operating parameters are the same as the pilot-scale concentrator. Drum size is the same as the conventional intermittent concentrator developed in the 1960s in China. feed volume flow rate was controlled by an adjustable valve located below the feed box with a volume of 0. and 91 .8 mm in an axial direction are detectable while the drum rotates at a speed of 200 r/min (around 48 g). Figure 4 — Effect of water spray pressure on concentration continuity. two lean hematite ore processing plants and a sulfur-rich lean hematite ore processing plant. feed size = 92. Conditions: feed volume flow rate = 10 m3/h. hematite is the dominant mineral in the feed material.2. a vibration at least 7 .6 MPa. Experimental Full-scale continuous centrifugal concentrator. The 1600 × 900 mm (drum diameter × length) full-scale continuous centrifugal concentrator as shown in Fig. 4 = pressure gauge.. with the primary gangue minerals being quartz. Two scaleup conditions are used in the full-scale concentrator: 1. The material is characterized by fluctuations in feed conditions. And as shown in Fig. respectively. i. 3. This fluctuation is mainly due to the frequently disrupted operations of one or two of the four hematite ore processing plants itemized above. garnet and barite. The tailings treated at the plant are from a rich hematite ore processing plant. iron grade varies in the 48 . 2009). accounting for more than 96 % and 70 % of the iron values.. While the concentrator is being operated. A pressure pump was installed in the pipeline to produce highpressure water sprays.9 T at the tailings recovery plant of the Hainan Iron and Steel Company (Chen Luzheng et al. one of the essential features of this full-scale concentrator is a horizontal cone drum similar to that of the multi-gravity separator. feed grade = 49.0. It should be noted that. 27 No. notably iron grade and particle size.5°. The reciprocating mechanism ejects high-pressure water sprays against the rotating drum. 2. feed % solids = 30%. The fine hematite material fed to the full-scale concentrator was from the magnetic preconcentration product stream of a SLon-2500 pulsating HGMS separator operating at a background magnetic induction of 0. The required water spray pressure was achieved through another adjustable valve located between the MINERALS & METALLURGICAL PROCESSING 135 Vol. Methods. however.e. 3 = adjustable valve. centrifugal acceleration is 0 . 2 = pressure pump. The slurry is forced onto the drum wall and rotates with the drum in the form of flowing film. 2.50 × 0. 5 = feed box. Heavy particles in the film settle down onto the drum surface. Thus.10 mm in a radial direction and a vibration at least 6 .e.
Conditions: water spray pressure = 0.13 40. feed grade = 52.73 33.48 12.29 56. Due to the fluctuations in feed material.15 64. the water spray pressure has a dominant influence over the concentrate weight.75 52.34 8. 2009) and the impact energy of the sprays was kept sufficient to flush down the bed using nozzles with different diameters.36 56. the settled bed obtains a higher rotating energy as the acceleration (i. The feed volume flow rate and feed % solids were measured and examined periodically to keep a steady feed flow to the concentrator. % Fe 55. 4 that when all the other variables are kept constant.73 67. % 78. a typical sample was collected from the concentrate stream for analysis.99 58.. Effect of water spray pressure on concentration continuity. concentrate weight increased drastically as the water spray pressure increased.85 61.36 70.56 52.60 11.66 14. 61.68% (-74 μm).After sufficient time was allowed for the concentrator to achieve steady operation. First.09 52.07 Grade. Results and discussion Figure 5 — Effect of centrifugal acceleration on performance.5 % when the centrifugal acceleration increases from 22 g to 40 g and 60 g.07 58.8 m3/h. feed volume flow rate = 9. August 2010 • Vol. the impact angle of the water sprays with respect to the drum surface was fixed at 45° (Ren Nanqi et al.15 52.89 53.45 52. The separation results indicate that the maximum concentrate weights are approximately 44 %. 31.70 52. drum rotation speed) increases.50 48.28 29.39 52.51 59. water spray spacing = 100 mm.06 74.65 64.29 58. feed size = 91. the aggregating force between heavy particles in the settled bed on the drum surface increases as the centrifugal acceleration increases.56 6.45 52.22 57.61 60.17 58.69 65.68 68. Operating parameters Feed volume flow rate (m3/h) (Feed % solids. 3 136 MINERALS & METALLURGICAL PROCESSING .61 Iron recovery..30 .48 MPa.63 62. Centrifugal acceleration is adjustable through an AC transducer connected to the drum driver and the reciprocation of the sprays is adjusted through another AC transducer connected to the reciprocating mechanism of the concentrator.25 52.31. this maximum increased as the acceleration increased. Continuous concentration is achieved as the concentrate weight approaches an invariable value with the increase of water spray pressure.89 20.00 58.36 58. For each acceleration. Second. pressure pump and the reciprocating mechanism and a pressure gauge was used to indicate the operating pressures of the sprays.22 58.40 52.86 Table 1 — Effects of feed volume flow rate and feed % solids on performance.36 58. as a result of their exposure to a stronger centrifugal force. % 81.53 10.88 61.04 64. until it reached a maximum.08 58.56 35.37 Feed grade.49 58. water spray reciprocation = 50 mm/s. centrifugal acceleration = 48 g. water spray reciprocation = 50 mm/s. The effect of the impact pressure of the water sprays on the concentration continuity was first studied with the concentrator at different centrifugal accelerations. Concentrate Weight.38 52. Two main factors contributed to this result.62 52.91 65. 9.e. 27 No. the effect of changing the operating variables on the separation performance of the concentrator was assessed only when the feed to the concentrator was found to be basically steady.83 63.81 61.45 MPa.59 61.21 67.67 52.54 52. water spray spacing = 100 mm.27 58.78%) 4.41 Feed % solids (%) (Feed volume flow rate. It can be seen from Fig. % Fe 52.52 9.80 9. water spray pressure = 0.77 58.69 67. respectively.18 52.35 Conditions: feed size = 90% (-74 μm).41 58.52 69.17% Fe. feed % solids = 32%.85 m3/h) 16.35 66.61 61.35 56.56 25. For all tests in this investigation.5% and 70. The combination of these two factors requires a higher impact pressure in order for the water sprays to flush down the settled bed of heavy particles completely.
11. resulting in less time for the settling of well-liberated fine hematite minerals.53 . feed grade = 51. while iron recovery increases throughout. Combining the results of the pilot-scale and full-scale concentrators in reconcentrating this fine hematite. increasing the centrifugal acceleration increases the settling velocity of very fine particles in the flowing film and thus the concentrator achieves a higher processing capacity. the centrifugal acceleration has a very significant effect on the performance of the concentrator.. respectively. Effect of centrifugal acceleration on performance. For example. Centrifugal acceleration has the most significant effect on the separation performance of an enhanced gravity concentrator.28 to 33. the concentrate grade decreases. feed volume flow rate and feed % solids. as illustrated in Fig. From the separation results in Table 1. acceleration is the dominant force determining the number of particles going into the concentrate. As illustrated in Table 1. the concentrator mainly concentrates partially liberated larger hematite minerals.33. beyond the 40 .48 g range. 27 No.5% is suitable for the materials tested in the present investigation.8 m3/h. Thus.86 % Fe and 67.5 . Conditions: feed volume flow rate = 9.10. As the acceleration increases from 20 g to 60 g.45 MPa. continuous concentration is possible only when the water sprays have a sufficiently high pressure..5% . As explained elsewhere (Chen Luzheng et al.67 . an increase in feed volume flow rate allows for an increase in feed % solids. because these two variables also contribute to the centrifugal force acting on particles in the flowing film. where the concentrate grade and recovery vary in the narrow regions of 58. when the feed volume flow rate is restricted within the range of around 9. The effect of feed conditions.68.45 MPa was studied.73 . continuous concentration is achieved using reciprocating water sprays to remove the settled bed of heavy particles on the drum surface. 3 • August 2010 . water spray pressure = 0.48 g.56%. This effect reduces the recovery but increases concentrate grade. thus improving processing capacity. the grade deteriorates markedly.44 %.5 m3/h and feed % solids of 25. feed % solids = 32%. Analyzing the results in Table 1. the effect of centrifugal acceleration on the performance matches well. As the reciprocation and spacing MINERALS & METALLURGICAL PROCESSING 137 Vol.. The highest performance is achieved when the concentrator operates at an acceleration of 40 . particularly on iron recovery. reaches a plateau and then begins to decrease. Effect of feed volume flow rate and feed % solids on performance.g. feed % solids may vary from 25. the effect of acceleration on recovery is more pronounced at low levels. which results in a low concentrate grade and recovery. a particular feed volume flow rate is needed to achieve selective concentrations of iron values from slurry. increasing feed % solids obviously decreases the concentrate grade but increases the recovery. for an optimized feed volume flow rate of around 9. with the processing capacity of the concentrator varying from 2. with feed volume flow rate and feed % solids separately fixed at around 10 m3/h and 32%. the critical spray pressure for continuous concentration is related to the iron grade and particle size of the feed material.6 m3/h. as many lighter gangue minerals go into the concentrate. As noted above. It was demonstrated during the industrial test that the optimum feed volume flow rate is closely correlated with feed % solids. 5. and more fully liberated finer hematite minerals go into the concentrate and the performance improves tremendously. it is concluded that a combination of a feed volume flow rate of 8. because it determines the centrifugal force on the particles to be separated. on the performance of the concentrator operating at an optimum acceleration of 48 g and at a sufficient water spray pressure of 0.Therefore.68 to 5. which decreases the concentrate grade and increases the recovery. the flow depth and axial velocity of the film increase. 5. the effect of centrifugal acceleration on the separation performance of the concentrator was studied during the industrial test.58. When operated at an insufficient acceleration. water spray spacing = 100 mm. ing in the settling of partially liberated hematite and gangue minerals onto the drum. result- Figure 6 — Effect of water spray reciprocation on performance. centrifugal acceleration = 48 g. thereby affecting the settling trajectories of particles in the film. Therefore. In a limited range.5 % (-74 μm).23 % Fe. The centrifugal force acting on particles increases as the acceleration increases.8 m3/h. 2002). As seen in Fig. due to their being subjected to an excessively strong centrifugal force. i.e. An increase in feed volume flow rate increases the concentrate grade but reduces the recovery rapidly for a steady feed % solids of around 31. feed size = 91. concentrate grade increases.8 m3/h. Furthermore.50% and the highest performance is achieved when the feed volume flow rate is in the narrow region of 9. with almost no negative effect on separation results. when the concentrator is operated at an excessive acceleration. As the feed volume flow rate increases.16 t/h. An insufficient feed volume flow rate decreases the flow depth and axial velocity of the film. feed volume flow rate and feed % solids both have significant effects on performance. 2008). iron grade and particle size) and the centrifugal acceleration. In addition. it should be noted that the optimum feed volume flow rate and feed % solids are dependent on such factors as the characteristics of the feed (e. Effect of water spray reciprocation on performance. However. This action allows for a high flexibility in operating the concentrator. Increasing the feed volume flow rate over an inclined deck increases the flow depth and the axial velocity of the film (Ergün and Ersayin.
48 % Fe. resulting in the improvement of concentrate grade and the reduction of iron recovery (Fig. these barriers decrease as the spacing of water sprays increases. Evaluation of full-scale continuous centrifugal concentrator In summary. it is predicted that a higher concentrate grade may be achieved if a spray spacing larger than 100 mm is used. Most light and partially liberated particles escape being flushed into the concentrate via the spacing between the sprays (schematically illustrated in Fig.Figure 7 — Effect of water spray spacing on performance. each spray of water creates a barrier. feed size = 90. The test results indicate that when the spacing is adjusted from a minimum of 50 mm to a maximum of 100 mm. in 2008. Conditions: feed volume flow rate = 9. As mentioned above. a larger spacing of the sprays necessitates the redesign of the reciprocating mechanism in the concentrator.45 MPa. Therefore. feed grade = 51. 7. This test confirmed that the negative flushing effect of the water sprays can be minimized by optimizing the water spray reciprocation. as shown in Fig. As seen in Fig. a suitable reciprocation improves the concentrate grade significantly but slightly reduces the recovery. August 2010 • Vol. as schematically presented in Fig. feed % solids = 32.82% recovery at a reciprocation of 40 mm/s and then decreased as the reciprocation progressed. this in turn has a significant effect on the performance of the concentrator. because the number of sprays decreases with increasing spacing. An increase in the spacing increases the concentrate grade but reduces the recovery. water spray pressure = 0. Figure 8 — Photographic diagram of barriers generated by the water sprays (reciprocating at an excessively low rate of 10 mm/s) in the film. The grade increased and reached a high point of 58. From Fig. centrifugal acceleration = 48 g. continuous concentration is achieved using reciprocating water sprays to remove the settled bed of heavy particles on the drum surface.02 % recovery) found with the pilot-scale concentrator in reconcentrating this fine hematite.86 %. When the reciprocation of water sprays is fixed at the optimum value of 40 mm/s. when all variables were set at optimum levels. 3 138 MINERALS & METALLURGICAL PROCESSING . Also. as the water sprays reciprocating at a fixed reciprocation remove the settled bed on the drum surface. with a corresponding reduction of recovery.7% Fe with 66 . 7). with a very few such particles inevitably flushed down into the concentrate.66% Fe with 68. As can be seen from Fig. the concentrate grade increases from 55.9 % Fe with 65. It should be noted that.82 m3/h.69 % Fe to 59. water spray reciprocation = 40 mm/s. in order to flush down the settled bed of heavy particles on the drum surface completely. this result is due to the fact that the spacing determines the quantity of light particles to be flushed into the concentrate. 2. 8.3%. The spacing is changed by altering the number of nozzles fixed on the reciprocating mechanism of the concentrator. 1) and instead flow out as tailings. The reciprocation has a profound effect on the thickness distribution of the settled bed on the drum surface and hence generates a significant influence on the characteristics of flowing film. as illustrated in Table 2. the spacing of water sprays has a significant effect on the separation performance of the concentrator. the nozzles on the mechanism are designed to be capable of traveling through the whole separation width of the drum.38 to 67.7. their effects on the performance were studied in detail. the effect of the spacing of the sprays on separation performance is shown in Fig. this full-scale concentrator achieved a concentrate grade improvement of 6 . it is apparent that the quantity of light particles flushed down by the sprays decreases with the increasing spacing of water sprays. 7. Recovery decreased continually with the increase of the reciprocation from 20 to 60 mm/s.7% (-74 μm). In other words. while the recovery drops from 75.69% recovery.63% Fe. Effect of water spray spacing on performance. 6. (or number) of water sprays are the two dominant operating parameters affecting the performance of the concentrator in terms of the reciprocation. 27 No. which is slightly inferior to the best separation result (concentrate grade improvement of 9. A more detailed description on the effect of the reciprocation of water sprays on the separation performance of a continuous concentrator was reported by Chen Luzheng et al.
27 No. it produces a high-grade marketable concentrate in the recovery plant. with a sulfur-rich lean hematite ore processing plant of HGMS-reverse flotation flowsheet going into operation in late 2007.64 40. Apparently. northeast China). Also. This full-scale concentrator was also tested for its ability to reconcentrate the fine hematite minerals from HGMS concentrate from a refractory hematite ore discarded by the Donganshan processing plant (Anshan Iron and Steel Company.15 mm. feed % solids around 31. 2007).02% Fe with 79.47 41. radial 7-10 mm.78 Iron recovery. as the aggregating force between heavy particles in the settled bed and the rotating energy of the bed increase with the increase of centrifugal acceleration. generating remarkable MINERALS & METALLURGICAL PROCESSING 139 Vol. because it determines the centrifugal force on particles to be separated and thus presents the dominant force determining the number of particles going into the concentrate. it is the result of the limitations in the scale-up design of the concentrator. This plant contributes about 40% by weight of the total tailings to the recovery plant. i. % 63. axial 10. The maximum critical water spray pressure necessary for achieving continuous separation increases with increasing centrifugal acceleration. Concentrator Full-scale a Grade.52 41.0% Fe.27 65.37 62.13 30.05 Concentrate 61. water spray reciprocation at 40 mm/s. however. water spray spacing at 100 mm and water spray pressure of 0. the centrifugal acceleration has a very significant effect on the performance of the full-scale concentrator. 9 compares the separation results of two full-scale concentrators of different radial and axial vibrations at the tailings recovery plant.45 MPa. As can be seen. axial 6-8 mm. % 79. reducing iron grade and particle size of the tailings fed to the recovery plant. it provides a potential way to achieve continuous concentration and to obtain a high-grade concentrate Figure 9 — Effect of drum vibration on performance: 1) Vibration: 1#. Although the concentrator has not reached its optimum scale-up design and the performance may be improved as discussed above. notably iron grade and particle size as described above. drum vibration has a significant influence on the iron recovery. the separation performance of this concentrator is in close correlation with the characteristics of the feed material..32 58. . The feed to the concentrator is also characterized by wide fluctuations in iron grade and particle size (Chen Luzheng et al.Table 2 — Performance of pilot-scale and full-scale.88 Weight.02 66. however. This inferiority is the result of the fluctuations involved in the feed material during the industrial test. The performance of the full-scale concentrator cannot be compared to the pilot-scale trials and to its performance in reconcentrating the refractory hematite ore..69 58. radial 1418 mm. the concentrator achieved a better performance (concentrate grade improvement of 12. Another reason for the inferiority is that the tailings pumped to the recovery plant have become more complicated and difficult to treat than those tested in the pilot-scale concentrator. it has no marked effect on concentrate grade.42 51.As with the pilot-scale concentrator. % Fe Feed 49.41 Efficiency. feed grade around 51.22 Feed type Refractory hematite ore Fine hematite tailings Pilot-scale Full-scale b a b 52. the highest performance was achieved when the concentrator operates at an acceleration of 48 g. As such. A typical separation result for this hematite ore is illustrated in Table 2. 5#.0 % below 74 μm. a higher concentrate grade may be achieved with a larger water spray spacing.41% recovery) compared with those of the concentrators in reconcentrating the fine hematite tailings. Fig. % 52. feed volume flow rate around 9.Feed volume flow rate and feed % solids affect the characteristics of the flowing film significantly. 3 • August 2010 . feed size around 90. . Conclusions It can be seen from the discussion above that: .99 Typical separation achieved by a full-scale concentrator with refractory hematite ore (Anshan Iron and Steel Company) Average separation achieved by ten full-scale continuous concentrators over 72 hours with fine hematite tailings (Hainan Iron and Steel Company). Obviously. particularly on iron recovery. they are operated under the same conditions.0 %. 7. from tailings.22 54. As shown in Fig.07 Tailings 27.Continuous separation is achieved only when the reciprocating water sprays have a sufficiently high pressure to flush down the settled bed of heavy particles on the drum surface.e.6 m3/h.
