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Lithium extraction from mechanically activated of petalite-Na2SO4 mixtures after isothermal heating
Minerals Engineering 151 (2020) 106294
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Lithium extraction from mechanically activated of petalite-Na2SO4 mixtures after isothermal heating
T
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Nader Setoudeha,b, , Ataollah Nosratib,1, Nicholas J. Welhamb,c a
Materials Engineering Department, Yasouj University, Yasouj 75918-74831, Iran Edith Cowan University, School of Engineering, Chemical Engineering Department, Perth, Australia c Welham Metallurgical Services, South Lake, Australia b
A R T I C LE I N FO
A B S T R A C T
Dedication: Dr. Ataollah Nosrati passed away from cancer before submission of this paper. His co-authors would like to dedicate this paper to his memory.
Mixtures of a petalite flotation concentrate and sodium sulphate (Na2SO4) with mass ratios of 1:0.5 and 1:1 were prepared and milled for 5 h using zirconia media in a planetary ball mill. The milled mixtures were heated at 800–1000 °C for 1 h in air in a muffle furnace. The XRD patterns for the calcines indicated that reaction between petalite and sodium sulphate results in formation of LiNaSO4, albite and spodumene phases. The results indicated that increasing temperature and/or amount of sodium sulphate in the mixtures both play a significant role in decomposition of petalite concentrate and formation of LiNaSO4 phase. Leaching the calcines in hot water (80 °C) selectively dissolved the LiNaSO4. Solution analyses indicated that > 99% lithium dissolution can be achieved for mixtures with 1:1 mass ratio after heating at 1000 °C for 1 h. The presence of phases such as quartz (SiO2) and albite in the leach residues showed that roasting petalite concentrate with sodium sulphate (Na2SO4) and followed by hot water leaching is a sufficient process for selective lithium dissolution from a petalite concentrate.
Keywords: Ball milling Calcine Lithium Mechanical activation Petalite concentrate
1. Introduction In the past few years the demand for lithium has substantially increased due to the prevalence of small electronic devices requiring batteries which are both lightweight and high capacity. The forecast global demand for lithium carbonate shows doubling requirements between 2015 and 2025 (Welham et al., 2017). Lithium-ion batteries (LIBs) are considered the most promising power sources for electric vehicles (EVs) owing to the higher energy output, longer storage life, lower maintenance and higher energy density than other secondary batteries, (Lou et al., 2017). LIBs are also widely used in a multitude of portable electronics, especially mobile phones, personal computers, cameras, etc. (Guo et al., 2018). The rising demand for lithium and lithium compounds in future years necessitates the development of an increased range of natural resources for recovery of lithium. Historically, more than 80% of produced lithium in the world has come from brines; but recent projects have increased the production from hard rock to over 50% (Kuang et al., 2015; Luong et al., 2013; Welham, 2019). Although there are many lithium bearing minerals in nature, only a few are of commercial potential for lithium processing. The most
promising lithium minerals are aluminosilicates compounds such as spodumene and petalite, and micas such as lepidolite and those in the polylithionite group (including the now discredited, but commonly referenced, mineral zinnwaldite) (Meshram et al., 2014). There are many processes for recovery of lithium from lithium ores/ concentrates. These processes are based on breaking down the lithium aluminosilicate minerals during heating with additives including sulphuric acid, limestone/lime, sodium sulphide and sodium/potassium salts, and then followed by water/acid leaching of the calcine products. Some processes for lithium recovery from minerals such as spodumene and lepidolite have been recently reported (Vieceli et al., 2017a; Lee, 2015; Yan et al., 2012a; Meshram et al., 2014; Chen et al., 2011; Luong et al., 2013). Chlorination process is another process for lithium extraction form lepidolite using of chlorine gas or HCl (Meshram et al., 2014; Yan et al., 2012b). Some investigations have been done for treating and extraction of lithium from β-spodumene using hydrofluoric acid leaching in literatures (Rosales et al., 2016, 2014). Preparation of lithium carbonate salts from alkaline leach liquors originating from processing of zinnwaldite with CaCO3 have been performed by Jandová et al. (2010). Sintering zinnwaldite with CaCO3 and water leaching the obtained sinters was also done by Vu et al. (2013) for recovering
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Corresponding author at: Materials Engineering Department, Yasouj University, Yasouj 75918-74831, Iran. E-mail address: [email protected] (N. Setoudeh). 1 Deceased. https://doi.org/10.1016/j.mineng.2020.106294 Received 18 July 2019; Received in revised form 27 November 2019; Accepted 20 February 2020 Available online 06 March 2020 0892-6875/ © 2020 Elsevier Ltd. All rights reserved.
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Table 1 Chemical composition of petalite concentrate by X-Ray Fluorescence and AAS (Li) analysis. Element % Petalite Element % Petalite
Al2O3 16.49 Na2O 0.48
BaO < 0.01 P2O5 0.02
CaO 0.03 SO3 < 0.01
Cr2O3 < 0.01 SiO2 77.04
Fe2O3 < 0.01 SrO < 0.01
K2O 0.97 TiO2 < 0.01
MgO 0.09 Li2O 4.367
Fig. 1. XRD pattern of petalite concentrate as starting material.
Fig. 2. TGA curves of the petalite concentrate and 5 h milled mixtures of petalite-Na2SO4 with mass ratios of 1:0.5 and 1:1.
2
MnO < 0.01 L.O.I 0.64
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Fig. 3. XRD patterns of TGA solid residues for petalite-Na2SO4 mixtures with mass ratios of 1:0.5 (a) and mass ratio of 1:1 (b).
as a product and the preference for petalite over spodumene by ceramic manufacturers. Petalite concentrate from the Bikita deposits in Zimbabwe was processed to high-purity Li2CO3 by roasting petalite concentrate with concentrated sulphuric acid (H2SO4) followed by water leaching to produce Li2SO4 solution which was purified and ultimately precipitated to give high purity lithium carbonate (Sitando and Crouse 2012). Although acid digestion is largely effective, the omnivorous nature of the process leads to significant requirements to purify the solution prior to lithium recovery. Alternative processes which have greater selectivity for lithium do not have such problems and would
lithium and rubidium. Despite this considerable body of work, only spodumene is presently used to economically produce lithium chemicals via the conventional calcine, acid roast, leach, purification, crystallisation process (Welham, 2019). The few plants processing micas are at the high end of the cost curve. Among lithium minerals, there is very limited published work on the processing of petalite concentrates to battery grade materials. As far as the authors are aware there are no plants currently operating on petalite. This is believed to be due to the comparative rarity of petalite 3
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Fig. 4. XRD patterns for calcines from petalite-Na2SO4 mixture with mass ratio of 1:0.5 after heating at temperatures of 800, 900 and 1000 °C for 1 h (a), and more detailed XRD pattern of calcine after 1 h at 1000 °C (b).
greatly simplify the flow sheet. Work on other lithium minerals have shown that roasting of lithium concentrates or ores with sodium sulphate (Na2SO4) followed by water leaching may be an alternatively route for lithium extraction (Setoudeh et al., 2019, 2018). The extraction of metals from ore/concentrate is typically improved by mechanical activation/mechanical milling of starting materials using high energy ball milling. Mechanical activation process is one of the most important pre-treatment methods which can affect the leachability of a solid phase (Fletcher and Welham 2000; Welham, 2001, 2002; Zhang et al., 2010; Setoudeh et al., 2018; Vieceli et al., 2017b, 2018). The works of Vieceli et al. (2017b, 2018) indicated that mechanical activation of lepidolite concentrate can improve the
reactivity of lepidolite during sulphuric acid digestion and water leaching. Recent results have shown that sulfation roasting of spodumene concentrate or lepidolite ore milled for 5 h with Na2SO4 result in the conversion of lithium in the concentrate to a > 99% water-soluble form (Setoudeh et al., 2018, 2019; Setoudeh, 2019). Improved extraction of cobalt and lithium from spent lithium-ion batteries was also done using mechanical activation process (Guo et al., 2018). There does not appear to be any literature about the influence of mechanical activation (ball milling) on lithium extraction from petalite roasted with Na2SO4. Therefore, investigation the effect of mechanical activation on the petalite-Na2SO4 mixtures can be useful to study the phase changes/formations in the milled mixtures during subsequent 4
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Fig.5. XRD patterns for calcines after heating milled 1:1 mass ratio petalite-Na2SO4 mixture at temperatures of 800, 900 and 1000 °C for 1 h (a), and more detailed XRD pattern of produced calcine at temperature1000°C for 1 h (b).