Vol. 1. 1999.. pp. 17. R. Chen Luzheng. Majumder. “Impact energy analysis of turbulent water beams for continuous centrifugal concentration. 37. No.” Minerals Engineering. 2006.. Chen Luzheng. 9. N. although there will be a corresponding reduction in the recovery. Cao Yijun.influences on the performance of the concentrator. 25-29 (in Chinese). P. 2004. 17-19 (in Chinese). Honaker. pp. Coulter. Aspects. “Experimental study on performance of a continuous centrifugal concentrator in reconcentrating fine hematite. 63-66 (in Chinese). and Ersayin..” Nonferrous Mining and Metallurgy. Acknowledgments The project was supported by the Educational Key Program of Yunnan Province of China (Grant No. 11.. 27 No. 2009. 15. pp. pp. 1. an increase in feed volume flow rate allows for an increase in feed % solids and thus an improved processing capacity. 1003-1007. an increase in the spacing increases the concentrate grade but reduces the recovery.. However. 14. pp. Although the performance of the full-scale concentrator is slightly inferior to pilot-scale trials in reconcentrating the fine hematite. Vol.” International Journal of Mineral Processing. 437-446. “Utilization of humic acid as a depressant for hematite in the reverse flotation of iron ore. “Test research on cleaning of various kinds of magnetite ores with Yufeng magnetic separation column and its industrial application. Yu Yongfu. August 2010 • Vol.” in Proceedings of XX IMPC. G.. Vol. and Subasinghe. 1117-1122. R. 09Z0014).. Zhu Gaoshu. 4. dos Santos. Vol. pp.. S. Chen Luzheng.” Minerals & Metallurgical Processing. Li Lianbo. Vol. K. 1.” Colloids and Surfaces A: Physicochem. Water split behavior. L. 16. Zen Li. No. as the spacing determines the quantity of light particles to be flushed into the concentrate. simple operation and flexibility. Karimi. 2008. T.. 2009. No. and Ho. 80. 1996. Vol. Aachen. Liu Yang. Part I: Characterization of flow over pinched sluices. Vol. P. Ren Nanqi. 1997. and Xiong Dahe. 17-25. No. 20. pp. Xiong Dahe. No. K. 2009. Wang. 71-77. it is still significant compared with other separation methods (such as flotation).” Minerals Engineering. D.Due to the limitations in the scale-up design. “Application of the Falcon concentrator for fine coal cleaning. M. pp. 11. I. Yuan Zhitao. and Xiong Dahe. Vol. Momber. G. 1. Chen Luzheng. 2-3. 58.” Metal Mine.” Separation and Purification Technology. Vol. G. pp.” Minerals Engineering. Xiong Dahe. u0837602. 1-2. pp.The reciprocation and spacing of water sprays have significant effects on the concentrate grade. Ren Nanqi. pp. which in turn have a significant effect on the performance of the concentrator. As the concentrator is not in its optimum scaleup design and the performance may be improved as discussed above. 1997. Xu Xinyang. Eng. “A mechanistic approach to modeling Knelson concentrators. “Removal of hematite from silica sand ore by reverse flotation technique. 2005.. J. “The role of gravity concentration in modern processing plants. 18.. I.F.. J.. 1. “Adsorption of starch. 10. No. pp.. 2007. R. D.” The Chinese Journal of Nonferrous Metals. A. A. pp. No. Also. 3. . “Recovery enhancement of magnetic fines in magnetic separation. 26. No. 100-106 (in Chinese). 3. No. 2000. “Industrial test for recovering microfine iron minerals by SLon continuous centrifugal separator.” Minerals Engineering. amylopectin and glucose monomer and their effect on the flotation of hematite and quartz. 21-26. and Aydogan.Q. 2002. “Advances in iron ore dressing technology at home and abroad and their influence on iron-smelting.. and Huang Huichun. Pavlovic.. Lyman.” Journal of China University of Mining & Technology. the fluctuations of the feed material.. “Research on cationic reverse flotation of magnetite using a flotation column. 4. An optimized reciprocation improves the concentrate grade significantly but slightly reduces the recovery. pp. and Kovacevic. “Development and applications of SLon vertical ring and pulsating high gradient magnetic separator. . pp. Vol. 163-168. 1. 34. 12. Ren Nanqi. 2007. and Zheng Longxi. No. amylose. R.W. 2003. O. pp. it was not possible for the concentrator to obtain a separation performance comparable to the pilot-scale concentrator in reconcentrating fine hematite or to its own performance in reconcentrating refractory hematite ore in earlier studies. 6. “Test parameter analysis in abrasive water jet cutting of rocklike materials. Jin Wenjie.” Metal Mine. No. pp. Wang Yongtian. and Xiong Dahe. “Magnetic aggregation and magnetic separator. Zhang Haijun.. Vol. and Ostadnezhad. Vol. 151-154. 3. 45-47 (in Chinese). the Yunnan Provincial Foundation for Applied Basic Research (Grant No.. Vol. In a limited range. 67-71 (in Chinese). K. The reciprocation affects the thickness distribution of the settled bed on the drum surface and the characteristics of flowing film. 99-103.. due to its low cost. 232. “Modeling of flowing film concentrator Par 1. “Studies on pinched sluice concentration. 1291-1300. No. G. A. A. Brennan. 2008. 16.” International Journal of Rock Mechanical and Mining Science. 9-17. 2004. N.) References Arol.. 11. No. No. No. pp. 2009ZC007X) and the key program of the National Natural Science Foundation of China (grant No. Liu Jiongtian.” Minerals Engineering. 419-423. and Holtham. Mowla. No. Ergün. the continuous concentrator produces a high-grade marketable concentrate from the tailings in the recovery plant.. “Experimental research on applying magnetic separation column in separating the rougher concentrate of Panzhihua Steel Co’s Concentrator. and Brandao.” Minerals Engineering. the optimum feed volume flow rate is closely correlated with feed % solids. 3 140 MINERALS & METALLURGICAL PROCESSING .D. and Liu Bingyu. 87. Vol. No. No. Burt. pp. pp. 1143-1156. and Oliveira. a higher concentrate grade may be achievable if a spacing larger than 100 mm (the maximum of the concentrator) is used. 1. S. it is thus concluded that it provides a potential way to achieve continuous concentration and to obtain a high-grade concentrate from tailings. 2008.” International Journal of Mineral Processing. 2001. Vol. Vol. 9-16.” Metal Mine. No. and Ma Zilong. “Pulsating high-gradient magnetic separation of fine hematite from tailings. K.” Journal of Harbin Institute of Technology (New Series).
an amount that demands further processing of the slag. 2007). Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Accordingly. E-mail: imihajlovic@tf. 1997. such as smelting in a reverberatory furnace. Mining and Metallurgy Institute. University of Belgrade. Copper/ copper ores. Serbia. The results of calculations obtained using MLRA were compared to actual measured results and found to have a large degree of correspondence. 1991. These components influence the oxide (Cuox). Mihajlovic Professor. Processing of such copper-rich slag is facilitated using flotation or electroprecipitation of remaining sulfides. Copper losses in silicate smelting slag depend on a large number of factors. Jalkanen et al. Technical faculty in Bor. It was determined that. In recent investigations it was determined that there is a connection between individual components of the slag composition. Bor. Živkovic Professor. 2009). Partially dissolved copper and unsettled copper matte droplets present in the waste slag result in copper losses (Biswas and Davenport. such as the composition of the input materials or the overall physicochemical structure of the smelting products. Society for Mining.SiO2). Numerous investigations have revealed that slag composition has a dominant influence on its copper content (Matousek. to subjective factors. INCO. resulting in about 0. 2003). the prevailing compound in the slag is fayalite (2FeO. smelting follows the oxidative roasting of the concentrates. This paper uses multiple linear regression analysis (MLRA) to determine the degree of influence. Bor.975. Fe3O4.rs ´ Đ. Imriš et al. Key words: Smelting.ac.bor. A relationship between the copper in Paper number MMP-09-047. Serbia ´ I.. respectively.. Nikolic Professor. this loss is about 0.Copper losses in sulfide concentrate smelting slag are dependent on slag composition ´ Ž. Serbia N. University of Belgrade. such as those depending on the management of the process (Jalkanen et al. Metallurgy.. Mitevska Research engineer. 1996. 2003. 2003).. because such slag is disposed of in the waste yard. and that this ratio is not dependent on the slag or matte composition. the copper content in the silicate slag can reach 2%. Multiple linear regression analysis Abstract Introduction During pyrometallurgical copper extraction. 2003). prior to February 28. and Cu. These products are differentiated along the melting zone length by gravitational settling. 2011.. 3 • August 2010 . With stationary smelting processes. Habashi. MINERALS & METALLURGICAL PROCESSING 141 Vol. Bor. Revised manuscript accepted for publication March 2010. according to their specific gravities. Bor. Serbia The silicate slag and copper matte that are the byproducts of smelting copper in a reverberatory furnace contain SiO2. Thus.. With dynamic smelting processes such as Flash. 2009). Fe and S. Copper losses. Technical faculty in Bor. Sarrafi et al. copper content in the matte and the copper content in the slag (Živković et al. CaO and Al2O3. Original manuscript submitted October 2009. Inc. Global annual slag production resulting from copper smelting operations is above 25 tons (Gorai and Jana. resulting in the development of two main products: silicate slag and copper matte. 74% is in sulfide and 26% in oxide form.5% Cu in the remaining waste slag (Živković and Savović. Copyright 2010. FeO. and Exploration. These results indicate that slag composition and copper content in the matte influence the copper losses in the waste slag with a probability of above 97%. copper loss to waste slag strongly influences the worldwide rise of the copper extraction process (Maweja et al.. of the total copper content of the slag. Slag.5% Cu and is permanent. 2003. sulfide (Cusul) and total (Cutotal) copper content lost in the waste slag. with the coefficient of determination R 2 = 0. with SiO2 and FeO as dominant constituents. University of Belgrade. The slag is a silicate solution. ranging from objective ones. 2009). etc. Goni and Sanchez. both operations are performed in the same unit. Technical faculty in Bor. 27 No. In the modern pyrometallurgical processes of copper extraction.
.76 3.49 4.78 45.94 44.65 0.78 43.48 44. Liu et al. as a function of the input materials composition.51 0.73 3.48 0. Magaeva et al.63 3. Živković et al.59 0.62 43.13 0. 2007.7 mm and a length of 6.66 31.44 25.12 29.06 7.44 33.03 7.58 32.51 0.40 46.14 0.20 43.95 3.15 0.80 44. and the copper in the matte during copper sulfide smelting has also been derived by Sridhar et al.62 31.55 0.71 32. The sampling probe is a pipe made of steel (1). To obtain a clear picture of the real conditions in the reverberatory furnace.41 0.35 0.32 0.the slag.24 Copper matte 36. 1992.. Experimental Figure 1 — Schematic presentation of the sampling places (MM=measuring points) in the reverberatory furnace (a) and schematic presentation of the sampling probe (b).000 tons of anodic copper.31 4.65 25. For the analysis of the influence of slag composition on copper losses.17 0.44 0.29 4. having an inner diameter of 12. 2000.80 40.47 33.14 0.67 30.62 42.58 25. With the aim of obtaining the most reliable results possible about the conditions of an industrial furnace with stable operation.28 7.62 0.65 31. which is connected to the steel Table 1 — Concentrations of the main slag and matte constituents in the samples collected along the furnace length (measuring points MM3-MM6) and at the different distances from the slag surface (samples I – IV).63 32.62 3.52 32.63 3.18 0.75 7.000 mm.66 4.34 0.38 42. 2009.80 31.18 7. (Serbia).69 7.18 0. Sample MM3 I II III IV I II MM4 III IV I II MM5 III IV I II MM6 III IV Smelting slag Cusulfide [%] Cuoxide [%] CuΣ [%] SiO2[%] FeO [%] Fe3O4 [%] CaO [%] Al2O3 [%] Cu [%] Fe [%] S [%] 0.53 4. Cocić et al. Also.67 42.42 4.27 0. a special experiment was designed that included sampling of the slag and matte from the furnace roof using so-called deep sounding during stable operation of the furnace (Mitevska.46 0.59 0.39 0.15 0.47 0.68 7. 2000).08 7.90 3. The smelting process in this company is done in a reverberatory furnace with an annual capacity of 60.77 30.35 0. 1994.67 3. 1996).08 44. due to the fact that regulation of input charge composition can be used to control copper losses in the smelting slag.14 4.54 0.17 0.16 0.87 3.57 4.46 0.28 7.38 4.55 4.84 30.60 31.12 0.16 0.73 7. we used data obtained from the Copper Smelter Company – RTB Bor.76 3. 27 No.67 3. the degree of desulfurization obtained during oxidative roasting can be used to control the copper content in the matte (Reuter et al.15 0.42 0.13 0.31 34. 3 142 MINERALS & METALLURGICAL PROCESSING .45 August 2010 • Vol.60 3.84 7.48 33.35 0.02 46. The plug (2) is positioned at the lower band of the pipe.56 3. The sampling of the slag and matte was performed during a tapping operation and the analysis of the composition was carried out on a daily basis for several years (Živković and Savović.96 45.54 32.47 4.26 7.38 0..51 0.91 26..61 4.31 0.86 7.67 0.42 0. The results obtained should be helpful for copper smelter management related to the input charge composition that will enable better management of the copper losses in the smelting slag.43 4. the complex sampling operation was performed at the industrial level. Aldrich et al.84 3...70 3.72 31.55 0.87 30. (1997).13 39.56 7.40 0.70 43. 2009).20 0.14 0.10 42.42 4. The motive for the investigations presented in this paper was to perform statistical analysis of the slag constituents that influence total copper losses to the smelting slag and to develop a mathematical model describing these influences.06 44.92 3. The position of the measuring points (MM) (which are the openings for sampling formed at the furnace roof) and the sampling probe shape are presented in Fig 1.68 4.69 7.50 0.38 4.91 7.44 0.
copper in the slag is detected in the oxide (Cu2O) and the sulfide (Cu2S) forms.wire that goes through the pipe.12% Cu in the cumulative sample. it is clear that the composition of the slag and the copper matte influences the copper losses in the slag. compared to the other measuring points. % compound is the concentration of the individual slag constituent (SiO2. For a quantitative determination of the elements with a concentration above 0. Because the temperature was too high at measuring points MM1 and MM2.50 %. During this process.1%. The copper smelter plant in Bor has had the same balance of the main slag constituents for many years: SiO2: 30 – 35%. 1. Metallic copper wasn’t detected in the slag.940 tons of slag with 0. which enters through the gap between the pipe and the plug. matte composition).420°C at MM5 and 1. the plug to close under pressure and the probe to lift through the furnace roof. %. the probe was sliced transversely to determine the border between the slag and the matte. Slag samples were collected from the surface of the slag (I). At this location. Results presented in Fig. 2003). an optical emission spectrograph OES JARRELL -Ash 70. for each particular component and for whole set. the gas temperatures in the furnace are decreasing from the measuring point MM3 to the measuring point MM6. Copper content in the matte ranges from 30 to 45% (Živković and Savović. In accordance with the results presented in Table 1. According to the results presented in Table 1. it can be stated that cooler molten material affects the melt’s viscosity. 2 suggest that an increase in the SiO2 content leads to a decrease in the copper content of the slag. % compound represents the concentration of the individual matte constituent (Cu.405°C at MM6. 27 No. thereby influencing slag losses with respect to copper content.570 tons of produced copper matte with a copper content of 42. It takes 30 seconds for the probe to reach the bottom of the furnace.. . The influence of each individual constituent on the slag’s copper content was analyzed using linear regression methodology. According to the copper contents in the slag detected at different measuring points (see Table 1).49% Cu in the cumulative sample. sulfide and total). CaO and Al2O3) and A and B are the constants of the linear equation.SiO2) + SO2 (2) Results and discussion Results presented in the literature indicate that the chemical composition of the slag has a strong influence on its copper content (Gorai and Jana. a mass spectrograph JOEL JMS-0.1%. Results obtained in the experiments and analyzed in this paper are within these ranges. since the reaction for Cu2O reduction requires mattes with copper content above 60% (Jalkanen et al.485°C at MM4. while for the elements with a concentration below 0. which happens at the phase border between slag and matte. Thus. The influence of the SiO2 content in the slag. the probe is filled with the molten slag and the matte. The technological parameters of the furnace operation. with the aim of determining the analytical dependence: (Cu) = f (slag composition. to the right: [FeS] + 3(Fe3O4) + 5(SiO2) → 5(2FeO. multiple linear regression analysis (MLRA) was used. The SiO2 and FeO represent more than 70% of the slag content and are bound in the form of fayalite (2FeO. Equation (1) was also used to define the influence of the copper matte composition on copper losses in the slag. Fe3O4. Figure 2 presents the dependence of the copper content in the slag on SiO2. The concentration of the main constituents of the slag and the matte is presented in Table 1. For processing of the obtained results. the highest copper content is detected at MM6 and the lowest at MM3. a decrease in the oxidation potential of the melt is occurring that leads to a decrease in the oxidation rate of MINERALS & METALLURGICAL PROCESSING 143 Vol. This kind of dependence results from moving the position of the equilibrium of the reaction.510° C at MM3. Figure 2 — Dependence between the copper content in the smelting slag and its SiO2 content. for the day in which the sampling was performed.SiO2).000 (USA) was used. Average gas temperatures in the reverberatory furnace measured during sampling were: 1. In this case. The measuring point MM3 is located closer to the front wall of the furnace. FeO: 40. copper losses in the slag are related to the position of the measuring point (MM) in the furnace. The thickness of each sample for chemical analysis was 10 mm. From each probe. they were omitted and measuring was performed only at points MM3-MM6. CaO : 4 – 6 % and Al2O3 : 3 – 6 %. 2003). 1996). presented in Table 1. at the distance of 60 mm below the surface of the slag (II). Fe and S). indicating that they can be regarded as representative for analyses described in the following text. The burners are located in the front wall of the furnace. These parameters indicate stable furnace operation. Also. four slag samples were obtained. Fe3O4: 5 – 8 Thus. 3 • August 2010 . 1. After cooling in the air. near the MM1 position. The matte sample was obtained at 10 mm below the border between the slag and the matte. the dependence obtained is in the form of a linear equation: (Cu) losses = A · (% compound) + B (1) Where (Cu) losses represents the copper losses in the slag (oxide. at the distance of 120 mm below the surface of the slag (III) and at the distance of 180 mm below the slag surface (IV). were: .1 MB (Japan) with the ionic optical system MatauhHerzog was used. FeO. This way. The probe is slowly lowered from the furnace roof and sunk in the melt at the location of each measuring point (MM) until it reaches the bottom of the furnace.
is presented in Fig. but is also added with the returned converter slag (Živković and Savović. As Fe3O4 increases in the slag.Figure 3 — Dependence between copper loss and the FeO content in the slag. (3) to the right. which increases the oxidation potential of the slag. 3 144 MINERALS & METALLURGICAL PROCESSING . Figure 3 presents the dependence between the copper content in the slag and the FeO content. 27 No. to a decrease in the amount of chemically dissolved copper in the slag (Gorai and Kana. The influence of the FeO content in the slag. August 2010 • Vol. the equilibrium of Eq. which indicates an increase of the Cu content resulting from the increase in Fe3O4. and in this way the chemical solubility of the copper in the slag becomes higher. Figure 4 — Influence of Fe3O4 content on copper loss in the slag. the copper sulfide oxidizing to Cu2O and. which is in the direction of increased copper solubility in the slag (Biswas and Davenport. (4) moves to the right. accordingly. formed during smelting process. [Cu2S] + 3(Fe3O4) → (Cu2O) + 9FeO + SO2 (4) The dependence between copper and magnetite content in the slag. An increase in the FeO content in the slag moves the equilibrium of Eq. 2003): [Cu2S] + (FeO) → (Cu2O) + [FeS] (3) The influence of the magnetite content in the slag. 4. 2003). 1996). Magnetite is an unwanted component in the copper slag. Figure 6 — Influence of Al2O3 on copper loss in the slag. Figure 5 — Influence of the CaO content on copper loss in the slag.
960 0. with development of the Al-O complex.856 0.882 .077 . Biswas and Davenport.303 8.0. 2003).036 1. the dependence between the content of each individual slag constituent and its oxide. Accordingly. Component SiO2 Coefficients A B R2 FeO Components in the slag A B R2 Fe3O4 A B R2 CaO A B R2 Al2O3 A B R2 Cu Components in the copper matte A B R2 Fe A B R2 S A B R2 Cuox .0. while two moles of Cu are attached to one mole of sulfur.034 . are presented in Table 2. which is why Al2O3 can be defined as a network-building compound (Kim and Sohn.006 0.168 0. 1998).1. 3 • August 2010 . interphasial tension increases between the matte and the slag.0.443 0.0.604 0.3.092 .960 0. Part of the copper matte is kept in the slag in the form of unprecipitated droplets.052 1.828 .Table 2 — Calculated values of the constants in the linear dependences between the copper content in the slag and the slag and matte constituent concentration.842 3.959 0.557 Cutot . an increase in the Al2O3 content of the slag leads to formation of Al-O complexes because of the high ionic potential of the Al3+ ions.153 0.496 0.347 .365 0.885 0. Influence of the CaO content in the slag. as well as the values of the coefficient of determination (R2) for obtained linear dependences.547 .28 0. sulfide and total copper content is obtained in the linear form (Eq.530 0.869 0.0. the copper loss to the slag also increases. Calculated values of the coefficient of determination (R2) (Table 2) indicate a good fit to the obtained results for all slag compounds.879 0. 27 No. 5 presents the dependence between the copper losses and the CaO content in the slag.0. it is clear that the content of each individual slag constituent has a significant influence on the copper content in the slag. which causes heterogenization of the silicate melt and a sudden increase in its viscosity.934 0.752 0. This formation amplifies the effect of the Si-O complexes. Influence of the matte composition on the copper losses to the slag.506 . Figure 6 presents the dependence between copper losses and the Al2O3 content in the slag. At the same time.010 4.0. In the case of the system described in this study.5.858 0.725 0.880 .04 . The Al-O complexes formed under the influence of Al2O3 decrease the oxidation potential of the copper melt and accordingly the amount of the copper oxides that are easily dissolved in the slag. since one mole of Fe is attached to one mole of sulfur. the influence of iron in the matte on copper content in the silicate slag is the opposite of the influence of copper content in the matte.355 9.518 0. and in this way increases the mechanical copper losses to the slag. In principle.0.613 0.464 0. Influence of the Al2O3 content in the slag.0.869 0. The sulfur content in the matte depends on its Cu/Fe ratio.046 0.137 .534 .777 0.042 1.075 0.779 4.4.0. 1996.874 .0346 0.0.0.357 0.0.097 0. The values of corresponding constants A and B.166 0.356 .531 The increase in the Fe3O4 content of the slag. besides moving Eq. Using the linear regression analysis.783 0.884 0.960 0. Fig. (4)’s equilibrium to the right.573 0.116 4. leads to the separation of the magnetite crystals. If these drops have a larger copper content. MINERALS & METALLURGICAL PROCESSING 145 Vol.0.0. The content of iron and copper in the copper matte (system Cu2S – FeS) are in inverse proportion. An increase of the CaO content in the slag leads to the destruction of its silicate network (Živković and Savović.855 0. For that reason.097 3.0.885 0. which results in a decrease in the slag’s viscosity and copper content.676 .2. 1).775 .018 0.0.732 0.015 .376 Cusulf . which leads to a decrease in the mechanical copper losses in the slag.814 .932 5.005 .
0. Those dependences enable prediction of the copper content in the slag according to its composition and according to the composition of the matte.175 h .424 0. Fe and S in the matte.sulfide. the copper content in the waste slag can be predicted with a probability of above 97%.486 3.975 0. 3 Where: a. Using MLRA in the SPSS software. iron and sulfur content in the matte.1%. corresponding coefficients of determination (R2) were obtained. as well as the degree of desulfurization during oxidative roasting (which determines the composition of the matte). (5)) was performed. c.9% can be regarded as under the influence of other parameters. 27 No.030 . and ( ). mostly related to the dynamics of smelting operations in the furnace. Furthermore. d. calculated values were compared to those experimentally obtained.237 . it should be noted that the amount of data available for analysis was smaller for the copper matte constituents than for the constituents of the slag (Table 1). Calculated dependences for the copper content in the slag as a function of the proportion of individual slag components.0.991 important information can be obtained using statistical analysis of the content of all compounds in the slag as well as copper.067 c 0. This dependence can be presented in the following form: (Cu) = a + b(SiO2) + c( FeO ) + d(Fe3O4) + e(CaO) + f(Al2O3) + g[Cu] + h[Fe] + k[S] (5) Figure 7 — Dependences between measured and calculated values for the copper content in the slag using MLRA methodology ( — ideal.0. as well as the values of the coefficient of determination for obtained linear dependences.0.083 .0.219 k 0.0.068 . However. f. mainly through their influence on slag viscosity. 5) with an accuracy of 99.0.126 0.241 e . as the function of the slag and the matte composition.464 R2 0. Calculating the values of the coefficients of determination (R2) indicate a high degree of fit in all three cases. Fe and S in the matte. This step would improve the overall management of the pyrometallurgical copper extraction process at the smelting stage. For the testing operation. Fe and S content in the copper matte. Coefficient Cuox Cusulf Cutotal a 0. considering that the Eqs. The reason for such behavior could be in the different influences of the slag and the matte composition on the copper losses in the slag. The slag’s constituents determine its copper losses. multiple linear regression analysis (MLRA) was used as part of the SPSS software application. Considering that the composition of the charge can be controlled.040 0.0.148 . 5). ○ .0. For determination of the quantitative dependence of the copper content in the slag on slag composition and content of the Cu. On the other hand.Table 3 — Calculated values of the constants in the linear regression equation (Eq. CaO. FeO. The remaining 0. 7.0.016 . e. Fe and S) and the copper losses in the slag are also calculated using linear regression (Eq. Obtained values for the coefficients in Eq. on copper content in the waste slag (Cu) using the linear regression method. × .085 d . even outside the narrow borders defined by the technology of the smelting operation.1) applied to the data from Table 1. obtained by MLRA methodology.004 . according to the MLRA. □ .694 b 0. The values of corresponding constants A and B. August 2010 • Vol.0.0.019 0. copper matte constituents influence copper loss in the slag via their relation toward the copper concentration in the part of the matte that remains dissolved or entrained in the slag. 2) Obtained values of the coefficients of determination 146 MINERALS & METALLURGICAL PROCESSING Conclusions . (3) and (4) happen at the slag-matte phase border. if the composition of the slag and the matte is known. 1) After examination of the influence of individual slag constituents in the reverberatory furnace smelting slag (SiO2. Al2O3) and Cu. h and k are the coefficients in the linear regression equation. while the content of all the other compounds is regarded as constant.027 .0.0.189 . (5).0. (2). are presented in Table 3.oxide.058 g . Determination of the copper content in the slag.208 3. for the matte compounds compared to the slag compounds. in all cases.067 0. Fe3O4. the degree of fitting is lower (lower values of the R2 coefficients). testing of the above model’s validity (Eq. because the slag is composed of complex compounds and its composition changes constantly.[ ] are the % concentrations of the slag and matte components. can result only in approximate information on each compounds’ influence. copper losses in the slag could be managed using by exploiting these dependent relationships (Eq. Dependence between measured and calculated values of the copper content in the slag is presented in Fig. are presented in Table 2. b. g. According to the results presented in Table 2. which strongly rely on human factors.99 0. using the multiple linear regression analysis (MLRA).119 . The MLRA defines the output of the linear correlation of one variable (copper content in the slag) depending on the slag composition (content of slag constituents) and the content of the Cu.045 .total ) The dependences between the individual matte constituents (Cu. Also.163 f .0.
and Hernandez.J..J.” Journal of Hazardous Materials. C. “Modeling of copper content variation during EI Teniente slag cleaning process. Toguri. Živković. using MLRA methodology. 77 – 92. H. “Recent trends in extractive metallurgy. 27 No. Živković. pp. 36.. S.indicated that the prediction of the influence of each slag component’s concentration on its copper content can be accurate (above 80%). Gorai. 2009.1% through the control of the input charge composition and the degree of desulfurization during oxidative roasting. pp. Goni. and Manasijević. 0. University of Belgrade –Technical faculty in Bor. “Recovery of copper from reverberatory furnace slag by flotation. J. Influence of the technological parameters and inner phase phenomena on copper losses in the smelting slag. Živković. pp. No. 1996.. R. Vol. Chile. 1997.” Journal of Mining and Metallurgy. 4) When considering the influence of all slag and matte constituents. Ž.. Jalkanen.G.. 6) It was also determined that the ratio of sulfide to oxide copper content in the slag is 2. 1. W. F. “Artificial neural network vs.. Cocić. Vol.. and Mutombo. J. Vol. A. Yuan.. Achura..G.K. Sarrafi. 7. B. 1. Imriš. Aldrich. References No.. 164. No.. New York. T. PhD Thesis. and Liao. Patronov. 643. “Copper in solidified copper smelter slags. 2007. 28. 856–862.. Cooler molten material affects the melt’s viscosity. and Poijarvi. 1992. “Modeling of metal – slag equilibrium processes using neural nets. H.. “Artificial neural network method applied for nonlinear multivariate problem. 2007. Pergamon Press. I. Savović. and Van Deventer. Ž. 71-84. Ž.21 . 583 – 590. “The application of neural nets in the metallurgical industry.W... Reuter.. Metallurgy. Cocić. pp. 299 – 313. J. 10397 – 10400. H. Pergamon Press.. Živković.A.. M. correlation among measured and calculated values of copper content in the waste slag is obtained with the determination coefficients (R2) equal to 0. pp. D. 32.” Serbian Journal of Management. Rebolledo. 4. Dj. Mihajlović. Vol.. and Simeonov. Extractive Metallurgy of Copper. January 18. K. A. pp. 2009. No. Section B: Metallurgy. 2009. J. Vol.. 45 B. Vol. 1997. 457-459.. 5/6. 2009. Y. No. 17. Vol. M. 5) Considering that results presented in this paper are obtained during the relatively stationary mode of furnace operation.Y.. M. No.. Vol. 1. “The effects of slag composition on copper losses in sulfide smelting.” Journal of Mining and Metallurgy. No. Sridhar.K. pp. pp. and Reuter.. pp.99 for the (Cu)ox.. G. 65-70.256.. Magaeva. Section B: Metallurgy. 123 pp.J. pp. “Effects of CaO. 3) The prediction of the copper losses in the slag as the function of the copper matte composition has an accuracy above 50%. C. N. 3 • August 2010 .S. A. pp.” Metallurgical and Materials Transactions B. Castro.. Van Deventer. 39..S. 2003. T.. and Sanchez. I. H.991 for the (Cu)total. Lenchev. 2. Maweja. M. 2.” Serbian Journal of Management. “Characteristics and utilization of copper slag – a review. S... Matović. Section B. 3.. pp.. 2000. 1994.” Minerals Engineering. S.” Journal of Mining and Metallurgy. Santiago . 191-200. (in Serbian) . 57 – 65.” The Canadian Journal of Metallurgy Science.. Van Derr Walt. M. 2009..” Copper COBRE. Vol. G. 657. thereby influencing slag losses with respect to copper content. Nikolić.. 143 – 155. pp. Vol. Lui. V.97 for the (Cu) sul and the 0. M. I.. 1-2. Rahmati. 29. Fluxes & Salts. S. 43B..” Scandinavian Journal of Metallurgy. and Davenport. J. R. “Energy analysis of processing SO2 containing gases in metallurgy into sulphuric acid and sulphur... G. 2003. “Copper losses and thermodynamic considerations in copper smelting.. 281-290. 2003.A. and MgO additions on the copper solubility. Vol. H. S. R. 793 – 809. 39. I..” Minerals Engineering. pp. This result indicates that management and control of copper loss to the slag could be achieved at an accuracy of over 99. pp. S. 1991. H. Physicochemical basics of the smelting and converting processes in the copper metallurgy.. (in Serbian). D. “Cleaning of a copper matte smelting slag from a water-jacket furnace by direct reduction of heavy metals. University of Belgrade – Technical faculty in Bor. and Shirazi. 230 pp. F. pp. 36B. A. Al2O3. This ratio is not dependent on the slag or matte composition during the smelting of sulfide concentrates. Biswas... it can be stated with a probability of 99. pp..2003. Kim. “The copper losses in the slags from the El Teniente process. New York. 1998. 1 – 13. and Jana. MINERALS & METALLURGICAL PROCESSING 147 Vol. M. “Mineralogical transformation in copper concentrate roasting in fluo-solid reactor. Vol. Logar. Vol. 7) Copper losses in the slag are also influenced by the temperatures in the furnace.8:1. under standard industrial conditions. B. Vehvilainen.. Sanchez.” Metallurgical Transactions B.” Expert Systems with Applications. B.” Resources Conservation & Recycling. and minor-element behavior of iron-silicate slags.. J.650.. nonlinear regression for gold content estimation in pyrometallurgy.” Metallurgical and Materials Transactions B. D. 267 pp. ferric/ferrous ratio. Dević.. and Sohn. Vol. Habashi. Matousek. Hassani.1% that the slag and copper matte composition influence the copper losses in the slag. Mitevska.” VIII International Conference on Molten Slags. Mukongo. “Investigation of the influence of technology life cycle on company life cycle Case study: Metallurgical production of copper in RTB Bor (Serbia). 2000.. Vol. The remaining influences mostly include human factors in the management of the technological process. at the same time. and Granchorov. 23.
cation exchange capacities around 60 to 170 meq/100g and property of thixotropy. They would be advantageous for minimizing the variations in quality of the pellets.5 to 0. and Exploration. 27 No.71 mm) sieve. sodium hydroxide. Bentonite Introduction Pelletization is a method of agglomeration used to turn fine fractions of iron ore into an adequate product (pellet) to be fed to blast furnaces and direct reduction reactors. The dry sample was disaggregated using a 28-mesh (0. Department of Chemical Engineering. Binder must be added to the pelletization mixture to raise the liquid phase viscosity inside the capillary spaces. Sao Paulo. different combinations of binders were compared to bentonite by examining the quality of pellets obtained by balling drum agglomeration. L. The moisture of bentonite was determined by drying it in an oven at a temperature of 105° C until constant weight. Original manuscript submitted July 2009. It was dried at a temperature of 100°C for 24 hours.Laboratory study of an organic binder for pelletization of a magnetite concentrate S. The choice of binders to be tested was based on the author’s previous experience using these binders in the agglomeration of hematite concentrate (Moraes and Cassola. Inc. In contact with water. great superficial area. Binders that would not leave a residue after ther- mal treatment would be extremely interesting. Sao Paulo. by contributing to the formation of ceramic or iron ore oxide bridges or to scorify discrete points during thermal treatment.7 kg each were produced. The typical dosage of bentonite as a binder for iron ore pelletization is 0. The disposition of bentonite plates in the point of contact between ore particles also enhances the pellet’s compressive strength. The sample of iron ore concentrate was received in three containers containing approximately 15 kg (wet weight) each. A sample of magnetite concentrate from the Empire Mine (Palmer. Metallurgy. Homogenization and reduction of sample mass. Michigan Abstract This study aimed to identify a way to reduce the use of bentonite in the pelletization of magnetite. Institute for Technological Research. Copyright 2010. Society for Mining. Brazil S. sodium metasilicate. Houghton. The work was developed using the following binders: bentonite. The best results use sodium silicate (1. Kawatra Professor. Revised manuscript accepted for publication December 2009. forming a colloidal gel. The moisture content of bentonite was 13% (dry basis). The sodium hydroxide and sodium silicate were used in the form of a 50% (w/w) solution in water. Binders. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Pellets were subjected to routine tests that included simple compression of the wet and dry 105°C pellets. sodium tripolyphosphate and carboxymethyl cellulose. Figure 1 shows the process of homogenization and reduction of mass Paper number MMP-09-029. With this goal. K. blended and split by a rotatory splitter. to maintain the cohesion of “green” pellets and to improve the compressive strength of the thermally treated pellets.05%. Magnetite. The average chemical composition of the sample is shown in Table 1. August 2010 • Vol. sodium carbonate. The typical chemical composition of bentonite is shown in Table 2 and the specification of the binders in Table 3. which is characterized by its high swelling power. dropping wet pellets to determine their ability to survive handling and submitting pellets to thermal shock to determine how they tolerate drying and preheating. Key words: Pelletization. the bentonite platelets separate. de Moraes Research engineer. 2008). Iron/ iron ores. raising the intensity of the Van der Waals forces.5%) as a binder and show that it is possible to pelletize iron ore without using bentonite. The classic binder for iron ore pelletization is bentonite. A disadvantage of bentonite is that it adds the undesirable contaminants alumina and silica to the pellet. where it will be reduced to pig iron or sponge iron. prior to February 28. 24 subsamples of approximately 1. MI) and received by Michigan Tech on 16/03/2009 was utilized. Materials and methods Sample ore and binders. 3 148 MINERALS & METALLURGICAL PROCESSING . Michigan Technological University. 2011. Environmental and Energy Technologies Center. lowering the dosage to be used to around 0. Bentonite enhances the strength of the iron ore pellets by the following mechanism: the presence of colloidal material shortens the distance between particles.7% of the ore mass (dry basis).
Analyte SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 MnO2 LOI LOI: Loss of ignition.014 1. 2) Add a small amount of ore mixture to drum rotating at 25 rpm. The tests were carried out using a laboratory-scale balling drum (Fig.01% NH4OH. The number of drops needed to crack each pellet is recorded and averaged.83 0.0%Na2CO3 ≤0. Characterization of the pellet properties. These tests are the “drop” test and the “compression” test.4 1.5% Granular Sodium metasilicate pentahydrate Sodium tripolyphosphate (TPP) Sodium carboxymethyl cellulose (CMC) Na2SiO3.06 and 0. Two standard tests are used to measure the strength of pellets. For each test the ore. % 35.0 0.” 3) Enlarge seeds by adding more concentrate while spraying with water.) in diameter.001% N. Pelletization tests. Compression strength is measured by compressing or applying pressure to a random sampling of pellets until the pellets crumble. 2a) for two minutes.7 mm (0. proceeding through the balling drum and subsequent conveyor belts. periodically removing and screening to keep uniform size. ≤0.41 96.6 23. Pellets are dropped repeatedly until the pellets crack.01% insolubles ------------- Sodium carbonate Na2CO3 Reagent anhydrous ≥99.8% Form White pellets Impurites ≤0. Pellets are finished when they are between 1.000 95. Product Sodium hydroxide Formula NaOH Table 1 – Iron ore concentrate chemical composition average.001% N.1 1. 3 • August 2010 . The drop test requires dropping a random sample of pellets from a height of 46 cm (18 in. ≤0. Concentration. Moisture content and binder dosages are shown in Table 4. H2O at 25 °C) = 115 cp White small beads White granular powder Off-white powder MINERALS & METALLURGICAL PROCESSING 149 Vol.59 6.98 Unit % % % % % % % None % Table 2 – Typical chemical analysis of the bentonite. ≤1.6 and 12. The balling procedure consisted of: 1) Delump mixed binder and concentrate through an eightmesh screen.5 in. These two tests are used to measure the strength of both wet and fired pellets.005% silica.2 Properties Grade Reagent Assay 98. The composition of each mixture is given in percentage by mass concentration based on dry components.3 0. ≤0.of the sample.46 1. Compound Fe SiO2 CaO MgO Mn Al2O3 P CaO/SiO2 Total oxides Value 58.5H2O Na5P3O10 Pure Technical grade Average Mw~ 90.0 13.25 0.02% NH4OH.) onto a steel plate.6 2. The pounds of force required to crush the pellets is recorded and averaged. experience frequent drops as well as compressive forces from the weight of other pellets Table 3 – Binder specifications.5 9.7 kg (dry basis) ore. ≤0. 2b) with aliquots of 1.7% (Titration) 85% Viscosity (C=4%.59 4. 27 No.04 0. binder and moisture were added to a laboratory mixer (Fig.2 5. moisten it with a water spray to produce pellet “seeds. The drop and compressive test measurements are important because pellets. whether the pellets are green pellets or fired pellets.
9±0.7±6.9±17.1 3. the pellets were subjected to a compression test and the result was expressed in kgf or N/pellet.9±0.7 of “fines” or coarse particles in the pelletized mineral ore.7 19.4 52. The pellets obtained were subjected to the tests for characterization described as follows. 3 150 MINERALS & METALLURGICAL PROCESSING . From the batch of green pellets.9 9.8 24.5 9.6 51.7±0.9 16.40%)+NaOH(0.2±16. 20 pellets were randomly subjected to automatic compression until breaking. Increases in a pellet’s thermal shock resistance improve the pellet’s ability to resist internal pressures created by the sudden evaporation of water when the pellet is heated in a kiln.4±0. 27 No.9±5.1±0. At this time the load was recorded and the arithmetic mean of the values represents the test result in kgf or N/pellet. about 300 g pellets were randomly sampled and dried in an oven at temperature of 105ºC until constant weight.3±2.4 11.9 26.6±7. Dry compression strength.6 14.04%)+NaOH (0.3 19.8±21.75%) 9.9 101.3±11.3±8. The result is the average of values given by number of falls per pellet.5 89. From each batch of pellets obtained.6 22.9±0.4±22.8±0.9±3. After cooling for 15 minutes.0±12.0 August 2010 • Vol.2±10.9±0.0 10.2 67.5 180. Thermal shock resistance is a factor which must be taken into consideration in any process for agglomerating mineral ore concentrate. the pellet has an increased tendency to shatter upon rapid heating.3 58.7±1. If the surface of the pellet is smooth and continuous.8±15. A binder which increases the pores formed in a pellet improves the pellet’s ability to resist thermal shock. If the pellet has numerous pores through which the water vapor can escape.2 Wet crush (N/pellet) ±P95 19. differentiated an additional step: the 20 pellets were dried in an oven at 105° C for 24 hours.8 74. traveling on top of them.0±5. 20 pellets were randomly selected and dropped freely from a height of 46 cm (18 in.8 19.0±18. This causes a concurrent increase in the amount Table 4 – Pelletization experiment results.8±1.8 40.0 9.9 43. groups of 15 pellets were selected at random.5±0.2 1.9 Crush after thermal shock (N/pellet) ±P95 300°C 500°C 700°C 900°C Bentonite (0.2±3.5%) Sodium carbonate (0.04%) CMC (0.2±3.5 9.0±12.8 141.5 32.0 20.3 119.9 14.0 8.1±1. After the pelletizing.0 18. The number of drops incurred by each pellet was recorded.0 10.6 51.6±30.) onto a platform with a steel shank.7 15.0 21.1 8.7±8. Determination of moisture. Drop number green pellet. Wet compression strength.8 99.02%) CMC (0.2 2.1 167.2 2. a b Figure 2 – Pelletization tests: (2a) Laboratory mixer (2b) Laboratory-scale balling drum. thermal shock resistance is improved.8±0.2±0.7±20.1±31.5%) Sodium silicate (1.0±0.6±0.04%)+TPP (0.7±1. Then Dry crush (N/pellet) ±P95 38.4±21.9±1.3±4.2±4.3 44.2 2.9 151.0±1.7±2.66%) Bentonite (0.Figure 1 – Sample preparation.6±4.3 16.2 2.4 33. without pores.9±22.5±1. Each pellet was dropped repeatedly until the first fractures appeared. Thermal shock resistance test.4 89.02%) CMC (0.7 36.7 19.02%) Sodium carbonate (1.78±5.2±0.2 108.6 17.5 120.5±8.3 123.3±2.9±4.8 54.75%)+ sodium silicate (0.5 36.8 19.6 9.9±0.4±0.2 2. This test is similar to that done with green pellets. Binder dosage Moisture % Wet drop (18 in) ±P95 3. From each batch of green pellets obtained.