(contained lithium ~2.03%) and > 99% sodium sulphate (Na2SO4). The chemical composition of the petalite concentrate in Table 1 indicates that concentrate has a very low level of impurities. The X-ray diffraction (XRD) trace in Fig. 1 shows that the concentrate contains primarily petalite (JCPDS 005-0381), quartz (JCPDS 87-2096) and spodumene (JCPDS 33-0786). There are also a few unassigned weak peaks (i.e. at 2θ ~31.9°) which are probably related to minor impurities. From the chemical formula of petalite and its head grade, it is estimated that the concentrate was ~90% petalite. Mixtures of petalite and Na2SO4 (combined mass ~4.12 g) were prepared with two different mass ratios of 1:0.5 and 1:1. These mixtures were mechanically milled in a closed zirconia chamber using a planetary ball mill (PMQW series Planetary Ball Mill) for 5 h. The milling
roasting process. This study gives detailed information on the characterization and phase changes/formations of mechanically activated of petalite-Na2SO4 mixtures in a planetary ball mill using zirconia medium. After finishing milling processes, the milled samples were isothermally heated at different temperatures. Water leaching of the produced calcines was done using hot water and characterizations of all solid phases/residuals were studied using XRD techniques. Thermogravimetric analyses for petalite concentrate and milled mixtures of petalite-Na2SO4 were also done under flow of air atmosphere. 2. Experimental The starting materials were a petalite flotation concentrate 5
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Fig. 6. XRD patterns of dried solid residues after hot water leaching of calcine produced for petalite-Na2SO4 with mass ratio of 1:0.5.
residues however these peaks are shifted to higher angles in the mixture with mass ratio of 1:1. The presence of petalite peaks in the solid residues of TGA analysis (Fig. 3) show that reaction between petalite and Na2SO4 was not complete after heating to 950 °C. The relative intensities of petalite peaks at 2θ ~22.2° and ~27.7° in the XRD pattern of 5 h milled mixture with a mass ratio of 1:0.5 are lower than those for the 1:1 mass ratio. Sodium sulphate (Na2SO4) is softer than petalite and therefore, the amount of Na2SO4 plays a significant role in mechanical activation of petalite-Na2SO4 mixtures. The 5 h milled mixtures of petalite-Na2SO4 with mass ratios of 1:0.5 and 1:1 were heated in a muffle furnace. Fig. 4a shows the XRD traces of the residues after heating 1:0.5 mass ratio petalite-Na2SO4 mixtures at 800 °C, 900 °C and 1000 °C for 1 h. The peaks for petalite at 2θ ~27.7° and ~28.3° are seen in the sample heated at 900 °C, however these peaks weaken after heating at 1000 °C (Fig. 4b). New peaks for LiNaSO4 are present at 2θ ~26° and ~27° indicating that reaction between petalite and Na2SO4 takes place at increasing temperatures. The peak for spodumene at 2θ ~37.3° is observed at temperatures of 800 °C and 900 °C, however the relative intensity of this peak is decreased at 1000 °C suggesting consumption by reaction. Peaks for albite (the Na analogue of petalite, NaAlSi3O8) are present in the samples heated at all temperatures suggesting that there may be an ion exchange occurring between the two major phases present in the mixture (reaction (1)).