3. As shown in this figure there are no significant Results and discussion differences between the results at 300°C and 500°C. the groups were left to cool in industrially acceptable that is 22 N/pellet. These results show that is possible to reduce the amount 20 pellets. Two tests were carried out with bentonite at the dose of 0.9 drops. However. The authors found that CMC (sodium carbomethyl cellulose) +TPP (sodium tripolyCMC alone as a binder is not effective. because the pellets do not resist heat. Figure 4 – Compressive strength of magnetite concentrate pellets bonded with bentonite. The error bars shown on the graphs represent the of bentonite without reducing the quality of the pellets. respectively. the mean and standard deviation were determined for again.66%. Chaves (1992) with hematite concentrate showed the results Pellets bonded with sodium carbonate.1 N/pellet) is still greater than each group was placed in a muffle furnace at temperatures the minimum industrially acceptable standard. The aim of using CMC and CMC+NaOH and CMC+TPP in this work was to check if the same dispersant effect happens when pellets are made using a magnetite concentrate. 5).4%)+NaOH with iron ore concentrate and different binders. Figure 4 shows the compressive strength of pellets bonded with bentonite. 27 No. This that the dose of bentonite and NaOH can be adjusted to reach step also evaluates the percentage of pellets that crack and/or the target strength. dry). 700°C and 900°C for 10 minutes at each pressive strength result (20. There were no explosions test CMC + NaOH and the smallest in the test with sodium during thermal shock resistance tests in pellets bonded with carbonate.5% to 9. explode. 4. After this time. In 1998. The highest value observed was that of the tests bonded with bentonite. Pellets bonded with bentonite presented cracks in all temThe variation of the moisture content in each test was from peratures during thermal shock resistance tests (Fig.2 drops. These results suggest the air and subjected to a test of compressive strength.02%) falls and at 900°C the compressive strength improves reported. bentonite and bentonite + NaOH.phosphate) show the same result of 2. CMC and the additive TPP present the greatest potential for use as binders. This value is not the minimum industrially acceptable. Cassola and Chaves found that the dispersion of limonite from the surface of particles of hematite due to the dispersant effect of TPP was the fundamental mechanism for the process. the result of the wet compression (18.3 N/pellet.9 drops each.8%.02%) during thermal shock can be seen in Fig. higher than the minimum industrially acceptable (9 N/pellet. At 700°C Table 4 shows the results obtained in the pelletization tests the performance of pellets with bentonite (0. bentonite+NaOH and using CMC and CMC + TPP as binder.7 N/pellet) is almost the minimum temperature. The use of CMC in iron ore pelletization the value of reference. For each value (0.66%. 95% confidence intervals calculated using the t-distribuition.66%) and bentonite (0. They showed wet and dry compressive strength results of 19 N/pellet and 38. wet and 22 N/pellet. Effect of bentonite. The dry comof 300°C. which only lasted1. it should be noted that TPP adds phosphorus to the pellets. which survived 3. Studies carried out by Lima (1991) and Lima and lets bonded with sodium silicate. which is an undesirable contaminant. but in this case will be Effect of CMC. The wet drop results are shown in Fig. Figure 3 – Strength of magnetite concentrate pellets bonded with different binders. Figure 6 shows the compressive MINERALS & METALLURGICAL PROCESSING 151 Vol.02% showed less wet and dry compressive strength compared to plain bentonite at 0.4%)+NaOH (0. Pellets bonded with bentonite at 0. 3 • August 2010 . However. 500ºC. The behavior of pellets bonded with bentonite (0. The 8.4% and NaOH at 0. The biggest moisture value was observed in the cracks increase the formation of dust. The worst result was observed for pelis not new.
but was still insufficient. Magnetite pellets made using 0.5% sodium carbonate as a binder showed overall better results than pellets bonded with 0. This dispersion is very intense and saturates the pores of the pellet with water and solids.66%).66% bentonite. preventing the passage of gases of the evaporating water during the drying step. The addition of 1. Pellets made with sodium carbonate as a binder can be seen after explosion during the thermal shock resistance test (Fig. August 2010 • Vol. Effect of sodium carbonate and sodium silicate. Similar results were found with the thermal shock resistance test.5% sodium silicate improved the compressive strength. The explosions may have occurred because the sodium carbonate should be acting as a dispersant over the fines particles contained in the magnetite concentrate.5% sodium silicate as a binder.04% CMC alone as a binder had insufficient dry compressive strength. Similar results were found with the thermal shock resistance test. Pellets bonded with CMC and TPP showed better results than pellets bonded with CMC and NaOH.66%). There was no formation of cracks and dust and no explosion occurred. The behavior of the pellets during the thermal shock resistance test did not provide enough compressive strength to survive the drying and firing steps. 27 No. The addition of 0. The choice of these binders was made primarily to check the effect of the binder in the firing step. 7.02% TPP improved the pellet dry compressive strengths to the minimum industrially acceptable (22 N/pellet). However.75%) were made in a effort to eliminate explosions during thermal shock resistance test. Specifically. The pellets bonded with sodium carbonate (0. In this case there were no cracks or explosions during Figure 6 – Compressive strength of pellets bonded with CMC and the additives NaOH and tripolyphosphate (TPP). This test showed that by reducing the dosage and using a combination of sodium carbonate and sodium silicate. However. the compressive strength of pellets bound with sodium carbonate is higher at 700°C and 900°C than that of pellets bonded with bentonite (0. The compressive strength of the pellets made with sodium silicate as a binder was higher at 700°C and 900°C than that of the pellets bonded with bentonite (0. 27% of these pellets exploded during the thermal shock resistance test at each temperature (300°C. This result demonstrates that the dose of sodium silicate can be reduced. Pellets using 1. 500°C and 900°C). 8). the dry compressive strength increased.66%).Figure 5 – Cracks in a pellet bonded with bentonite after the thermal shock resistance test (900°C). The compressive strength results for pellets bonded with sodium carbonate and sodium silicate are shown in Fig. When NaOH was added together with CMC to the magnetite concentrate pellets. The behavior of sodium-silicate-bonded pellets during the thermal shock experiments was excellent. 3 152 MINERALS & METALLURGICAL PROCESSING . There were no cracks or explosions during thermal shock resistance during all tests. it was determined whether it would be possible to decrease the temperature of sintering. strength of magnetite concentrate pellets bonded with CMC and the additives NaOH and TPP. These results suggest that dispersants are beneficial in making pellets with magnetite concentrate. The best results obtained were those of the pellets made with 1. to well above the minimum industrially acceptable values. it is possible to get the same results as that of the pellets bonded with bentonite (0.75%) and sodium silicate (0.
75%) showed that reducing the dose and using the combination of sodium carbonate and sodium silicate. Ripke. 1992. Sao Luis. P. No. The addition of 1.5% sodium silicate improved the compressive strength to over the minimum industrially acceptable value.4%) + NaOH (0. B. This result demonstrates that the dosage of sodium silicate can be reduced..66%) showed that is possible to reduce the bentonite dosage without reducing the quality of the pellets..66%)..” 3rd International Meeting on Ironmaking and 2nd International Symposium on Iron Ore. MA. 136-142.” São Paulo: EPUSP. but not enough. 16. 464-471. 145 pp. and Chaves. “Estudo da carboxi-metil-celulose como aglomerante para pelotização. S. Michigan Technological University. (Boletim Técnico da Escola Politécnica da USP. • The best results were achieved with pellets made with 1. Escola Politécnica. it is possible to get the same results as that of pellets bonded with bentonite (0. and Chaves. 2004. Similar results were obtained in the thermal shock resistance test. MINERALS & METALLURGICAL PROCESSING 153 Vol. • The pellets bonded using sodium carbonate (0. Master’s thesis. S.75%) and sodium silicate (0.66% bentonite.66%). J. L. “Microstructure of iron ore pellets – organic and inorganic binders. Estudo da carboxi-metil-celulose como aglomerante para pelotização. 3 • August 2010 . 80 pp. 27% pellets exploded during thermal shock resistance test at 300°C. 2002. Cassola. J. However. A. Departamento de Engenharia de Minas. Michigan. September 22-26th. Escola Politécnica. Comparação de desempenho de aglomerante orgânico em relação à bentonita na operação de pelotização de concentrados de minério de ferro brasileiros de diversas procedências. • The addition of 0. 2004. • Magnetite pellets made using 0. • When NaOH was added together with CMC.Figure 7 – Compressive strength of pellets bonded with sodium carbonate and sodium silicate. “Effect of the addition of organic binders on the behavior of iron ore pellets. S. Moraes.. the dry compressive strength increased. 500°C and 900°C. pp.04% CMC alone as a binder had insufficient dry compressive strength. Advances in iron ore pelletization by understanding bonding and strengthening mechanisms.. 2008. These results suggest that dispersants are beneficial in making pellets with magnetite concentrate. Conclusion • The results of magnetite concentrate pellets bonded with bentonite (0. and Cassola. The thermal shock resistance test gave insufficient compressive strength to survive the drying and firing steps. • Pellets bonded with bentonite presented cracks at all temperatures during thermal shock resistance tests. R.5% sodium silicate as a binder. R. Universidade São Paulo. Cracks increase the formation of dust. M.02% TPP improved the pellet dry compressive strength to the minimum industrially acceptable (22 N/pellet).5% sodium carbonate showed better results than pellets bonded with 0.. • Pellets made with 1. S. In this case there were no cracks or explosions during the thermal shock resistance test. São Paulo. J. Universidade São Paulo. Lima. 1992. P.. 1998. These preliminary results suggest that is possible to optimize the sintering temperature of the pellets by adjusting the amounts and types of binders. 1991. There were no explosions during the thermal shock resistance tests of pellets bonded with bentonite and bentonite + NaOH. • The compressive strength at 700°C and 900°C of pellets made with sodium carbonate and sodium silicate is higher than that of the pellets bonded with bentonite (0. References Lima. S. Osaka. pp. 27 No. the thermal shock resistance test.02%) compared with pellets bonded with bentonite (0. Moraes.. L.” KONA: Powder and Particle. M. 186 pp. PhD Dissertation. Figure 8 – Pellets made with sodium carbonate as binder after exploding during the thermal shock test. São Paulo. 2008. Similar results were obtained in the thermal shock resistance test. A. B. Brazil. PhD dissertation.. BT/ PMI/014).
000 tons annually (MKE Technical Report. The main focus of this study is to selectively separate Ni from the FALL by chemical precipitation. 1996). Texas KEN Research Center. The activity of Ni in the NH3H2O and H2O systems was calculated to determine the yield of Ni by precipitation in each system. Metallurgy.. Seoul. 2007.. The activities were calculated using MathCAD software from the thermodynamic data in Table 1. The precipitation of Ni(II) ion forms Ni(OH)2(s) and NiO(s) as the pH of the solution increases (Chang et al. the chemical precipitation method produced a high yield of Ni by precipitation from the fly ash leach liquor. 1998. fly ash is an ever-increasing industrial waste that is a functional byproduct of power plants accumulating 25. Uddin et al. Fly ash was widely used in the past as an additional fuel in the cement industry (Korea Cements Industrial Association. August 2010 • Vol. The activity of Ni(II) and Ni ion complexes in the NH3-H2O system as a function of pH was analyzed with the thermodynamic data and the predominant species at various free ammonia concentrations were established in the Eh-pH diagrams of the Ni-NH3-H2O system (Meng and Han. In the pH range of 7-9. a chemical precipitation method was used to selectively precipitate Ni(II) from the FALL. In order to selectively separate Ni(II). Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. prior to February 28. For this reason. The distribution of Ni species in ammonia solution as a function of pH was analyzed using thermodynamic data (see Tables 1 and 2). and Exploration.3-2. 2009). 2001. Ssangyong Cement Industrial Co. The pH was then increased from 3 to 11 to see the effect of pH on separating Ni from V in the FALL.600 ppm of V along with trace amounts of Fe. Vitolo et al. Experimental Thermodynamic observations In order to examine the surface morphology and particle size distribution of the fly ash. of Metallurgical and Materials Engineering. environmental regulations in South Korea prevents the use of fly ash as a fuel. 2007.Ammonia separation of Ni from spent fly ash leach liquor S. Hwang N. 2000.3. El Paso. Society for Mining. Galvez et al. The pH was controlled by adding either NH3 or NaOH per 100 ml of FALL. the pH and the concentration of ions in solution. 3 154 MINERALS & METALLURGICAL PROCESSING . 27 No. this activity decreased with an increase in the pH of the solution. Inc. numerous studies have been conducted seeking to remove heavy metals from fly ash and to produce an environmentally safe material.6. Currently. Kim Dept. Republic of Korea Abstract An ongoing problem for industry in Korea is effective removal of heavy metals from and safe disposal of spent power plant fly ash. Peacock and Sherman.675 US$/ton (London Metal Exchange. This process may be economically viable in view of the recent price of Ni at $22. 2007). Table 2 shows the Gibbs free energy of formation for various Ni(II) ammine complexes..-Y. Ltd. Copyright 2010. These studies include the extraction of V and Ni (Abdel-latif. The Ni can then be reused as a valuable metal. the FALL was diluted to a ratio of one part fly ash to ten parts water. Seokyeong University. 2011. Stas et al. Tsai and Tsai. This research endeavor attempts to develop selective separation of Ni from leach liquor using a selective chemical precipitation method. 2001. A FALL that contained 2. The research was conducted by changing two variables..300 ppm of Ni and 1. Khorfan et al. The precipitation reaction was continued for one hour and then the supernatant was separated from the precipitation Paper number MMP-09-054. The purpose of the current research is to recover Ni from a fly ash leach liquor (FALL) in order to develop an economical approach to recover Ni from FALL. 2007) and the production of activated carbon from fly ash (Caramuscio et al. Original manuscript submitted November 2009.. Murase et al. In this experiment. 1998. Selective separation. 2008).. Key words: Chemical precipitation. 2009). 2007. JSM-6390) and a particle size analyzer (PSA. Mn and Zn has been prepared for the study... The effect of other ions present in the system on the separation efficiency of Ni species was also investigated by adjusting OH and NH3 concentrations. The activity of Ni(II) in the H2O system and the NH3-H2O system as a function of pH was analyzed to compare the empirical data of FALL with the theoretical data from the Eh-pH diagrams of the Ni-NH3-H2O system. with an initial pH of 2. The concentration of NH3 in the NH3-H2O system was calculated using MathCAD and shows an increase in the concentration of NH3 at a pH above 9. Elemental analysis was also carried out using SEM-EDX. CILAS-1064) were used. University of Texas. 2010). Ni species. March 1.-S. 2002.. Fly ash Introduction In South Korea.. Revised manuscript accepted for publication April 2010. Vitolo et al. Figure 1 shows the activity of Ni(II) as a function of pH. a scanning electron microscope (SEM. 2003.
4. the surface morphology of fly ash was characterized using SEM (JSM-6390).01 Zn 0. There are many miTable 3 — Chemical composition of the tested fly ash (unit: wt. 2009). Fig. 3.600 Table 2 — Thermodynamic data of Ni(II) for various ammines (Meng and Han.600 -211.022 -22. fly ash particles were distributed from 1 to 200 micrometers. Figure 4 — Particle size distribution of the fly ash.842 -162. J/mol -26. The metal ion concentration was measured using an inductively coupled plasma (PerkinElmer5300DV).7 Fe 0.%) C 80.4 cro. Species NH3 NH4+ Ni2+ NiO ∆Go.5 MINERALS & METALLURGICAL PROCESSING 155 Vol. As seen in Fig. As seen in Fig. Figure 1 — Activity of Ni(II) in Ni-H2O systems as a function of pH at 25°C..647 -252.931 Figure 2 — TG analysis data of fly ash (Hwang et al. Results and discussion The chemical composition of the dried fly ash was determined by wet chemical analysis and a ThermoGravimetric Analysis (TGA) and is shown in Table 3. 1996). Mn 0. The volumetric mean particle size (d50) was 65 micrometers.981 -196.4 V 1.570 -79. 4 shows the particle size distribution of the fly ash. 27 No. J/mol -87.370 -45.02 Ash 16. It is believed that these mesoscale pores are channels for the reactant and product ions mass transfer. 3 • August 2010 . Species Ni(NH3 )2+ ∆Go. 1996).Table 1 — Thermodynamic properties (Stumm and Morgan. It is believed that the carbon in the dried fly ash started to oxidize at 400°C.sized pores on the surface of the particles. Figure 3 — Surface structure of fly ash. 2). which resulted in decreasing weight loss of 80% until 620°C (see Fig.814 -126.and nano.9 Ni 0. compound using a centrifuge.
V. possibly due to a large quantity of NiO and Ni(OH)2 being formed as the OH concentration increased. Mn and Zn separation from the FALL. 3 156 MINERALS & METALLURGICAL PROCESSING .3. Figure 7 shows that most Fe was precipitated at a pH above 7 in the NH3-H2O system. Mn and Zn in the H2O system. Fe and Zn ions were precipitated at a pH above 9-10 without a complexing agent when NaOH was used to adjust the pH. NH4(I) is predominant at pH below 9. Figs. the precipitation yield of Ni in the H2O system increased by increasing the pH. 1. However. Figure 8 — Ni and V precipitation in the NH3-H2O system. 5 and 6 show most Ni. However. which is expected in view of Fig. At pH 9. As seen in Fig. without complexing agents. 1. while it decreased to 13% when the pH was increased above 10. Mn and Zn precipitates started to dissolve back into the FALL solution. Chemical precipitation could be interpreted in view of the August 2010 • Vol. vanadium oxide redissolved at a pH higher than 11. From an economic point of view. at a pH above 9.Figure 5 — Precipitation yield of Ni(II) and V in the H2O system. The concentration of free ammonia in the range of pH 3-9. In this system. the activity of Ni(II) in the Ni-H2O system continuously decreases with the increase in pH of the system. most Fe ions in the FALL precipitated out of the NH3-H2O system (see Fig. for economic reasons. the precipitation of Ni increased to 68% at pH 9. It is believed that the amount of Ni precipitation increased as the pH increased. which explains why the Ni(II) precipitation rate decreased from 68% to 13% at pH 10 (Fig. 27 No. Likewise. Mn. 8). It is noted that Mn and Zn are soluble in the wide range of pH 9-11 in the presence of ammonia as a lixiviant. Figure 7 — Precipitation rate of Fe. It is confirmed that NH3 is more effective than NaOH at selectively separating Ni from other metals. V and Fe (see Table 3). Mn and Zn in the NH3-H2O system. in the FALL. Figure 6 — Precipitation yield of Fe. It is reported that Mn and Zn are soluble in the range of pH 6-10 in the presence of NH3. Without any complexing agent in the FALL.3 was believed to be too little to make ammonia complexes in the FALL. Ni and V separation from FALL were highlighted and less attention was focused on Fe. It is noted that some of these metal oxides are soluble at high pH and vanadium is soluble over the wide pH range of oxides. 7). In this study. but in the FALL the relative amount of Zn and Mn was too small in comparison to Ni. This is due to a predominance of NH3 at the elevated pH. Ni can be selectively separated from FALL using the NH3 chemical precipitation method.
Z.3 in the presence of ammonia. March 19. Rev. http://www. 16.. Proc. Seggiani. pp. 3. Y. Machida.. Seggiani. N. Yu. Eng. “Recovery of vanadium from heavy oil and orimulsion fly ashes... N. third edition.. “Recycling of power plant fly ash for construction materials by removal of heavy metals..” Hydrometallurgy. New York. 23-61.. Chang. the predominant species was Ni(NH3) 62+ (Deng and Chen.” Periodica Polytechnica Ser.” Materials Letters. M. Hwang... “Routine to estimate composition of concentrated metal-nitric-hydrofluoric acid pickle liquors.lme.. Y. Vitolo.com/nickel..” Chemical Geology. pp. pp. & Ext. 345-351. 206-212. K. Stas. however. 2004).. X. due to the precipitation of Ni by increasing pH without complexing agents in the H2O system. MINERALS & METALLURGICAL PROCESSING 157 Vol. Meng. G. Wahoud. 2000. 9. Ssangyong Cement Industrial Co. 2007. Kim. Ni was formed as ammine complexes with various ammines at a pH above 9. Tsai.Figure 9 — The Ni species in the NH3-H2O system as a function of pH by changing the concentration of NH3. pp.. Stefano. 3 • August 2010 . Conclusions Acknowledgments This work was supported by the Energy Efficiency & Resources of the Lorea Institute of Energy Technology Evaluation and Planning (2007-R-RU-11-P-14-3-010-2007) grant funded by the Korea government Ministry of Knowledge Economy. 23. Eng. 2009..A. It has been shown that by using the NH3 chemical precipitation method. Y. Ozaki. P.. and Al-chayah.” Ministry of Economy Knowledge.” Periodica Polytechnica Ser. Figure 9 shows Ni activity as a function of pH by changing concentration of NH3... M. pp. and Han. Vol. Vol. 953-961.. ionic strength and temperature. and Brocchini. D.S. co. 2002. 2007. and Falaschi. 1996. pp. Caramuscio. 264. Therefore. pp.. “Recovery of vanadium pentoxide from spent catalyst used in the manufacture of sulfuric acid.. T. http://www. http://www. W.kr/kor/new/environment/environment03_1. Vol. Vol.A.asp. 2003. pp.. S. Stumm. 2010.htm. “Preparation of activated carbons from heavy-oil fly ashes. Vol. pp. T.J. and Reda. C.” Hydrometallurgy. The adjustment of the pH of the solution at about pH 10 using NH3 proved to be effective and economical in the selective separation of Ni from V in FALL. 58.. 22.” Hydrometallurgy. and Suda. 2001. Uddin... X. M.. Vol. The activity of total Ni(II) complexes was increased with the increase of the concentration of free ammonia. London Metal Exchange. and Narducci.R. Anal. Conservation and Recycling. S.3. C. Vitolo. S. Yamada. NH3 is predominant at a pH above 9. Republic of Korea. 2001.3. “Recovery of vanadium and nickel from petroleum flyash. 276-280..S. 2004. “The principles and applications of ammonia leaching of metals-A review... Yamaji.163-176. F. Vol.. No. Eng. Vitolo. P..kr/tech/ resource. “Sorption of Ni(II) on Na-rectorite from aqueous solution: Effect of pH.” Waste Management.D. Adachi. Chem... and Lopez-Mateos..” Korea Society of Waste Management. Filippi. John Wiley & Sons.N.151-156.asp. M. “Sorption of Ni by birnessite: Equilibrium controls on Ni in seawater. Deng. Galvez. 2009. Seggiani. J. “Recovery of vanadium. 94-106.cement. Vol. Negro.3. 2. 45.” Min. “A study of the extraction of vanadium and nickel in oil-fired fly ash. The Ni precipitation yield was increased by increasing the pH from 3 to 9. Vol. “Recovery of vanadium from a previously burned heavy oil fly ash..” Colloids and Surfaces A: Physicochem. Peacock. Vol. Vol. Vol. a finding that agrees well with the empirical data at pH 9-10. 51.M. Ltd. M. S. 2007. and Kim. Furusawa.. J. Korea Cements Industrial Association... pp.. while NH4(I) is predominant at a pH below 9. Vol..or. and Tsai. nickel and molybdemum from fly ash of heavy oil-fired electrical power stration. 96. Figure 9 shows the relationship between the NH3 species and the Ni activity. Vol.. Nishikawa. Eh-pH diagrams of the Ni-NH3-H2O system. and Chen. 131-137.” Resources. pp. pp. and Sasaoka.. A. E. 1996. F. based on thermodynamic calculation and compared to empirical data. L..145-150.. pp. Appl. S. 57.141-149. Dufour. 67-70.” Minerals Engineering. Ni separation from V can be 32-51% achieved in the FALL at pH 7-9. As seen in Fig. Dahdouh. T.. 26. Ni returned to solution when the pH was increased above 9. The activity of Ni decreased with increasing pH in the range of pH 3-11. 2008. K. The Ni species in the NH3-H2O system were calculated by MathCAD software. M. pp. 1998. S. Shinozaki. C.ssangyongcement. in the presence of NH3. Khorfan. MKE Technical Report. Wang. 15. “Recovery of vanadium.L. W.. Wu. 27 No. K..Y. 238. 78. 302. and Morgan. nickel and magnesium from a fly ash of bitumeninwater emulsion by chlorination and chemical transport. Murase.... 75-81. Chem. X. K. L. “Preparation of nano-NiO by ammonia precipitation and reaction in solution and competitive balance. 1998. S. “Preparation of activated carbon from asphalt and heavy oil fly ash and coal fly ash by pyrolysis. A.L. S.. Vol. 2007. and Sherman.. 88-94. 337-342. O. 62. Pyrolysis. “A study on fabrication of functional deodorized panel and commercialization that use for carbonaceous circulate materials. Aquatic Chemistry. No. 2007.. 2009. J... References Abdel-latif. P. USA.S.” Journal of Alloys and Compounds.” J. J. pp. Inc..
. Flotation. Rashchi et al.. Koleini Professors. August 2010 • Vol. Witne and Philips. Department of Mining. 1989. Metallurgy. Original manuscript submitted January 2009. 2005) Direct flotation of zinc oxide minerals by applying the appropriate collectors eases the above problems. have been employed to extract metals (such as Pb and Zn) from oxide ores. Khodadadi and S. 1998. Analysis of variance (ANOVA) was used to determine the optimum conditions and the most significant parameters affecting the reaction rate. 2002. 1994. sodium citrate. and Exploration. Inc. bioleaching and flotation. 2005.. Oxine. including four levels of pH. Iran. 3 158 MINERALS & METALLURGICAL PROCESSING . Revised manuscript accepted for publication September 2009.ir A.. the system is depressed once more due to sulfide ion adsorption in preference to collector adsorption (Rastas et al. Mulligan et al. 2001. 1999. 1990. 2002. 2011... Barbari.. prior to February 28. 2005). as well as the extensive hydration of oxide surfaces (Fuerstenau et al. 1985. Wang et al. This paper reports an attempt to recover zinc oxide mineral from mining waste through flotation without surface sulfidation. Önal et al. oxine/dithizone. Önal and Abramov. Oxidized minerals are frequently treated with sulfidizing agents prior to flotation. sodium silicate. Dithizone. Society for Mining. 1993. depending on the type and concentration of minerals and also the type of impurities involved (Hoffmann et al. such as groundwater pollution due to the release of zinc and toxic elements (including such heavy metals as Pb. 2005. Cr. Iran E-mail: am_hajati@iust. such as leaching. The zinc residues are stockpiled until the recovery of valuable metals in the residues becomes economical. The Taguchi approach has been shown to be an effective means for the improvement of Paper number MMP-09-002. Tehran.0% and 24. Freeman and Nightingale.9 ± 3. Iran. Marabini et al.ac. Different technologies. 1999. it is generally known that oxidized minerals of zinc are more difficult to float than their sulfide counterparts. Consequently. 1994. recovery of zinc oxide from tailings will help reduce environmental hazards and create a new source of raw minerals (Kerfoot et al. Önal and Abramov. few attempts have been made to float zinc oxide minerals using chelating agents (Marabini and Rinelli. However.2% using oxine and dithizone. The recovery conditions were optimized using a Taguchi orthogonal array L32 (48) design. corn starch. Iran University of Science and Technology. 2005). 2005).. Hg and Co). 1980). Eight control factors. Önal et al. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. pH Introduction There are two million tons of mine tailings deposited around the zinc processing plant at the Goshfil Mine (BAMA Co. respectively.. Hajati Instructor. Arak.Flotation of zinc oxide minerals from lowgrade tailings by oxine and dithizone using the Taguchi approach A. due to the lack of feasible techniques for the recovery of zinc and other valuable metals. 27 No. under optimum conditions with a confidence level of 90%. sodium thiosulfate.4 ± 3.) in Esfahan. Haddadin et al. Key words: Tailing.. Iran Abstract The main purpose of this study was to find the optimum values for factors affecting the Zn recovery rate using oxine or dithizone as a chelating agent collector during flotation in a Hallimond tube. Cd. Copyright 2010. An L32 orthogonal array was applied to determine the signal-to-noise (S/N) ratio. Zinc oxide. 1973. using oxine and dithizone as chelating collectors. The aim was to evaluate the optimum experimental conditions that provide the highest flotation recoveries of zinc metal from a solid matrix. Department of Mining-Mineral Processing. Pereira and Peres. The stockpiled residues cause serious environmental problems. Analysis of the experiments using the Taguchi approach indicated that pH had the highest contribution to the recovery rate of zinc oxide particles. Tarbiat Modares University. conditioning and floating durations were considered in a Taguchi experimental design technique. When more sulfide ions are added. However.. such as the ore wastes around the openpit lead and zinc mine at Goshfil in Esfahan. This fact is due to the higher solubility of oxide minerals.. M. The results showed that the recovery rate of zinc increased by 43.. Gomez et al. Yianatos et al.
16 g/mole (Fig. The Taguchi approach was used in the present work to determine the optimum recovery conditions for maximizing the zinc content of the flotation concentrate using oxine and dithizone as chelating agent collectors without surface particle sulfidation. 297. 53.6 % L. 27 No.. Experimental Sampling and treatment.4 % MgO: 6. XRF: XRD: ZnO: 5. a height of 300 mm and two MINERALS & METALLURGICAL PROCESSING Figure 1 — The percent cumulative passed material as a function of particle size for eight grinding times (t in minutes). Iran). By grinding the samples at -95 microns and desliming at 37 microns. Reagents. -95. The samples were crushed by a jaw crusher and ground with a ball mill (Bond model) to obtain a homogenized final sample that included 5.3% iron oxide (hematite and goethite) (Oliazadeh and Abdoulzadeh. For the flotation tests. 3 • August 2010 159 .5 mg/ml) (Fig. goethite.I: 3. In order to determine the effect of different particle size distributions on the flotation recovery.0 % Fe2O3: 13.0% lead oxide (galena and cerussite) and 13. 2003). The oxine concentration was kept below 2%. Desliming and magnetic tests. Moghaddam et al. which may remove oxine from the system. acetone was employed as a solvent. feeding parts. The grinding time with the least production of fine particles in the sample feed flotation and the lowest degree of liberation of zinc oxide (smithsonite) and iron oxide minerals was 10 minutes (Figs. Eight different curves were plotted as mass cumulative passing percentages versus particle size (microns). because of the solubility of acetone in water. The limit of -95 microns was deemed most suitable for further study. A comparison of the liberation degree of smithsonite and iron oxide minerals was necessary to select a suitable size limit. the liberation of smithsonite was greater than that of iron oxide.. dolomite. At this size. 1 kg of the homogenized sample was sieved and divided into several limit sizes in different time durations of 0. 20. 2 shows the liberation degree of smithsonite and iron oxide minerals. Hajati et al. 149. 3a) and dithizone (C6H5N or H2Dz) is a purplish black solid soluble in both chloroform (20 mg/ml) and CCl4 (0.3 % TiO2: 0. sodium Vol. a Hallimond cell was used. 2006).4 % Al2O3: 5. The frothing time was 12 minutes. conditioning time. It has been applied to a wide range of industrial fields worldwide (Opur et al. Weller et al. cerussite. The presence of fine particles of iron oxide minerals is one of the main problems in the flotation process. Fig. 50 and 60 minutes using 1000. the samples were passed through a wet magnetic field with an intensity of 2 Tesla. +37 microns the size limit was achieved in the feed flotation tests.4 % CaO: 15. Figure 2 — Degree of liberation of iron oxide and smithsonite based on the size of the particles. The samples were fixed and the surfaces of the particles were polished to determine a suitable size limit according to the degree of liberation of zinc oxide (smithsonite) and iron oxide minerals. The Hallimond cell consists of a Pyrex tube with a fixed diameter of nearly 20 mm. Oxine and dithizone were used as chelating agent collectors (Merck.Table 1 — Results of feed analysis by X-ray fluorescence and X-ray diffraction. The upper part of the tube is inclined 30 degrees to collect the floated minerals. sphalerite. galena productivity at the research and development stage.23 % SiO2: 27. Samples were obtained from oxide dam tailings of the Goshfil mine of BAMA Co. Oxine (C9H7NO) is a white crystal with the molecular weight of 145. There is a sinter glass at the bottom of the tube for air bubble flow... Microscopic tests to define degree of liberation. 74. Micro flotation cell. smithsonite.O. Pine oil with a range of 120 g/ton was selected as frother.8 % SO3: 4. At -95 microns. Fuel oil (gasoline) was also added. The results are shown in Table 1. 44 and 37-micron ASTM standard sieves. floating time and concentration of oxine and/or dithizone. Liberation of minerals can significantly affect the flotation process (Trahar. 2.3% zinc oxide (smithsonite and sphalerite). 3b). 1976.3 % PbO: 2.9 % barite. 1995.. 40. Darmsdat. so that high quality items can be produced quickly at low cost. one for pH control and the other for injection of the materials. The main parameters used for flotation tests were pH. (Esfahan. 2003. Germany). The particles were suspended by a gently rotating magnetic stirrer. Since chloroform and CCl4 are insoluble in water. more than 80% smithsonite and 60% iron oxide minerals were liberated. sodium thiosulfate. 1997. 1 and 2). Hajati et al. In order to reduce the iron content. 2003). 30. quartz. Microscopic analysis enabled the counting of the number and percentage of liberated minerals. 10. 5. corn starch. hematite.
Four different concentrations were chosen mal condition. By obtaining the Basically. respectively.536 experiments to capture the influential between 1950 and 1960 to improve the implementation of total parameters. as the variability characteristics are inversely as shown in Table 2. 3 160 MINERALS & METALLURGICAL PROCESSING . ANOVA can estimate the effect of a factor on the characteristic properties and the experiment can be performed with minimal replication using the orthogonal arrays. is L32 orthogonal array of the mentioned eight parameters at complicated and not easy to use. concenorthogonal array for the experiment was determined by the trate and tailing flotation tests were analyzed at BAMA Co. The Taguchi method uses the S/N ratio to measure the quality characteristic citrate and sodium silicate. 1. 27 No. The Taguchi approach uses orthogonal August 2010 • Vol. All control factors have four levels. weight vs. Montgomery. the Qualitek-4 software (version 7. quality and cost (Roy. classical parameter design. The experimental condition in order to evaluate the effectiveness of various concentrations having the maximum S/N ratio is considered to be the optiof the key reagents. 1999). sodium citrate (g/t). the signal-to-noise (S/N) ratio. 32 experiments with differincreases. Parameters (A) (B) (C) (D) (E) (F) (G) (H) pH Oxine/dithizone as a collector (g/t) Corn starch (g/t) Sodium thiosulfate (g/t) Sodium citrate (g/t) Sodium silicate (g/t) Time conditioning (min) Time floating (min) Level 1 3 20 500 20 20 20 5 10 2 6 60 1000 60 60 60 10 20 3 9 180 1500 180 180 180 15 30 4 12 540 2000 540 540 540 30 40 arrays and analysis of variance (ANOVA) as the tools of analysis. ~0. while the Taguchi method can determine the experimental conditions having the least variability as the optimal conditions.. 1990). A well-designed experiment can substantially reduce laboratories by an atomic absorption spectrophotometer (AABthe number of experimental tests required. time conditioning (min) and time floating factors is known as the design of experiments (Roy. 1993). soall the possible conditions in an experiment involving multiple dium silicate (g/t). the number of experiments required was reduced must be conducted when the number of process parameters to 32 (Table 3). eight control factors at four different levels were examined in this study (Table 2). The terms ‘signal’ and ‘noise’ represent the desirable and undesirable values Figure 3 — The chelating of zinc by oxine (a) and dithizone (b). To solve this problem. This method is a simple and systematic approach to tailings are smithsonite (Table 1). For the Taguchi design and subsequent analysis. Fig. the experiments. 1996. b. developed by Fisher. Mineralogical and magnetic test results.2 g of the sample (dry wt. The goal is to find out the optimal and robust product or process Results and discussion characteristics that have a minimized sensitivity to noise. The variability is expressed by a. Temperature was kept at 20 °C during proportional to the S/N ratio (Roy. The Taguchi techPerkin Elmer. The appropriate AAB analysis. to reduce the number of experiments.5+) was used. In other words. The plot of accumulated optimize the design for performance. 1990). software.Table 2 — Experimental parameters and the levels tested. Through 2 ml concentrated nitric acid. For metal analyses. Concentrations of Zn in the feed. quality control in Japan (Taguchi and Yokoyama. A large number of experiments four levels. the Taguchi method uses a ent combinations of factors should be conducted in order to special design of orthogonal arrays to study the entire parameter study the main effects and interactions. Park. combination method using full factorial experimentation means The Taguchi method was developed by Genichi Taguchi we will need 48=65. oxine/dithizone (g/t). Increasing the grinding time causes the percentage of Mousavi et al. was digested in a Teflon bomb for four hours at 140 °C with meanwhile obtaining statistically meaningful results. for the output characteristics. (min). which in the classical space with only a small number of experiments (Nian. USA) using the standard addition nique applies fractional factorial experimental designs. 2007). 2001. Cox and Reid. Orthogonal arrays and experimental parameters These control factors included pH. The results of Taguchi design can determine the effect of flotation factors mineralogical analysis through X-ray fluorescence demonon characteristic properties and the optimal conditions of the strated that nearly 80% of the zinc minerals in the Goshfil factors. 2000. observation and review of literature. sodium thiosulfate (g/t). Model 100. corn (Taguchi method). called technique. micron size for different grinding times is shown in 1990.) orthogonal arrays (OA). The technique of defining and investigating starch (g/t). Preliminary tests were carried out deviating from the desired value. Conventional statistical experimental designs can determine the optimal conditions on the basis of the measured values of the characteristic properties.
7 14.7 26.3 18.1 13.8 23.4 22.8 20.2 7.0 4.0 13.0 11.7 5.9 16.0 16.0 13.2% to 7.3 21.4 11.3 22.0%.1 18.4 3.5 5.5 S/N ratio 13.3 6.9 11.4 38.7 26.8 20.3 16.0 29.4 18.3 22.0 6.0 22.5 3.9 11.3 27. 2003).9 18.4 5.5 6.2 9.3 17.3 10.3 11.7 20.5 7.9% StDev = 5.1 14. in the part to be used as a flotation feed.2 4.4 12.2 4. Eight-factor. Also.2 13.5 25.2 14.6 21.3 7.6 14.3 10.4 9.3 2.2 32. However.1 20.7 4.3 19.1 13.1 9.6 20.0 10.9 9.2 9. reducing the slope of the curve or increasing the grinding time makes smithsonite.3 16.6 14.2 2.8 7. more than 80% of the smithsonite and 60% of the iron oxide minerals are liberated.8 6.1 7.5 13.2 13. hematite and goethite more likely to be ground into fine particles.4 2.2 25.0 30. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 A 1 2 3 4 4 3 2 1 3 4 1 2 2 1 4 3 2 1 4 3 3 4 1 2 4 3 2 1 1 2 3 4 B 1 2 3 4 3 4 1 2 2 1 4 3 4 3 2 1 3 4 1 2 1 2 3 4 4 3 2 1 2 1 4 3 C 1 2 3 4 3 4 1 2 1 2 3 4 3 4 1 2 2 1 4 3 4 3 2 1 2 1 4 3 4 3 2 1 D 1 2 3 4 2 1 4 3 4 3 2 1 3 4 1 2 4 3 2 1 3 4 1 2 1 2 3 4 2 1 4 3 E 1 2 3 4 2 1 4 3 3 4 1 2 4 3 2 1 1 2 3 4 2 1 4 3 3 4 1 2 4 3 2 1 F 1 2 3 4 1 2 3 4 2 1 4 3 2 1 4 3 4 3 2 1 4 3 2 1 3 4 1 2 3 4 1 2 Average recovery = 16.3 8.7 5.6 10.8 15.5 4.2 12.1 26.1 9.0 23.9 3.5 23.3 7.4 2.9 27.7 33.3 22.6 25.4 26.6 3.9 15.5 28.6 25.8 19.3 7.9 3.1 25.0 21.3 3.5 8.9 12.9 5.6 15.8 7.4 27.0 17.9 28.9 8.9 16.5 4. at -95 microns.8 28.3 28.0 14.9 25.5 Rj: Recovery Average recovery = 8.9 11.8. fourlevel factorial designs were used for evaluating the effects of the Vol.7 13.9 23.6 18.7 15.3 6.5 2.5 20.5 14. 27 No.7 6.9 14.2 Avg 4.2 5.7 21.8 23.7 3.9 9.3 9.1 8.5 9.9 23.4 Avg 4.3 8.6 27.Table 3 — Results of an orthogonal array L32 (48) test of Zn flotation recovery using oxine and dithizone.7 9.9 29.2 7.9 10.3 12.5 and 12.7 22.0 30.0 26.1 18.5 14.9 5.5 14.9 5.4 4.3 12.9 17.4 11.2 16.6.7 20.6 14.7 9. 5.8 10.0 11.1 13.0 % StDev = 8.3 11.8 21.6 5.6 5.3 Dithizone R2 5.5 12.8 16.5 2.2 9.7 5.8 14.8 11. under the best conditions 35% of the weight percentage of iron oxide is removed and the grade of Zn.6 17.1 5.3 11.5 7.6 16.9 8.8 10.8 16.0 4.3 6.1 9.5 15.3 7. By desliming and submitting MINERALS & METALLURGICAL PROCESSING the samples to magnetic tension. 3 • August 2010 161 .9 22.6 10.5 7.. Pb and Fe changes from 7.0 8.3 17.5 18.7 16.9 22. respectively.7 7.7 coarse particles converting to fine particles to increase.1 22.8 32.3 8.1 4.0 8.1 18.5 15.8 6.8 R1 5.1 24.0 7.6 14.7 26.9 S/N ratio 12. Experimental design and data analysis.1 29.4 9.1 24.6 35.6 11.6 9.2 18.8 32.4 13.5 Trial No.5 4.0 and 3. The results of counting the number of minerals and the percentage of liberated minerals can be found in our previous work (Hajati et al.8 10.6 22.3 8.6 12. 3.5 27.7 12.1 21.9 24.8 4.1 4.0 39. Parameters and their level Recovery (%) Oxine G 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 H 1 1 1 1 2 2 2 2 3 3 3 3 4 4 4 4 1 1 1 1 2 2 2 2 3 3 3 3 4 4 4 4 R1 4.7 12.9 20.4 8.3 6.6 R2 4.1 19.6 9.0 19.3 5.5 21.4 9.7 7.3 12.0 6.8 23.6 20.