conditions for all samples were the same: rotation of speed of 600 rpm, zirconia chamber, zirconia balls and the ball-to-powder weight ratio of 20:1. After milling, ~2 g samples were placed into alumina crucibles and heated in a muffle furnace at 800–1000 °C for 1 h. After heating, the calcined products were stored in sealed containers for further experimental and/or characterization. Thermogravimetric analysis (TGA) was carried out on un-milled petalite concentrate and the 5 h milled mixtures of petalite-Na2SO4 a heating rate of 10 °C min−1 up to 950 °C under a flowing air atmosphere using a Perkins Elmer 4000. The samples were held at 950 °C for one minute then cooled to room temperature at 50 °C min−1 under air flow. The produced calcine was subjected to agitated deionised water leach at 80 °C for 1 h using a slurry density of ~40 g L−1 (i.e., one gram of calcine was dissolved in 25 mL of deionised water). After the required time, the slurry was filtered and the solution analysed for lithium by MP-AES (Agilent Technologies 4200). The leach residues were dried at 120 °C in an oven for two hours. All solid products were analysed using X-ray diffraction (XRD, Co kα radiation, 40 kV, 40 mA) over a 2θ range of 15–60° with a count time of 2 s per 0.026° scan step. 3. Results and discussion 3.1. TGA results
LiAlSi4O10 + Na2SO4 = NaAlSi3O8 + SiO2 + LiNaSO4
Fig. 2 shows the TGA mass loss curves for petalite concentrate and the 5 h milled mixtures of petalite-Na2SO4. The mass loss was < 0.5% up to 950 °C for all samples, this was reasonably expected since the reactions were expected to be solid state and not involve either mass gain or loss.
(1)
Fig. 5 shows the XRD traces for petalite-Na2SO4 mixtures with mass ratio of 1:1 after heating at 800 °C, 900 °C and 1000 °C for 1 h. The major peaks of petalite at 2θ ~27.7° and ~28.3° were absent after heating at 1000 °C. The main peak for spodumene at 2θ ~37.3° was clear at 800 °C but weakened with temperature. New peaks at 2θ ~29.8°and ~36.8° were observed at 900 °C and their intensity decreased at temperature of 1000 °C. These peaks can be assigned to βspodumene phase, however these also overlap with albite peaks (Fig. 5b). Earlier work on spodumene concentrate (Setoudeh, 2019) showed that conversion to β-spodumene was required for reaction with Na2SO4. Thus, the appearance of β-spodumene is a kinetic effect at
3.2. Phase changes/formations XRD patterns for the residues after TGA analysis are shown in Fig. 3 along with patterns for unheated samples. The traces of starting materials (petalite concentrate and Na2SO4) are clearly observed in the 5 h as-milled mixtures (Fig. 3a and b). The main peaks of petalite at 2θ ~27.7° and ~28.3° are also observed in the XRD patterns of TGA 6
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Fig. 7. XRD patterns of dried solid residues after hot water leaching of calcine produced for petalite-Na2SO4 with mass ratio of 1:1 (a) and more detailed XRD pattern of solid residues for 1000 °C (b).
react directly with sodium sulphate or transformed to β-spodumene form which then reacts with Na2SO4. The presence of peaks for βspodumene, albite and LiNaSO4 phases in the produced calcine (Fig. 5) after heating are in good agreement with thermodynamic assessments of reaction (2). The LiNaSO4 phase was also observed in the reaction between lepidolite and mixtures of sodium and calcium sulphate during heating at 750–900 °C for 0.5 h (Vieceli et al., 2017a). Similar results showed that the peaks for NaAlSi3O8 were very weak at 750 °C but strengthened at 800 °C (Yan et al., 2012a). The XRD patterns of Figs. 4 and 5 reveal that presence of some of the spodumene may have been due to decomposition of petalite
800 °C with conversion to β-spodumene occurring more rapid than the reaction with Na2SO4. The results from Figs. 4 and 5 indicate that reaction between petalite and sodium sulphate is given by reaction (2). 2LiAlSi4O10 + Na2SO4 = LiNaSO4 + 3SiO2 + NaAlSi3O8 + LiAlSi2O6 (2) A thermodynamic appreciation using HSC software (HSC, version 6.12, 2007) indicated that reaction (2) is thermodynamically feasible at 520 °C (ΔG°520 = –177 kJ). If reaction (2) occurs between petalite and Na2SO4 at higher temperatures, the product phases can be expected in the produced calcine. With increasing temperature, the spodumene can 7
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Fig. 8. Solubility of lithium as a function of mass ratio and calcination temperature.