9 (pooled) 2. time conditioning (min) and time floating (min). Dithizone (A) pH (B) Oxine/ dithizone (g/t) (C) Corn starch (g/t) (D) Sodium thio-sulfate (g/t) (E) Sodium citrate (g/t) (F) Sodium silicate (g/t) (G) Time conditioning (min) (H) Time floating (min) Error Total 3 3 (3) (3) (3) 3 (3) (3) 7 31 276.6 42.6 35.6 0. respectively. 27 No. the focus was on the main effects of the eight most important factors on Zn recovery.4 (pooled) 3.2 19. In order to estimate the best condition for the recovery of zinc metal from the oxide minerals.9 1. For the dithizone collector they were 9.6 2.3 10.3 8.6 0 10. The optimum values of the selected factors (pH.3 13.2 (pooled) 2.8 1.1 31. dithizone (g/t) and sodium citrate (g/t) were most important when using the dithizone collector. 10. 3 162 MINERALS & METALLURGICAL PROCESSING .4 0 2.2 (pooled) 1.2 11.5 38. oxine/dithizone (g/t). The remaining Table 4 — ANOVA Results of Zn recovery by oxine and dithizone and S/N ratio analysis. sodium silicate (g/t).6 12.7 35. sodium citrate. 1500. oxine (g/t) and sodium thiosulfate (g/t) play the most important roles in Zn recovery using the oxine collector.1 (pooled) 37.6 100% Degree of freedom (f) Sum of squares (S) Variance (V) S/N Ratio 102.3 87.7 8. in each of which the parameter of interest was kept constant.2 0.5 12.7 (pooled) 0.1 699.9 31.7 3. 500.9 1. corn starch. concentration of oxine/dithizone.7 99.8 29.5 3 3 (3) 3 (3) (3) (3) (3) 7 31 307.5 14. corn starch (g/t).7 9.5 12.4 10.8 64.2 30. sodium silicate.2 (pooled) 33. 180. 180. 32 experiments were performed. The mean values of each recovery yield for the corresponding factors and at each level are presented in Fig. sodium thiosulfate.3 0.7 58.2 17.3 21. In this study.7 53. 540. respectively. 60. 540. The results of these experiments are given in Table 3.6 0 0 49. duration of conditioning and duration of flotation) for Zn recovery using the oxine collector were 9.4 (pooled) 0. Oxine (A) pH (B) Oxine/ dithizone (g/t) (C) Corn starch (g/t) (D) Sodium thio-sulfate (g/t) (E) Sodium citrate (g/t) (F) Sodium silicate (g/t) (G) Time conditioning (min) (H) Time floating (min) Error Total 2. each reported recovery is the average of four measurements. Parameters 1.4 1.9 S/N Ratio 92. 20. while the other parameters were changed (Table 3).0 59.5 4. following factors on zinc recovery: pH.6 33.4 100% F-ratio (F) Percentage contribution (%) August 2010 • Vol.8 2. 30. sodium citrate (g/t).8 0. 10 and 30.6 (pooled) 1.3 (pooled) 1.ery floating Figure 4 — Response graph illustrating the zinc recovery ratios plotted against various flotation parameters by oxine and dithizone chelating agents as a collector flotation.6 115.7 3.6 6. In all cases. 540.8 6. while pH. sodium thiosulfate (g/t). The ANOVA results for the calculated models (Table 4) indicated that the levels of pH.1 10.9 95. 540.8 747. 4.9 37.0 3.
the degree of freedom (DOF) for each factor was 3 and the total DOF was 31. Regardless of the category of the quality (thelower-the-better. (1) and those obtained under optimum conditions. oxine is more effective than dithizone in achieving zinc oxide recovery. The most important parameters affecting the ratio of Zn flotation recovery were analysed as follows: Effect of pH. Tables 3 and 4). sodium silicate. 3 • August 2010 163 . The S/N ratio analysis was used to compute the signal-to-noise ratio for each level of the process parameters.9 90% 24.9 and 8. 33. In the optimum conditions.4 and 10. which were 3. respectively. 1990). a pooled ANOVA was applied. According to the ANOVA results.2. sodium citrate. The floatability of particles in Zn oxide minerals using oxine and dithizone depends on the pH level.0 43. a larger S/N ratio corresponds to better quality characteristics (Yoon et al. the performance was estimated using only the significant factors for oxine and dithizone (Roy. so the DOF for error was 7. n2. Table 5 shows that the obtained recovery for Zn under optimum conditions using oxine (43.. The confidence intervals of zinc recoveries by oxine and dithizone are ± 3. including corn starch. N is the total number of results.6%. Ve is the variance of error term (from ANOVA) and Ne is the effective number of replications (Yamini et al. obtained by calculating the error sum of squares and dividing by the error degrees of freedom. The percentage contribution of the initial pH by oxine flotation was the greatest. compared to those of dithizone and sodium silicate concentrations. is shown in Table 4. it was possible to calculate the F-ratio. the higher-the-better criterion was applied when evaluating the S/N ratios of various extraction parameters. F (1. it can be concluded that pH was the most influential factor.9 24.0 Level 3 3 1 4 1 4 2 3 Dithizone Optimized level 9 540 1500 180 180 60 10 30 8. the-higher-the better and the-more-nominalthe-better). Since the current study took the percentage recovery of zinc (w/w) as the quality characteristic. Therefore. The initial oxine and sodium thiosulfate concentrations for the MINERALS & METALLURGICAL PROCESSING oxine collector and sodium silicate and dithizone concentrations took the second and third places in the recovery flotation tests (Table 4). defined as the variance of each factor divided by Ve.I. Under this condithon. Parameters (A) pH (B) Oxine/ dithizone (g/t) (C) Corn starch (g/t) (D) Sodium thiosulfate (g/t) (E) Sodium citrate (g/t) (F) Sodium silicate (g/t) (G) Time conditioning (min) (H) Time floating (min) Current grand average of performance (%) Expected results under optimum conditions (%) Confidence level: Expected results: Oxine Optimized level 9 540 500 540 20 540 10 30 16.4 ± 3.) of performance was calculated using the following expression: (2) Where. n2) is the F value from the F table at a required confidence level at a degree of freedom (DOF) 1 and DOF of error. time conditioning and float time using dithizone had the least significant effects on zinc recovery from oxide matrix minerals.7. the pH of zinc oxide flotation plays an important role in the floating of these particles from the solid matrix samples. 2008).4%) is larger than that obtained using dithizone (24.2 Level 3 3 3 3 3 2 2 3 parameters. time conditioning and float time using oxine and corn starch. was calculated. respectively (Table 5). Accordingly. These factors are listed in Table 4. Further experiments were performed under the proposed conditions and the results obtained from the L32 (48) matrix (Table 5) showed that under the optimized conditions. Yopt is the performance under optimum conditions and are the average performances of the pH and concentration of collectors at optimum levels.. sodium citrate. Further. Finally the variance for the error Ve. This means that Zn Vol.9%).0 and ± 3. sodium thiosulfate. In order to calculate the DOF from the error. On the other hand. 37. which were 9.7 %. as compared to those of oxine and sodium thiosulfate concentrations. Therefore. the initial pH had the largest variance for oxine and dithizone.Table 5 — Estimation of Zn recovery with two chelating agents under optimum conditions. 4. which is calculated by the ratio of the variance for each factor to the total variance. Estimations of all performance parameters under optimum conditions using raw data and the results of S/N ratio analysis of zinc recovery are shown in Table 5. since both of the chelating agent collectors are controlled by this factor. respectively. S/N ratio analysis. the recoveries were similar to the optimum performance calculated using the following expression: (1) Where T is the grand total of all results. the percentage contribution of the initial pH by dithizone flotation was the greatest.4 90% 43. Analysis of variance. 2002). The impact of all parameters was calculated from the results of ANOVA flotation tests after conducting the S/N ratio calculations (Fig. Table 4 shows that there are satisfactory agreements between the results for zinc recovery from the solid matrices estimated based on Eq. 27 No.9 ± 3. The percentage contribution of each factor to Zn recovery. respectively. the confidence interval (C. As can be inferred from the results.3%.
Effect of oxine/dithizone concentration. The effect of oxine/ dithizone concentration on the recovery of Zn (oxide phase) was investigated by the addition of various concentrations of oxine/dithizone in acetone solvent to the Hallimond flotation cell and the results are shown in Fig.3 7.9 28.5 Grade (%) 6.1 8. 4). In this study.5 8.5 12. pH affects the flotation of zinc oxide minerals for both oxine and dithizone. In this condition. If the new design does not meet the specified requirements. These results indicate that zinc recovery using dithizone is higher compared to recovery using oxine.1 22.2% and 12.7 55.6 38 36 29.2% respectively. 4.2 47.9 6.2 10.1 Dithizone Recovery (%) 7. At a low concentration of either chelating agent. Fig.5 8. Concentration (g/t) 20 60 180 540 750 1000 1250 1500 1750 2000 2500 3000 Oxine Grade (%) 7.5 10 9. running the confirmation test is necessary to show the optimum conditions and compare the results with those of the expected performance. An increase in pH causes an increase in the concentration of electrical charge on the surface of the particles and an increase in collector selectivity to higher recovery. At higher concentrations of the chelating agents.9 flotation recovery is usually enhanced as the pH rises from 3 to 9.6 12 9.65 8. The final step is to predict and verify the improvement of performance characteristics.7 7. Figure 5 compares the grade and recovery of zinc oxide flotation recovery by variation in oxine and dithizon concentrations. after which they decrease. respectively. Zn recovery increases.9 21. above pH 9. As shown in Fig. Thus.7 7. the recovery of Zn with oxine fluctuates widely.86 7.9 33. the dithizone curves tend to decrease compared to those of oxine. the optimized pH for Zn recovery is 9. This result means that the Zn-oxine interaction is stronger than that of Zndithizone.Table 6 — The effect of oxine and dithizone concentration on the grade and recovery of Zn under optimum conditions.97 8. 4. 3 Figure 6 — The relation between Zn recovery and grade using oxine and dithizone under optimum flotation conditions (pH 9).7 37.4 36. the process must be reiterated using new systems until the criteria are met.6 10.8 37.75 9. increasing the oxine/dithizone concentration to more than 540 g/t caused the best recovery.7 6.6 15.1 24 30. 2006.6 32. The confirmation test indicated that the zinc recovery rates were maximized by increasing oxine and dithizone concentrations to 1000-2000 g/t and 1250-1500 g/t. the grade and recovery of zinc increase with the increase of both collectors up to an optimal condition around 1500 g/t at a pH level of 9.6 15. when the concentration of oxine/dithizone increases. However. recoveries and grades of zinc were 38%. Zn recovery decreases (Fig.5 Recovery (%) 16. In fact. Spread over all concentrations of the chelating agents. Flotation using dithizone also Figure 5 — Comparison of the recovery and grade of zinc oxide by varying oxine and dithizone concentration under optimum conditions (pH 9).7 23. The confirmation test is a crucial and highly recommended step to verify the experimental conclusions. 27 No. 4 also shows that the optimum concentration of agents for the maximum Zn recovery is more than 540 g/t. Several confirmation experiments were carried out at the optimum levels of flotation parameters for zinc recovery (Table 6). Zn recovery using both collectors is similar. the recovery of Zn for oxine is better than that for dithizone. This result could be due to the lower solubility of the collector. As shown.5 9. 164 MINERALS & METALLURGICAL PROCESSING .86 10 11. while its grade is lower. Confirmation and comparison of Zn recovery by oxine and dithizone. As can be seen.4 10 11 11.4 53. but increases steadily with the use of dithizone.11.6%. Similar results have been found by Natarajan and Nirdosh. August 2010 • Vol. 53.
M.. M.M. a flotation time of 30 min. Arnold. R.. Rome.. A.. No. 2005.” U. M. 3.” International Journal of Mineral Processing. 1973. No. Montgomery. 540g/t. 14. and Reid.. C. 90–96. of the International Biohydrometallurgy Symposium. A. Vol. Bergh. (Esfahan.. Fuerstenau. Part A..M. and Nirdosh. 1980. “Optimization study of the leaching of roasted zinc sulfide concentrate with sulfuric acid solutions. 1996. 11.9 ± 3.... pp. Leppinene.2 using dithizone at optimum conditions with a confidence level of 90%. Yianatos. 205-212.. 2005.. M. Opur. 355-366. pp.” Minerals Engineering.” US Patent 5. 18. and Koleini. 27 No. K. No. 2.G. Li. S. “New collectors for sphalerite flotation..” MP3 Conference.T. “Anglesite flotation: a study for lead recovery from zinc leach residue. Vol. Tech. Vol. J. Roy. G...” Chem. pp. Society of Manufacturing. India. A. As Fig.” Mineral Processing Institute.. The results also showed that the recovery rate of zinc increased to 43.. S. pp.. and Kim. Saleh A. 257-277.D.. Vol. pp.” International Journal of Mineral Processing. Natarajan.A.Y. W.O. 2. V. Wang. Y. G. E.” Minerals Engineering. Vol. Bulut. August. Miller. 20g/t. C. corn starch. J. J. 43. Collins. CNR. N. 101–104.. 1994. Gomez.” U.. Vol.. Gül.E.. 2006. J. C. England. F.. 173-180.... References Marabini. 935-940.. Fick.. V. and Nightingale. J... American Supplier Institute (ASI) Press. Taguchi Methods/Design of Experiments.S. Yazdi M. 3 • August 2010 . J.” Lead–Zinc’90. 1993. Chapman & Hall. 1985.” Minerals Engineering. 79. 1976.. 247 pp. Hajati. Vol. Park.” Minerals Engineeing.. “Recovery of metal values from zinc plant residues. and Ghobadi. Li. Cox. pp. pp.18. “The selective flotation of galena from sphalerite with special reference to the effects of particle size. a conditioning time of 10 min and the following concentrations of reagents: sodium silicate. R.. A Primer on the Taguchi Method. 107–108. 1999. A. Y. Vol. pp. Vol. V. “Optimization of turning operations with multiple performance characteristics. dithizone is better than oxine. Design and Analysis of Experiments. Iran) for providing the necessary facilities for carrying out this work.. Vol. 51.. pp.. Mulligan. Sarraf-Mamoory.. M. “Comparison of Pb-Zn selective collectors using statistical methods. “Effect of different carbon dioxide concentrations on ferrous iron and pyrite oxidation by a mixed culture of iron and sulfur-oxidising bacteria. and Li. Taguchi. Mousavi.A. Vol. pp.S. Barbaro. H. 279-282. S. M.. but to attain the highest zinc grade..... 2006. 12. 1093-1098. Vol. 2001.. “Bioleaching of a Spanish complex sulfide ore bulk concentrate. A. “Mixing characteristics of industrial flotation equipment. pp. 672 pp.: Mater.. D. Vossoughi. Cho. 2002.... The relation between Zn flotation recovery and its grade was interplotted using oxine and dithizone results (Table 6 and Fig. W. and Rodríguez. “Treatment of zinc plant leach residues for recovery of the contained metal values.” Separation and Purification Technology. “Bioleaching of Ok Tedi copper concentrate in oxygen and carbon dioxide-enriched air. D. C. John Wiley & Sons. 1990. 2. S. A. F.. June. and Philips. 1998. G. F. and Yamini. Conclusions This study attempted to optimize Zn flotation recovery from low-grade tailings. 4. J. 109–114.. No. Ozmetin. and Kuhn. J. Kangal. 18.” International Journal of Mineral Processing. 1989. 1996.. L.C. 177 pp. A. and Arslan. 2000. 336 pp. E.seems to produce a higher error rate. Tarbiat Modares University and BAMA Co.).H. 2008.. Marabini. Process.Y. R. and Ballester. K. pp.. D. pp..348. Alesse.” Chemical Engineering Science.. 2005. P.713. Mater. Trahar. 46. CRC. W. 1999.” J. No.” Minerals Engineering.” In: IX International Mineral Processing Symposium. R.” In: Proc. 1999... “Optimal conditions for oxide lead minerals flotation. Hoffmann. M. M. N. L. C. Eng. and Stephanopoulos.225. Ollivier.. E. pp. J. Patent 5. “Purification of zinc ammoniacal leaching solution by cementation: Determination of optimum process conditions with experimental design by Taguchi’s method. “Flotation of Aladag oxide lead–zinc ores. 61.” Minerals Engineering. 93–106. C. 8/9. “2-mercaptobenzoxazole derivatives as collectors for the selective flotation of metal ores. 151-166. pp.880. Jafari. April. 2..S. “Microbial reduction of iron ore. Amils and Ballester (ed. London. Bornengo.. 2002.E. Yoon. 6). the relative contributions of different parameters for maximum Zn recovery were investigated using oxine and dithizone. Vol. London... 453-461. “Recovery of lead.. silver and gold from zinc process residue by a sulfidization-flotation method. 10. oxine is better than dithizone.. January. 1.B. 25–48. R. “A new process for leaching metal values from ocean polymetallic nodules. “Flotation of zinc and lead oxide–sulphide ores with chelating agents.. Using the Taguchi method of experimental design and analysis of the S/N ratio.310. and Peres. No. Process. R. Chapman and Hall. O. 344 pp. a sodium thiosulfate concentration of 540g/t. Dashti. 2273–2282. 193–209. pp. Önal. “Comparison of Pb-Zn selective collectors using statistical methods.. and Bergamini. The maximum Zn recovery rate for dithizone was obtained at a pH of 9. “Use of grinding and liberation models to simulate tower mill circuit performance in a lead/zinc concentrator to increase flotation recovery. R.C. A. 2005. 683-702... 44-45.....740. Vol. “Optimization of ferrous bio-oxidation rate in a packed bed bioreactor using the Taguchi approach. and Gottlieb.9% for dithizone. March. 1-29. No. Freeman. No. J. Önal. 3. M. Rastas. Robust Design and Analysis for Quality Engineering. “Beneficiation studies of BAMA oxidized lead and zinc ore.” Separation and Purification Technology. “The study of degree of liberation of zinc and iron oxide minerals ore in Bama Goshfill Mine. Cappadocia. 2007. Rashchi. and Renaud.S.” International Journal of Engineering. The Theory of the Design of Experiments.. Z.4 ± 3. 1993... 95.. 18. Weller. an oxine concentration of 1000-2000 g/t. the maximum zinc grade will be 20. pp. S. L.. Perek. Vol. Yamini Y. M. The Minerals. and Yokoyama. 141-148.. and M. Littleton. MINERALS & METALLURGICAL PROCESSING 165 Vol. T. 1990. 2003. Witne. 1996. Patent 4. 1994. 1997.M.C. Nian. Tokyo. September.” US patent 4.. pp.” Enzyme Microbiological Technology. 3.505.. No. 1999. Sci. Y..R. pp. Society of Mining Engineers. and Rinelli. Abdollahy. to attain the highest zinc recovery. a sodium silicate concentration of 540g/t and a sodium thiosulfate concentration of 180g/t. and Kocakerim. M. E. 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Design, operation and control of a teeterbed hydroseparator for classification
J.N. Kohmuench, E.S. Yan and M.J. Mankosa
Manager, R&D process group, senior research scientist and vice president of operations, respectively, Eriez Manufacturing, Erie, Pennsylvania
G.H. Luttrell and R.C. Bratton
Professor and senior research associate, Dept. of Mining and Minerals Engineering, Virginia Tech, Blacksburg, Virginia
Teeter-bed (i.e., hindered-bed) separators are used throughout the mineral processing industry for both classification and density separation. The high capacity and sizing characteristics of these units make them ideal for feed preparation prior to coarse flotation (+0.100 mm) circuits. Teeter-bed separators are typically easy to control with two basic operating parameters, including fluidization water rate and bed level. However, data show that these two parameters greatly interact with one another. Given this finding, a high-level automatic control scheme was developed and implemented on a full-scale separator. In addition, dialogue with plant operators has led to several simple changes to an already established design that improves operational and maintenance characteristics.
Key words: Teeter-bed separators, Hydroseparation, Separation
Hydraulic separators are frequently used in mineral processing for sizing applications. Of these devices, the teeter-bed or hindered-bed separator (TBS) continues to be a mainstay within the mining industry. Typically, these devices are open-top vessels through which elutriation water is injected. This teeter water is commonly distributed across the base of the cell through a network of distribution pipes or perforated plating. During operation, feed solids are introduced into the upper section of the separator and are influenced by the teeter water. While the smallest/lightest particles are hydraulically carried over into the collection launder, the coarser/denser particles have sufficient mass to settle against the fluidization water and create a “teeter bed” of suspended particles. The small interstices within the bed create high interstitial liquid velocities that resist the penetration of the slower settling particles. As a result, intermediate fine/ light particles continue to accumulate in the upper section of the separator and are eventually carried over the top of the device into a collection launder. Large or heavy particles, which settle at a rate faster than the upward current of rising water, eventually pass through the fluidized bed and are discharged out one or more restricted ports through the bottom of the separator. The separation provided by a teeter-bed separator is governed by the following:
(1) where Ut is the hindered-settling velocity of a particle (m/ sec), g is the acceleration due to gravity (m/sec2), d is the particle size (m), ρs is the density of the solid particles (kg/m3), ρf is the density of the fluidizing medium (kg/m3), η is the apparent viscosity of the fluid (kg·m-1·s-1), φ is the volumetric concentration of solids, φmax is the maximum concentration of solids obtainable for a given material, and β is a function of Reynolds number (Re). It should be noted that Eq. (1) was derived from an expression advocated by Masliyah (1979) and modified utilizing relationships offered by Richardson and Zaki (1954) and Swanson (1989). An in-depth derivation of Eq. (1) is not reviewed here but is offered elsewhere (Kohmuench et al. 2002 and 2006). By inspection of Eq. (1), it can be determined that both the size of a particle and its density greatly influence how that particle will settle within a hindered state. As such, teeterbed separators are frequently used in the minerals processing industry to segregate fine particles according to size, shape or density (Wills, 1997). Typically, if a size distribution is very narrow and there is a large variation in particle specific gravity (e.g., mineral sands), then a teeter-bed separator can be used to segregate material based on density. Likewise, if a size distribution is very wide and the density distribution is relatively tight (e.g., silica sands), a teeter-bed separator can be successfully utilized as a classifier.
Paper number MMP-09-040. Original manuscript submitted October 2009. Revised manuscript accepted for publication December 2009. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. prior to February 28, 2011. Copyright 2010, Society for Mining, Metallurgy, and Exploration, Inc.