4. Conclusions
concentrate with sodium sulphate by reaction (2). Therefore, this is maybe the main reason for occurring α → β spodumene phase transformation with increasing heating temperatures. The α → β spodumene phase transition was also observed in previous research with increasing heating temperature (Setoudeh, 2019; Setoudeh et al., submitted for publication; Salakjani et al., 2016; Meshram et al., 2014; Chen et al., 2011).
The results indicated that heating of 5 h mechanically activated petalite-Na2SO4 mixtures leads to significantly increased lithium solubility in water. Increasing temperature and amount of sodium sulphate in the mixture resulted in decomposition of petalite and formation of LiNaSO4, quartz, spodumene and albite. Of these phases, only LiNaSO4 is water soluble. The absence of any lithium bearing phases in the residue after heating a mixture with mass ratio of 1:1 at temperature of 1000 °C for 1 h indicated essentially complete conversion to water soluble LiNaSO4. Solution analysis indicated > 99% Li solubility for these conditions.
3.3. Leaching experiments The samples heated at 900 °C and 1000 °C were leached in hot water. The XRD traces of the leach residues are shown in Figs. 6 and 7. Comparing the XRD patterns for solid leach residues in Figs. 6 and 7 indicates that hot water leaching for calcines produced at 900 °C did not dissolve all contained lithium in the petalite concentrate owing to incomplete reaction. Fig. 7 shows that increasing the amount of sodium sulphate in the mixture is very important. All peaks for petalite disappeared after heating at 1000 °C. The peaks for quartz (SiO2) and albite phases in the dried residues (Fig. 7b) indicate that reaction (2) occurred between petalite and sodium sulphate during heating. Fig. 8 shows the lithium dissolution during water leaching of the calcines after heating at temperatures of 900 °C and 1000 °C. Clearly, lithium recovery increases with both increasing temperature and sodium sulphate content. However, the effect of temperature on lithium recovery is more significant than the amount of sodium sulphate in mixture. The > 99% Li recovery after heating the 1:1 mass ratio sample at 1000 °C is consistent with the XRD trace (Fig. 7b) with only peaks for insoluble quartz and albite phases present, lithium bearing phases were absent. The absence of petalite peaks in the leach residues indicates that heating at 1000 °C was sufficient to convert all contained lithium to the water soluble phase. Further refinement of the amount of Na2SO4 would seem to be possible, the lower mass ratio giving 70% Li extraction suggests a ratio closer to 0.71 could be expected to give 100% Li extraction.
Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgment This research work was undertaken at Edith Cowan University (ECU) as part of a larger research project entitled “Lithium Ore Processing” during Dr. Setoudeh’s sabbatical leave from Yasouj University. The authors thank Yasouj University for granting sabbatical leave to Dr. Setoudeh and the School of Engineering at Edith Cowan University for hosting Dr. Setoudeh. Financial support for the project was provided by the Deputy of Research and Technology of Yasouj University, Edith Cowan University (ECU) and Welham Metallurgical Services. The authors gratefully acknowledge Dr. Guanliang Zhou for his kind cooperation in the chemical laboratory at ECU. Also gratefully acknowledged are the anonymous providers of the petalite concentrate. References Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011. Preparation of lithium carbonate from spodumene by a sodium carbonate autoclave process. Hydrometallurgy 109, 43–46.