August 2010 • Vol. 27 No. 3
MINERALS & METALLURGICAL PROCESSING
Teeter-bed separators are considered operator-friendly and simple to control. Traditionally, there are only two primary control variables, which include i) the fluidization rate and ii) the teeter-bed level. The fluidization rate is the amount of water or other fluidizing medium that is injected into the cell against which the material must settle. This parameter is typically reported as the volume flow of liquid required for a given cross-sectional area (m3/hr/m2); however, it can also be reduced further and reported as a liquid rise velocity (cm/ sec). The teeter-bed level is essentially an indication of the mass of the settled material held up within the device and is typically reported as a relative level reading, or as an average bed pressure. This basic control scheme is illustrated in Fig. 1. In this approach, feed is presented to the separator and allowed to settle against the upward current of the fluidization medium, which in most cases is process water. The water rate can be controlled manually or automatically using a simple PID control loop. In this latter approach, a flow meter (FIT) provides feedback information to a flow-indicating controller (FIC) that makes adjustments to an automatic flow control valve (FCV) in order to maintain the fluidization flow constant. The bed level is controlled in a similar manner, where the weight of material within the separator is measured using a pressure-sensing device. The pressure-sensing device is typically a pressure or level transducer (LT) that can be mounted to the side of the unit or suspended from above. It should be noted that this indication of level is commonly, but incorrectly, referred to as a density reading. Regardless, the pressure sensor provides a feedback signal to a level-indicating controller (LIC) that makes adjustments to an automatic underflow control valve (LCV) to maintain a constant bed level. Fluidization (teeter-water) rate. Given that the particles must settle against the upward current of fluidization flow within a teeter-bed separator, it is clear that this operating parameter has the most direct influence on separation cut size (d50) which is defined as the particle size having a 50% probability of reporting to either the overflow or underflow product stream as determined from a Tromp separation curve. As a result, the teeter-water rate is considered a coarse tuning parameter and must be sufficient to maintain the bed fluid. If the teeter-water rate is insufficient, the material within the separator will sand out and no separation will occur. Data show that there is generally a linear relationship between the fluidization rate and the separation cut-point (d50). The relationships for two different mineral applications are shown in Fig. 2. Included in this figure are data for classification of 1.00 x 0.106-mm phosphate ore. As seen, a fluidization rate between 0.5 and 1.5 cm/s provides a range of cut points between 0.25 and 0.65 mm. Also shown in Fig. 2 are data for a 3.00 x 0.85-mm potash application. In this case, cut points range from 0.4 to 1.2 mm for fluidization rates of 0.6 to 2.5 cm/s. As expected, the denser phosphate requires a higher fluidization velocity to affect the same cut-point as the less dense potash (2.7 vs. 2.0 SG). However, there is only a moderate difference in the medium-rise velocity for a given cut-point. This result can be attributed to the influence of other process variables, including the feed particle size distribution and the liquid medium characteristics. In this example, the potash is significantly coarser than the phosphate. In addition, it should be noted that the potash classification is carried out using saturated brine as the liquid medium (ρf = 1.24 SG) which influences the
MINERALS & METALLURGICAL PROCESSING
Typical control parameters and response
Figure 1 — Typical control system for TBS units.
Figure 2 — Cut point vs. fluidization rate.
hindered-settling velocity as seen in Eq. (1). The higher liquid specific gravity effectively raises the apparent density within the separator and increases the cut point when compared to process water (ρf = 1.00 SG). The effect of mineral density is more clearly seen in Fig. 3. In this figure, cut size (d50) is shown as a function of upward current velocity for various mineral densities. As seen, denser material requires a greater rise in velocity in order to achieve the same separation cut point. In other words, it takes a greater amount of flow to adequately fluidize denser particles and maintain them in a hindered suspension. Teeter-bed level (bed pressure). Unlike the fluidization rate, which expands or contracts the teeter bed, the bed-level adjustment is used to modify the proportion of coarse/heavy material retained inside the separator. As such, bed level can be considered a fine-tuning parameter that essentially modifies the height or accumulation of these particles within the teeter
Vol. 27 No. 3 • August 2010
Figure 5 — Separation curves for industrial sizers. Figure 3 — Cut point vs. teeter rate using water as a fluidizing medium for various particle densities.
bed. A typical response shows that the relative reading provided by the level transducer rises as the amount of coarse/heavy particles increases. In other words, as more coarse material is held up within the separation chamber, the apparent weight of the suspension is increased. As a result, a specific level reading can be maintained as a control set point that regulates the discharge from the underflow valve, thereby keeping this parameter constant. A typical response of separation cut point (d50) versus bed pressure is provided in Fig. 4. Two cases are provided that show the effect of bed pressure on the cut-point for both a relatively low (1.70 cm/s) and high (2.55 cm/s) fluidization rate. It can be seen in each case that as the bed pressure increases, the separation cut point also increases. This trend is not surprising, given that a teeter bed in a classification operation consists of particles that are being segregated based on size
and hindered-settling velocities. As such, the finest material with the slowest settling velocity will accumulate near the top of the teeter bed and the coarser particles with the highest settling rate will penetrate the teeter bed and accumulate at the bottom of the separation chamber. Changes in the bed pressure set point effectively dictate the overflow weir level with respect to particle size.
Design and control enhancements
Changes in equipment design and control are derived from a demand to enhance the separation that is currently achieved through existing means. In most cases, this implies improving the overall efficiency of the unit operation. For classification applications, the sizing efficiency is typically determined through inspection of the partition curve generated for the separation. An example of two partition curves is provided in Fig. 5. The partition factor represents the recovery of dry solids from the feed to the underflow (oversize) product for each size class. The partition curve is used to determine the separation accuracy by approximating the slope of the line at the cut point (d50). This value is typically reported as the Ecart probable (Ep) error, i.e.: (2) where d75, d50, and d25 represent the size at which 75%, 50%, and 25% of the feed mass reports to the underflow of the separator, respectively. It should be noted that a lower Ep value reflects a steeper curve and thus a better separation. A vertical line represents a perfect separation. Because Ep values vary with d50, a more useful term is imperfection (I), which allows for the direct comparison of separations that occur at different cut points. As seen in Eq. (3), imperfection is simply the Ep normalized to the d50: (3) As shown by Lynch (1977), an alternative approach to determining the relative sharpness of the separation is to fit
Figure 4 — Effect of bed level on separation cut point (d50).
August 2010 • Vol. 27 No. 3
MINERALS & METALLURGICAL PROCESSING
425 mm) was reduced from 9.162 420 μm 7. In this approach. solids content) do not impact separator performance. These nozzles are placed in close proximity to the fluidization system.g. and α is a parameter that reflects the sharpness of the size separation (defined as the slope at P = 50%). The CrossFlow design uses an improved feed delivery system that gently introduces the feed slurry across the top of the separator as opposed to injecting the slurry at a high velocity directly into the teeter bed. to which one or more underflow discharge nozzles are fitted. The discontinuity created by the feed water often results in a secondary interface of fluidized solids.109 729 μm 3.0% 362 μm 8.4 to 8. all other operating parameters were the same for each of the separators except for the feed arrangement. the sizing efficiency of the CrossFlow improved substantially as indicated by the increase in alpha from 3. the teeter water and bed level of the retrofitted unit were adjusted until the cut size between the two units was similar. Note that unlike Ep or Imperfection. the teeter-water velocity remains constant throughout the separation chamber and the overall design minimizes turbulent mixing. The separation curves for the two units normalized to their respective cut points are those shown in Fig. d is the particle size. A second round of testing was completed in order to compare the two classifiers at a similar particle size cut point. The resultant data from the full-scale. The design of the CrossFlow Separator is based on maintaining a constant. Since the separation cut point (d50) had been reduced simply by changing the feed arrangement. Some classifiers utilize a flat-bottom arrangement. It is easily seen that the retrofitted classifier offers a Table 1 — Comparison of full-scale classifiers.7% Existing CrossFlow separator Figure 6 — Water flow velocities in classifiers. Given this arrangement. Tonnages to both units were equal and left unchanged.425-mm Test 2 – Particle cut size Alpha value Imperfection 490 μm 3. In other words. quiescent and precise upward velocity within the separation chamber of the unit. Unfortunately. which can be detrimental to performance. Hydrodynamic studies indicate that quiescent flow/non-turbulent conditions must exist in a teeter-bed separator to maintain a high efficiency (Heiskanen. the CrossFlow significantly reduced the particle cut size from 729 to 362 microns. 6). 27 No.7%. as seen in Fig. side-by-side evaluation are presented in Table 1. 3 • August 2010 . the tangential feed introduction ensures that variations in feed slurry characteristics (e. Test variable Test 1 – Particle cut size Alpha value Misplaced +0. in which two units were compared side-by-side with respect to sizing efficiency. Figure 5 illustrates a case study. A larger issue with this type of feed injection system is the discontinuity in flow velocity created by the additional water that enters with the feed solids and reports to the overflow launder.. d50 is the particle size cut point (defined at P = 50%). conventional hydraulic separators typically utilize a feed injection system that discharges directly into the main separation chamber.2 0. a bottom plate is installed directly beneath the teeter zone.2 0. however.0% to only 1. one of two existing hydraulic classifiers was retrofitted with an Eriez CrossFlow feed presentation system. As a result. much sharper separation curve when compared to the existing unit. a larger value of α indicates a sharper (more efficient) particle size separation.1 1.4 9. 5.measured sizing data using an empirical partition function such as: (4) in which P is the partition factor. In the CrossFlow. the amount of misplaced coarse solids (+0. In this case. Furthermore. The conventional approach greatly increases the rising water velocity at or above the feed entry point.1. 1993). Excessive turbulence or changes in flow conditions can result in the unwanted misplacement of particles and a corresponding reduction in separation efficiency. with only the feed presentation system altered. which varies uncontrollably as the solids content of the feed varies (Fig. there is no clear MINERALS & METALLURGICAL PROCESSING 169 Vol. the volume of water entering with the feed slurry at higher feed rates is likely greater than the volume flow of teeter water required for proper particle fluidization. A comparison of the separation curves indicates that the retrofitted separator operated with a 33% higher efficiency. Compared to conventional systems. Feed is effectively presented horizontally across the top of the cell towards the overflow launder. which creates excessive turbulence. 6. As seen in this table.
In this approach (Fig. a new process control strategy was implemented by Eriez for managing the various operating parameters of teeter-bed-style separators. the sand is fluidized using 5 L/min of process water. the underflow solids content will vary significantly as the underflow valve opens and closes. the relative density of the teeter bed is quite low. As a result. 7b). Two cases were investigated that included the use of both high and low fluidization rates. the bed contracts and the voids between the suspended particles become smaller. the underflow stream will be relatively dilute. bed level readings are shown for the same application (i. Based on these observations. In this figure. the solids content of this underflow stream will remain very consistent (+/. Vz is the volume of the zone between the two sensors. they drop into this sanded zone and move via mass-action to the underflow valve. The complex interaction between fluidization flow. the bed is expanded to within 50 mm of the overflow weir. In essence. with the glass jar nearly submerged. 7a.. which is a clear indication of bed expansion.e. 7. small glass vial partially filled with sand. thereby creating a highly dewatered product. it can also be deduced from the discussion above that a greater degree of expansion will result in lower calculated bed densities. As a result. 8). 3 170 MINERALS & METALLURGICAL PROCESSING . This sensor provides the process input for a level indicating control (LIC) which proportionally opens and closes the underflow valve (LCV) to maintain the mass above the sensor constant. More importantly. the upward water flow rate also remains very consistent. each are measurable and therefore susceptible to automatic control. As particles settle past the teeter pipes. at the lower fluidization rate. Figure 8 — Updated control system for TBS units. It is seen that the higher fluidization rate resulted in lower bed level readings (at the same cut point). In the second example (Fig. Effective (calculated) teeter-bed density. the bed is highly fluidized and expanded. A is the cross-sectional area of the separator. which improves separation efficiency. 27 No. While the interaction between these parameters can be challenging to quantify. In the 5 L/min case. As a result. In this illustration. While the top of the teeter bed is high. As seen by the relative position of the sand-water interface. The importance of proper fluidization control and how this parameter can greatly influence particle setting rates through changes in the effective teeter-bed density is seen in Fig. The upper pressure transducer is used in conjunction with the bottom sensor in order to calculate the true density of the teeter zone located between the sensors. In Fig. water. To better manage these fluctuations and improve overall control. This bed density (ρb) is calculated using the following equation derived from first principles: (5) where ΔP is the differential pressure reading calculated from the two pressure transducers.2%). and H is the elevation difference between the sensors. In contrast. The purpose of the dewatering cone is to force the maximum amount of liquid out of the coarse stream. bed level and the true effective bed density is also revealed through further inspection of Fig. More importantly. the sand-water interface has dropped significantly. Under normal operating conditions. The higher density within the teeter zone provided additional buoyancy to the vial. given that the material is being pulled from an area of low percent solids. a free-floating. the same solids-specific gravity) while using two fluidization rates. It should be noted that no sand has been added or removed from the system during this exercise. two transducers are used instead of a traditional single-pressure sensor. with the glass jar less than half submerged. and air was positioned in the teeter zone to act as a visual reference for density. the sand is fluidized with only 3 L/min of process water. a known amount of silica sand is fluidized in a laboratory-scale (50 x 200-mm) CrossFlow separator. which can greatly vary the upward fluidization velocity within the separation chamber. the relative density is quite high. As a result. this cone is located underneath the separation chamber. delineation between the fluidization zone and the underflow discharge area.Figure 7 — Effect of water velocity on bed density. This calculated parameter is monitored by a den- August 2010 • Vol. The lower sensor is used to control the bed level as previously described. a dewatering cone is used to maintain a constant water split within the separator. However. These sensors are installed at different elevations but in close proximity to one another. 4.
g. a teeter-bed density of 1. leave the device susceptible to blockage/plugging due to contaminants in the process water. combined with the small injection hole diameters. a horizontal slotted plate is located at the base of the separation chamber. When several orifices become blocked. which resulted in misplacement of material during normal operation or when the feed size distribution became much finer.Figure 9 — Teeter water and density correlation. A teeter-bed-based separator was installed at a phosphate beneficiation plant. For example. particle size distribution or solids content). when the feed to the separator became significantly coarser.. As such. As a result.. the circuit was placed under automatic control. while water dispersion is achieved by the baffle plate. the teeterwater rate was reduced in order to maintain the calculated bed density of 1. Unlike existing separators. This control scheme can be advantageous in situations where feed or product characteristics change on a regular basis (e. operators hedged against this occurrence by operating at relatively high fluidization rates. These pipes and plates are perforated at regular intervals with large numbers of small-diameter holes. Figure 10 — Example of bed density control. This figure illustrates the controlled response during a period when the feed particle size distribution became significantly finer. 3 • August 2010 . it was found that with all other operating parameters equal. Unfortunately. In addition. 8. Prior to automating the teeter-water addition rate. In addition. as characterized by constant and uninterrupted fluid flow. sanded). the design of the water delivery system is an important issue in the development of a hydraulic separator. 27 No. the water distribution system incorporates a check valve to prohibit backflow and manifold valves that facilitate clean-out in the unlikely event of a plugging issue. due to variable operator settings and natural matrix inconsistencies. the feed characteristics were constantly changing. as shown in Fig. as demonstrated by the flat line trending produced by the plant’s distributed control system (DCS) as seen in Fig.25 cm) which are significantly larger than the largest particle. As a result. For the purpose of proving the concept. 9. the existing separator was outfitted with an automatic process water flow control valve and a separate differential pressure transducer. This allowed the separator to be controlled. Given the correlation seen in Fig. resulting in a loss of performance in this area. conventional teeter-bed separators have an inherent design flaw that limits both the capacity and efficiency of the unit. Elutriation water is injected through these holes over the entire cross-section of the separator. fine feed will result in a lower bed density and fluidization rate. The original control scheme for this separator included the use of manual control valves for the adjustment of the fluidization water rate. the teeter bed would be insufficiently fluidized (i. the density-indicating controller supplied a continuously updated set point for the teeter-water control in order to maintain a constant bed density.660 SG. A clear correlation between these two parameters was established as seen in Fig. The large water flow rates.660 SG was chosen as the operating set point. This arrangement includes manually actuated valves that are located on each end of the MINERALS & METALLURGICAL PROCESSING 171 Vol. As such. A novel approach has been developed that incorporates a slotted plate to disperse the elutriation water across the base of the separator. To combat these issues. 10. Accurate control of the teeter water requires a trouble-free fluidization system. As such. a dead zone occurs in the fluidization chamber. Full-scale case study – enhanced fluidization control. these orifices are located at distant intervals (typically >15 cm) and serve simply to introduce the water. the response of the calculated bed density with varying teeter-water rate was investigated. coarser feed will cause an increase in bed density due to its greater mass and required fluidization rate. In contrast. sity indicating controller (DIC) which then finely adjusts the fluidization flow in order to maintain the bed density stable. This modification essentially eliminates problems associated with plugging of distributor plates or pipes. In contrast. the CrossFlow separator incorporates another design feature that improves water distribution. This approach provided for an extremely stable process. Conventional teeter-bed designs use a series of lateral pipes or a steel plate located at the base of the separation zone. 9.e. Water is introduced beneath the plate through a series of large diameter holes (>1. In this design.
N. Masliyah J.J. Chapman & Hall. “Free and hindered settling. G. 3. J. 5. 7.Q. Design. No. coal industry. and Honaker. 23. Kohmuench. November.. M. Vol. Bratton. an Eriez CrossFlow Separator was shown to provide improved separation when compared to a traditional classifier. sharpness) of the slope of these separation curves at the process cut point. 1993.H. expertise and direct financial support are gratefully acknowledged.. As such. 2002. 1. 39. pp. K. The classification efficiency of teeter-bed separators is commonly quantified through examination of partition curves. Lynch. operating parameters were automatically adjusted to combat the changes in feed characteristics. Sixth Edition. 34. Optimisation. “Sedimentation and fluidization: Part I. 1989.e. Richardson J... pp. 1166-1168. By monitoring and correcting for the calculated bed density.T. November.H. “A process engineering evaluation of the CrossFlow separator. Mineral Processing Technology.. Mankosa. 43-49. manpower.” Minerals and Metallurgical Processing. “Hindered settling in a multi-species particle system.” Minerals and Metallurgical Processing.A. A second pressure transducer is required for this approach.. 2006. ButterworthHeinemann. Through the examination of partition curves generated from a full-scale investigation.S. The fluidization rate is considered a coarse tuning parameter. No. pp. 27 No. References August 2010 • Vol. 1979. Swanson V. Luttrell. additional improvements were made to the teeter pipe and manifold arrangement to facilitate clean-out of the fluidization system in the unlikely event of fouling. Given that ease of maintenance is an important aspect for reliable service. Boston. 1997. pp. February..” Chemical Engineering Science. In general: 1.N.” Minerals and Metallurgical Processing. Heiskanen. Vol. Vol. Vol.J. This control method involves adjusting teeter-water rates to maintain a constant calculated Acknowledgments The authors would like to acknowledge and thank the multiple industrial representatives who participated in the various test campaigns described in this work. and Adel. p.J. which provides additional control stability for variable processes.water supply manifolds..F. 6. Their contributions in terms of time. 486 pp. Bed level is considered a fine-tuning parameter. 4. Data show that there is a linear relationship between teeter-water addition rate and the separation cut point (d50). B. Wills. R. 3 172 MINERALS & METALLURGICAL PROCESSING .. 190-196. The Ecart probability (Ep). Kohmuench. Massachusetts.. An increase in bed level increases the d50 by allowing more coarse/dense material to accumulate within the teeter zone of the separator. 1977. bed density. This approach allows each manifold to be easily flushed by diverting flows from one side of the unit to the other.. 19. Mankosa. 1954. J.. 187-195. 116.” Transactions. G. London. Summary Teeter-bed separators are efficient classification devices that provide a means to separate coarse and fine material according to hindered-settling relationships. 321 pp. Institute of Chemical Engineering. An improved control strategy was implemented based on laboratory and field observations. Elsevier. pp. it is important to understand how these parameters interact with one another. “Applications of the CrossFlow teeter-bed separator in the U. A. allowing for subtle changes in separation cut point (d50). Material characteristics and operating variables. Particle Classification. This improvement is attributed to the more efficient management of the water that arrives with the feed solids. such as fluidization water flow and bed level.. and Control (Development in Mineral Processing I). and alpha (α) are common terms used to define the steepness (i. 2. M. Amsterdam. This improved control strategy was implemented on a production scale at an industrial phosphate plant. 4.. R. England. 35-53. imperfection (I). and Zaki W. can greatly affect the separation.. Mineral Crushing and Grinding Circuits: Their Simulation.
which allow for the QAS222 to be strongly adsorbed on the aluminosilicate minerals. N-(2-aminoethyl)-1-naphthalene-acetamide (Zhao et al. 2011. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. Inc. such as the excessive amount of foams. China The flotation of diaspore. 2009). they were positive in a wide pH range. 2003b). formation of the hydrogen bond and ammonium absorptions.D candidate. Society for Mining. 2008). 27 No. low selectivity. dodecyl tertiary amines (Liu et al. Therefore. Copyright 2010. quaternary ammonium salts (Zhao et al. kaolinite.. surface adsorptions cannot be formed effectively. 2009) and alkylguanidine (Guan et al. 2007). School of Chemistry and Chemical Engineering. illite and the diaspore-kaolinite mixture were studied with a new cationic organosilicon quaternary ammonium collector entitled QAS222. China Guangyi Liu Associate professor. Collectors Abstract Introduction In China there is abundant bauxite. however. many flotation collectors for aluminosilicate minerals in the reverse flotation process. The acting mechanism of the collector with the four minerals was analyzed by Zeta potential measurement and FT-IR spectrum analysis. dedecylguannidine sulfate (Zhong et al. resulting in reduced floatability. Hunan Province. these reactions between QAS222 and diaspore at pulp pH=11 are weaker than those of the aluminosilicate minerals. around 98% of the resource is diasporic bauxite and more than 70% of the resource has an Al2O3-to-SiO2 mass ratio (A/S ratio) lower than 7. Metallurgy. However. Paper number MMP-09-036. 2001). notably alkylamines (Jiang et al. The results indicate that the QAS222 was effective in the reverse flotation of the diaspore-bauxite mixture of different Al2O3 -to-SiO2 mass ratios (A/S ratio) at an optimum pulp pH of 11. indicating that QAS222 has a strong adsorption on the surface of the aluminosilicate minerals and thus that these minerals can be floated. 2003). methylnaphthalene amine (Du et al. 2003). its disadvantages. 2009) have been reported effective in collecting aluminosilicate minerals. Jiangxi University of Science and Technology.Reverse flotation of diaspore from aluminosilicates by a new cationic organosilicon quaternary ammonium collector Xinyang Yu Ph. Central South University.. besides electrostatic adsorptions. Gemini quaternary ammonium (Xia et al. N-dodecy1-1. etc.. especially at pH>9. γ-alkyl-propylamines (Cao et al. School of Chemistry and Chemical Engineering. especially the search for high-effective flotation collectors for aluminosilicate minerals. 3-diaminopropanes (Hu et al. is important to the Chinese bauxite processing industry. 2003a). MINERALS & METALLURGICAL PROCESSING 173 Vol.. Thus. pyrophyllite. Hunan Province. However. prior to February 28. Furthermore. Changsha. School of Chemistry and Chemical Engineering. The potentials of the four minerals increased when they were conditioned in the QAS222 solution.. Key words: Flotation. It is therefore necessary to desiliconize bauxite and to increase its A/S ratio if the low-cost Bayer process will be used to produce Al2O3 from the bauxite. 2004). the study of bauxite processing with a reverse flotation process. Changsha. Central South University. the potentials of the three aluminosilicate minerals increased faster than that of the diaspore. chemical adsorptions occur between QAS222 and the aluminosilicate minerals. Revised manuscript accepted for publication May 2010. China Hong Zhong Professor.. Hunan Province and School of Resource and Environmental Engineering. Changsha. Central South University.. N-(2-aminoethyl)-dodecanamide (Zhao et al. Original manuscript submitted October 2009. N-(3-aminopropyl)-dodecanamide (Zhao et al.. 3 • August 2010 . Bauxite. Ganzhou.. In recent years. The FT-IR spectra analysis further indicates that. however. Jiangxi Province. most of these collectors are not used in industry due to their deficiencies. 2003c).. have restricted its wide application in industry. high cost.. such as the difficulty in dewatering concentrate and its high reagent consumption. and Exploration. high reagent consumption. Though direct flotation is used in the bauxite processing industry.
50 13.094 0.67 59. pyrophyllite and illite as functions of pulp pH and QAS222 dosage. Diffuse reflectance infrared spectroscopy was used to characterize the surface species on the materials treated. All measurements were conducted in a 0. however. which was then filled with distilled water. Jiaxian of Henan Province. Zeta potential measurements. CA).01 0.074 mm in a porcelain mill..1 M) and HCl (0.1-M KNO3 background electrolyte solution. They were handpicked and then crushed and ground to less than 0. dried and weighed.51 Loss 14. Qingtian of Zhejiang Province and Ouhai of Zhejiang Province of China.32 0. 0. a new surfactant with bioactivity.0×10-4 M QAS222 was used. Pure minerals (3.29 0.98 39. under Experimental Results and discussion Materials and reagents.028 0.85 Cationic organosilicon quaternary ammonium.65 45.Table 1 — Chemical composition of minerals tested (w/%). kaolinite. i. Specifically.2 Na2O 0.. pyrophyllite and illite materials used for the present study were obtained from Xiaoguan of Henan Province.62 10. chemical engineering. pH<7. Materials were ground to less than 5 μm in diameter. the recoveries of kaolinite. The products were collected.98 6.007 0. The diaspore. and was presented without any baseline correction. The flotation was conducted for four minutes.0 g) or artificially mixed bauxite materials (3. 2007).98 0. The purities of the materials are higher than 95%.16 37.2 32. pyrophyllite. Materials were ground to a diameter of less than 5 μm as they were prepared for the microflotation tests.068 K2O 0.78 43.e.16 0. multifunctional and antibacterial (Liu et al. was synthesized and its performance in the reverse flotation of diaspore. 3 174 MINERALS & METALLURGICAL PROCESSING . The new collector of organosilicon quaternary ammonium has a microstructure as illustrated in Eq. NaOH (0. to show the collecting ability of the QAS222. Flotation performance of QAS222 with minerals.97 Fe2O3 0. Therefore.1. pharmaceuticals and agricultural chemicals (Su et al. Figure 1 plots the impact of pH on the floatability of the four pure minerals when 2.0 g) were placed in a plexiglass cell (40 ml). Under acidic conditions.025 0. Repeated tests showed that this conditioning procedure was capable of producing mineral surfaces suitable for studying the effect of various treatments. However.06 13. 27 No. kaolinite and pyrophyllite were higher than 80% and illite was higher than 60%.17 0. with chemical compositions as shown in Table 1.01 MgO 0. pyrophyllite and illite were found to be practically independent of pulp pH and all three achieved relatively high recoveries. it is now widely used in the fields of fabric finishing.(1): (1) Flotation tests. The recovery of diaspore increased with the increase of pulp pH and reached its highest point (>95%) at around pH=4. kaolinite.046 0.1 M) solutions were used as pH modifiers and distilled water was used in all experiments. The recovery was calculated based on the dry weights of the products obtained. is innocuous.33 4. The results presented in this paper are the average of three Figure 1 — Effect of pulp pH on the performance of QAS222.01 0. there is little information regarding the use of this surfactant for mineral flotation. illite and the diaspore-kaolinite mixture was investigated.84 1. The acting mechanism of this collector with the four above minerals was analyzed by Zeta potential measurement and Fourier transform infrared (FT-IR) spectrum analysis. Microflotation tests were conducted to show flotation behaviors of diaspore. Zeta potentials were measured using a Delsa−440SX Zeta potential instrument from the Beckman Coulter (Brea.01 0. then it decreased drastically with further increase of pulp pH until it approached nearly zero above pH 12.14 TiO2 2. kaolinite.20 0. As seen in Fig.019 0. FT-IR spectrum analysis. the suspension was agitated for three minutes and the pH was measured before flotation. August 2010 • Vol. respectively.71 SiO2 0. it affects the recovery of diaspore the most.05 g of material was placed in a 100-ml breaker for five min with 80 ml distilled water and the pH was adjusted and measured. effective. After adding the desired amount of reagents.068 0.03 4. a new cationic organosilicon quaternary ammonium collector..21 CaO 0. independent measurements with a typical variation of ±2 mv.22 Water 14. FT-IR spectrum analysis was performed with an AVATAR360 FT-IR from Nicolet Corporation of USA.5. entitled QAS222. the pulp pH has different degrees of influence on the floatability of the four minerals.65 6. Mineral Diaspore Kaolinite Pyrophyllite Illite Al2O3 80. 2008).
11 and 13. the recoveries of the three aluminosilicate minerals decreased at different rates with the increase of pulp pH.47% and 68. indicating a significant tendency for reverse flotation of the diaspore from the aluminosilicate minerals. and reached 90. the recovery of diaspore was very low. respectively.12%. the recoveries of the four minerals increased with the increase of QAS222 concentration. silicate minerals showed good floatability at a pulp pH<9. As shown in Fig. Although the three alumino- Figure 4 — Effect of QAS222 on the floatability of minerals at pulp pH=13.0×10−4 M. Reverse flotations of the artificially mixed bauxite of different diaspore-to-kaolinite mass ratios were carried out to investigate the possibility of separating diaspore from aluminosilicate minerals with QAS222 as collector. As seen in Fig. When the pulp pH is adjusted to 11. when the pulp pH is fixed at 9. The flotation of diaspore. and did not change with the increase of QAS222 concentration. 3. Figure 3 — Effect of QAS222 on the floatability of minerals at pulp pH=11. Thus. it seems that the pulp pH should be higher than 9 if these minerals are to be effectively removed from diasporic-bauxite with QAS222 as a collector in the reverse flotation process. 3 • August 2010 .0×10−4 M. 27 No. The pulp pH was further increased to 13 in order to further investigate the flotation behaviors of the four minerals with the QAS222 as collector. but they were still much higher than that of the diaspore. where the aluminosilicate minerals showed good floatability. Thus. Reverse flotation of the diaspore-kaolinite mixture.Figure 2 — Effect of QAS222 on the floatability of minerals at pulp pH=9. Such a pulp pH level is also favourable for a reverse flotation manipulation. the recoveries of diaspore and kaolinite are higher than 85% and the recoveries of pyrophyllite and illite are round 80%. as shown in Fig. less than 10%. pyrophyllite and illite were further conducted at pulp pHs of 9. pyrophyllite and illite when pulp pH is around 9. to study the impact of QAS222 dosage on their floatability. The recovery was calculated based on the dry MINERALS & METALLURGICAL PROCESSING 175 Vol. the recoveries of kaolinite. Therefore. kaolinite. alkaline conditions. their recoveries were similar to that of the diaspore as the QAS222 concentration increased and there was no favourable condition to perform reverse flotation. pyrophyllite and illite increased rapidly with the increase of QAS222 concentration. compared with the recoveries of the other aluminosilicate minerals. QAS222 may be an effective collector for the three aluminosilicate minerals. The concentrate and tailings products were weighed separately after filtration and drying and the A/S ratio was determined by silicon-molybdenum blue colorimetry. pyrophyllite and illite are much lower than those achieved at pulp pH=11. as the QAS222 concentration reached the maximum of 4. the diaspore may be effectively separated from kaolinite.1.2. it is difficult to separate diaspore from kaolinite. According to the results shown in Fig. 72. the diaspore achieved a much lower recovery at a pulp pH>9. pyrophyllite and illite under a higher pulp pH condition. the recoveries of kaolinite.74%. However. this is due to the fact that the three aluminosilicate minerals are depressed under an excessively high alkaline pulp condition. 4. respectively. In addition. It can be concluded from the results above that the optimum pulp pH is around 11. when the QAS222 concentration was 4.
obviously. In addition. respectively. illite and pyrophyllite in distilled water are 6. respectively.79% and 69.45 78. However.32 in distilled water to 10.74 81.5 and 3. 27 No. It is clear that QAS222 was more Figure 6 — FT-IR spectra analysis of diaspore conditioned with and strongly adsorbed on the aluminosilicate minerals and without QAS222. It achieves an effective reverse flotation at a pulp pH=11. under acid conditions the Zeta potentials of kaolinite. the A/S ratio.91 73. pyrophyllite and illite increased with the increase of pulp pH.0.Table 2 — Reverse flotation results of the diaspore-kaolinite mixture.91%. the IEPs of kaolinite. As shown in Fig. 77. the A/S ratio. As the A/S ratio of the feed increases. as shown in Fig.0×10-4 M QAS222 as above analysis is in accordance with the results of flotaa function of pH.01 15.75 77.0×10−4 M QAS22 solution.82. It is therefore concluded that the QAS222 is an effective collector in the reverse flotation of diaspore from aluminosilicate minerals. (2003c).36 69.9 when conditioned with the QAS222 solution. 5.75 18.53 5. August 2010 • Vol.45 6.13 77.4. and then these aluminosilicate minerals have good floatability.02 4. Diasporeto-kaolinite mass ratio of mixture 1:1 3:2 2:1 3:1 A/S ratio of mixture Concentrate grade (%) Al2O3 SiO2 Concentrate recovery (%) Al2O3 SiO2 A/S ratio of concentrate 2.32. 5. the IEP of diaspore increased from 6. When the A/S ratio of feed is 2. The flotations were performed at a pulp pH of 11 and at a QAS222 concentration of 4.30 12.7 3. After they were conditioned with 4.5. Al2O3 grade and Al2O3 recovery of concentrate product are 12. with the results illustrated in Table 2. Measuring the Zeta potential of the aluminosilicate minerals further confirmed the conclusions above. However.59 18.41 6. especially at pulp pH>9.86 22. in the absence of QAS222. as there are steady adsorptions of the QAS222 on their surfaces.0×10−4 M.07 5. the potentials of the aluminosilicate minerals decreased at different rates at pulp pH>8. which are in accordance with those reported by Zhao et al. The Zeta potentials of the four minerals conditioned with and without the QAS222 (4. 5. their Zeta potentials are all positive. may achieve higher selectivity for these minerals.4.0 and 2. kaolinite.7. pyrophyllite and illite are 3. As shown in Fig. The Figure 5 — Zeta potentials of minerals with 4. indicating that the adsorption of QAS222 on these minerals has decreased and thus their floatability has deteriorated. 2. tion tests above. 3. Zeta potential measurements of minerals. indicating that the adsorption of QAS222 on the surface of the diaspore has decreased and thus may lessen its floatability. the Zeta potential of the diaspore begins to decrease. 3 176 MINERALS & METALLURGICAL PROCESSING .21 weights of products obtained. It can be seen from Table 2 that the QAS222 has good selectivity and a strong collecting affinity for kaolinite.0×10−4 M) were measured as a function of pulp pH. indicating that QAS222 was adsorbed on the diaspore surface and thus may increase its floatability. respectively.58 4. 3.82 14. It should be noted that the iso-electric points (IEPs) of the diaspore.07 14.79 77. under alkaline conditions. the QAS222 has an effect on the Zeta potential of diaspore.17 27. grade and recovery of the concentrate product also increases.27 79. in the range of pulp pH 2-12 and their increased values of Zeta potential are always bigger than that of diaspore.
6. respectively. 753. 7.69 cm-1 is caused by the Al-O stretching vibration. being a representatively chemical adsorption. Figure 9 — FT-IR spectra analysis of illite conditioned with and without QAS222. indicating that there exist hydrogen bonds between the QAS222 molecule and the kaolinite (Liu et al. are due to the stretching vibration of the C-N of quaternary ammonium. Si-O and Si-O-Al on the surface. This peak shifts to the higher wavenumber when it was affected by the QAS222. These peaks broaden distinctly when the kaolinite is affected by QAS222. chemical adsorptions may exist between kaolinite and QAS222..50 cm−1 and 2855. as a result of the stretching bonds of CH3 and -CH2.43 cm-1 and 1267.18 cm-1 is due to the Si-O-Al stretching vibration.90cm-1 and 695. As there are Si-O bonds in the QAS222 molecule lattice. chemical adsorptions that link up bonds of Si-O-Si. 7. Si-O and Si-O-Al allow for the QAS222 to be strongly adsorbed on the surfaces Figure 7 — FT-IR spectra analysis of kaolinite conditioned with and without QAS222. In summary. 8 and 9.01 cm−1 respectively.FT-IR spectra analysis of minerals. there are no new spectrum adsorbing peaks on the diaspore surface when it was conditioned with QAS222. Another two peaks at 1309. leading to broadened spectra peaks. as shown in Fig.0×10−4 M QAS222 solution at a pulp pH of 11were measured and are presented in Figs. From the FT-IR spectrum analysis above. 8 and 9. result from the Si-O-Si symmetrical stretching vibration and the peak at 538. the Si and O atoms may link up with other Si and O atoms on the kaolinite surface and thus produce more bonds of Si-O-Si.64 cm-1. indicating that QAS222 is adsorbed on the kaolinite surface by physical electrostatic adsorption. Though there are no new strong adsorbing peaks in the spectra of kaolinite when it was exposed to QAS222. The peak at 1637. it is thus obvious that the acting mechanisms of QAS222 with pyrophyllite and illite are similar to that of QAS222 with kaolinite. indicating that little QAS222 was adsorbed on the diaspore surface. 3 • August 2010 . indicating that ammonium is adsorbed on the kaolinite surface. the spectra of pyrophyllite and illite are similar to that of kaolinite when they were affected by QAS222.27 cm−1 is attributed to the bending mode of H-O-H on the kaolinite spectrum. To further reveal the acting mechanism of QAS222 with the four minerals.47 cm-1. As shown in Figs. However.76 cm-1. 27 No. respectively. these peaks disappeared when the kaolinite was affected by QAS222. it is clear that the increased floatability of kaolinite is due to the affinity of QAS222. the spectra of kaolinite affected by QAS222 exhibit weak peaks at 2926. 2007). As shown in Fig. Figure 8 — FT-IR spectra analysis of pyrophyllite conditioned with and without QAS222. 7. Such a phenomenon is in accordance with the flotation results above. 6. respectively. the FT-IR spectra of the minerals conditioned with and without 4. besides physical electrostatic adsorptions between QAS222 and the three aluminosilicate minerals. the peaks in the 1000-1110 cm-1 region may be attributed to the Si-O stretching vibration and the peak at 912. MINERALS & METALLURGICAL PROCESSING 177 Vol. As shown in Fig. The peaks at 793.
11. Zhong Hong.” International Journal of Mineral Processing.” Journal of Chengdu Textile College. Vol. it is difficult for QAS222 to be adsorbed on its surface. “Study of structure and property of amine collectors. No. Cao Xuefeng. Hu Yuehua. 2003b. pp. Vol. Zhao Shimin.” Minerals Engineering. “The role of cationic polyacrylamide in the reverse flotation of diasporic bauxite. pp. resulting in lessened floatability. No.QAS222 has strong selectivity and collecting ability for aluminosilicate minerals in a wide pH range and by using it as collector the diaspore may be effectively separated from the three aluminosilicate minerals under a strong alkaline condition of pulp pH=11. “Flotation of aluminosilicates using N-(3-aminopropyl)-dodecanamide. chemical and physical electrostatic adsorptions exist between QAS222 and the three aluminosilicate minerals. 13. 2005CB623701). No.” Minerals Engineering. Vol. Hu Yuehua. Vol. 22. Hu Yuehua and Xu Jin. Vol. 1-4 (in Chinese). Zhong Hong. 228-234. No. Vol. 74-83.The Zeta potentials of the four minerals increased when they were conditioned with the QAS222 solution.of the three minerals. 1273-1277. 1031-1033. Zhao Shenggui.” Journal of Central South University of Technology. No. “Synthesis and application of Quaternary Ammonium Silane. 849-852. 3. No. 2008. 500-503. Su Xiaoming.The FT-IR spectrum analysis further confirmed the above analysis. 1191-1199. at the same pulp pH of 11. 4. 27-31 (in Chinese). 573-576.1055-1061. 2007B52). 50874118) and the Foundation for the Author of National Ex- August 2010 • Vol. 417-420 (in Chinese). Zhong Hong and Liu Guangyi. “Synthesis of N-decyl-1. Vol. 2003. 2003c. 92.” The Chinese Journal of Nonferrous Metals. Qin Wenqing and Wang Dianzuo.” Minerals Engineering. At a pulp pH of 11. 9-10. References Conclusions It can be seen from the results and discussion above that: . Accordingly. Vol. Zhong Hong and Liu Guangyi. Wang Dianzuo and Xu Jin. 21. Jiang Yuren and Du Ping. 19. Wang Dianzuo. No. Acknowledgments The work is supported by the National Program for Key Basic Research Projects of China (Grant No. “Flotation separation of the aluminosilicates from diaspore by a Gemini cationic collector. “Effect of quaternary ammonium salts on flotation behavior of aluminosilicate minerals. pyrophyllite and illite using three cationic collector.” Transactions of Nonferrous Metals Society of China. “Flotation of aluminosilicates using N-(2-aminoethyl)-1-naphthalene-acetamide. “Synthesis of γ-alkoxy-propylamines and their collecting properties on aluminosilicate mineral. 2009. 2008. 2007. Zhao Shenggui and Xia Liuyin. 16. floatability was weak. “Flotation of aluminosilicate minerals using alkylguanidine collectors. pp. pp. Zhao Shimin. pp. Hu Yuehua. It is thus concluded that QAS222 is effective in collecting the aluminosilicate minerals and provides an effective collector in the reverse flotation of diaspore from aluminosilicate minerals. pp. Vol. thus increasing their floatability. Hu Yuehua. “Mechanism of flotation for diaspore and aluminium-silicate minerals with alkylamine collectors. No. pp. pp. 1. 2009. 1. Hu Yuehua. However. Hu Yuehua. pp. 280-286. the adsorption of QAS222 on the diaspore surface was weak and it was difficult for the mineral to be floated. 2001. “Substituent effects in kaolinite flotation using dodecyl tertiary amines. pp.” Acta Physico-chimica Sinica. Du Ping. As for diaspore. 13. Zhao Shimin. 2004. the potentials of the three aluminosilicate minerals were positive in the wide range of pH=2~12. and Cao Xuefeng. 2003. 25.” The Chinese Journal of Nonferrous Metals. pp. No. No. the National Natural Science Foundation of China (Grant No. 1-2. Wang Dianzuo. No. 27 No. No. 2009. 6. pp. 2003a. Hu Yuehua and Xu Jing. Cao Xuefeng. 4. 6. which allows for QAS222 to be steadily absorbed on the surfaces of the three minerals and results in their increased floatability. 13. 2. Jiang Yuren and Li Haipu. No. Jiang Hao. Xia Liuyin and Liu Guangyi. Zhong Hong and Liu Guangyi.” Minerals Engineering. 20. 5.” The Chinese Journal of Nonferrous Metals. 688-692 (in Chinese). Xia Liuyin. 11. No. Liu Changmiao. 14. so that they show good floatability under alkaline conditions. indicating that little QAS222 was adsorbed. Vol. . Cao Xuefeng.” Light Metals. Guan Feng. as a result of the strong adsorption of QAS222 on their surfaces. 3 178 MINERALS & METALLURGICAL PROCESSING . Hu Yuehua and Xu Jin. “Investigation on the flotation of Aluminosilicates Using N-(2-aminoethyl)-dodecanamide. However.” Journal of Central South University of Technology. Li Haipu. Vol. Liu Guangyi. 12-14. “Flotation separation of diaspore from kaolinite. Zhong Hong and Yu Xinyang. pp. 2007. . pp. 19. the diaspore presents no new spectrum-adsorbing peaks on the surface. cellent Doctoral Dissertations of China (Grant No. 3-diaminopropanes and its flotation properties on aluminium silicate minerals. Vol.
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