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changes in mechanically activated spodumene-Na2SO4 mixtures after isothermal heating. To be submitted to. Minerals Eng. Setoudeh, N., Nosrati, A., Welham, N.J., 2018. Enhancing lithium leaching by mechanical activation. Mongolian Journal of Chemistry 19 (45), 44–48. Sitando, O., Crouse, P.L., 2012. Processing of a Zimbabwean petalite to obtain lithium carbonate. Int. J. Miner. Process. 102–103, 45–50. Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durao, F.O., Guimaraes, C., Margarido, F., 2017a. Optimization of lithium extraction from lepidolite by roasting using sodium and calcium sulfates. Mineral Processing and Extractive Metallurgy Review. 38 (1), 62–72. Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Paula Soares Dias, A., Durao, F.O., Guimaraes, C., Margarido, F., 2017b. Effects of mechanical activation on lithium extraction from a lepidolite ore concentrate. Miner. Eng. 102, 1–14. Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durao, F.O., Guimaraes, C., Margarido, F., 2018. Recovery of lithium carbonate by acid digestion and hydrometallurgical processing from mechanically activated lepidolite. Hydrometallurgy. 175, 1–10. Vu, H., Bernardi, J., Jandová, J., Vaculíková, L., Goliáš, V., 2013. Lithium and rubidium extraction from zinnwaldite by alkali digestion process: Sintering mechanism and leaching kinetics. Int. J. Miner. Process. 123, 9–17. Welham, N.J., 2001. Enhanced dissolution of tantalite/columbite following milling. Int. J. Miner. Process. 61 (3), 145–154. Welham, N.J., 2002. Activation of the reduction of manganese ore. Int. J. Miner. Process. 67 (1–4), 187–198. Welham, N.J., 2019, Lithium, in SME Mineral Processing and Extractive Metallurgy Handbook, ed. R.C. Dunne, S. Komar Kawatra and C.A. Young, Society for Mining, Metallurgy, and Exploration, Englewood, pp.1839-1854. Welham, N.J., Nosrati, A., Setoudeh, N., 2017. Lithium Ore Processing – an Overview of the current and new processes. In: Perth, W.A. (Ed.), metallurgical plant design and operating strategies – World’s Best Practice (MetPlant 2017) 11–12 September 2017. Australia, pp. 185–194. Yan, Q., Li, X., Wang, Z., Wu, X., Wang, J., Guo, H., Hu, Q., Peng, W., 2012a. Extraction of lithium from lepidolite by sulfation roasting and water leaching. Int. J. Miner. Process. 110–111, 1–5. Yan, Q., Li, X., Wang, Z., Wang, J., Guo, H., Hu, Q., Peng, W., Wu, X., 2012b. Extraction of lithium from lepidolite using chlorination roasting-water leaching process. Trans. Nonferrous Metals Soc. China. 22, 1753–1759. Zhang, Y., Zheng, S., Du, H.H., Xu, H., Zhang, Y., 2010. Effect of mechanical activation on alkali leaching of chromite ore. Trans. Nonferrous Metals Soc. China 20 (5), 888–891.
Fletcher, N.H., Welham, N.J., 2000. Enhanced dissolution following extended milling. J. Am. Inst. Chem. Eng. 46 (3), 666–669. Guo, Y., Li, Y., Lou, X., Guan, J., Li, Y., Mai, X., Liu, H., Zhao, C.X., Wang, N., Yan, Ch., Gao, G., Yuan, H., Dai, J., Su, R., Guo, Zh., 2018. Improved extraction of cobalt and lithium by reductive acid from spent lithium-ion batteries via mechanical activation process. J. Mater. Sci. 53, 13790–13800. HSC Chemistry for Windows, version 6.12., Outotec Research, 1974-2007. Jandová, J., Dvořák, P., Vu, H.N., 2010. Processing of zinnwaldite waste to obtain Li2CO3. Hydrometallurgy 103, 12–18. Kuang, G., Li, H., Hu, S., Jin, R., Liu, S., Guo, H., 2015. Recovery of aluminium and lithium from gypsum residue obtained in the process of lithium extraction from lepidolite. Hydrometallurgy 157, 214–218. Lee, J., 2015. Extraction of lithium from lepidolite using mixed grinding with sodium sulfide followed by water leaching. Minerals 5, 737–743. Lou, X., Lin, Ch., Luo, Q., Zhao, J., Wang, B., Li, J., Shao, Q., Guo, X., Wang, N., Guo, Zh., 2017. Crystal structure modification enhanced FeNb11O29 anodes for lithium-ion batteries. Chem. Electro. Chem. 4, 3171–3180. Luong, V.T., Kang, D.J., An, J.W., Kim, M.J., Tran, T., 2013. Factors affecting the extraction of lithium from lepidolite. Hydrometallurgy 134–135, 54–61. Meshram, P., Pandey, B.D., Mankhand, T.R., 2014. Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: a comprehensive review. Hydrometallurgy 150, 192–208. Rosales, G.D., Carmen Ruiz, M.del., Rodriguez, M.H., 2014. Novel process for extraction of lithium form β-spodumene by leaching with HF. Hydrometallurgy 147–148, 1–6. Rosales, G.D., Ruiz, M.C., Rodriguez, M.H., 2016. Study of the extraction kinetics of lithium by leaching β-spodumene with hydrofluoric acid. Minerals 6 (98), 1–12. Salakjani, N.Kh., Singh, P., Nikoloski, A.N., 2016. Mineralogical transformations of spodumene concentrate from Greenbushes, Western Australia. Part 1: Conventional heating. Minerals Eng. 98, 71–79. Setoudeh, N., Nosrati, A., Welham, N.J., in press. Lithium recovery from mechanically activated mixtures of lepidolite and sodium sulfate, Mineral Processing and Extractive Metallurgy, Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM, in press https://doi.org/10.1080/25726641.2019.1649112. Setoudeh, N., 2019. “Lithium Ore Processing”, The internal report of sabbatical leave for Yasouj University (in Farsi). This research work has been undertaken at Edith Cowan University (ECU) with cooperation of Dr. Ataollah Nosrati and. Dr. Nicholas J. Welham. Setoudeh, N., Nosrati, A., Welham, N.J., 2019;al., submitted for publication. Phase
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Lithium extraction from mechanically activated of petalite-Na2SO4 mixtures after isothermal heating
T
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Nader Setoudeha,b, , Ataollah Nosratib,1, Nicholas J. Welhamb,c a
Materials Engineering Department, Yasouj University, Yasouj 75918-74831, Iran Edith Cowan University, School of Engineering, Chemical Engineering Department, Perth, Australia c Welham Metallurgical Services, South Lake, Australia b
A R T I C LE I N FO
A B S T R A C T
Dedication: Dr. Ataollah Nosrati passed away from cancer before submission of this paper. His co-authors would like to dedicate this paper to his memory.
Mixtures of a petalite flotation concentrate and sodium sulphate (Na2SO4) with mass ratios of 1:0.5 and 1:1 were prepared and milled for 5 h using zirconia media in a planetary ball mill. The milled mixtures were heated at 800–1000 °C for 1 h in air in a muffle furnace. The XRD patterns for the calcines indicated that reaction between petalite and sodium sulphate results in formation of LiNaSO4, albite and spodumene phases. The results indicated that increasing temperature and/or amount of sodium sulphate in the mixtures both play a significant role in decomposition of petalite concentrate and formation of LiNaSO4 phase. Leaching the calcines in hot water (80 °C) selectively dissolved the LiNaSO4. Solution analyses indicated that > 99% lithium dissolution can be achieved for mixtures with 1:1 mass ratio after heating at 1000 °C for 1 h. The presence of phases such as quartz (SiO2) and albite in the leach residues showed that roasting petalite concentrate with sodium sulphate (Na2SO4) and followed by hot water leaching is a sufficient process for selective lithium dissolution from a petalite concentrate.
Keywords: Ball milling Calcine Lithium Mechanical activation Petalite concentrate
1. Introduction In the past few years the demand for lithium has substantially increased due to the prevalence of small electronic devices requiring batteries which are both lightweight and high capacity. The forecast global demand for lithium carbonate shows doubling requirements between 2015 and 2025 (Welham et al., 2017). Lithium-ion batteries (LIBs) are considered the most promising power sources for electric vehicles (EVs) owing to the higher energy output, longer storage life, lower maintenance and higher energy density than other secondary batteries, (Lou et al., 2017). LIBs are also widely used in a multitude of portable electronics, especially mobile phones, personal computers, cameras, etc. (Guo et al., 2018). The rising demand for lithium and lithium compounds in future years necessitates the development of an increased range of natural resources for recovery of lithium. Historically, more than 80% of produced lithium in the world has come from brines; but recent projects have increased the production from hard rock to over 50% (Kuang et al., 2015; Luong et al., 2013; Welham, 2019). Although there are many lithium bearing minerals in nature, only a few are of commercial potential for lithium processing. The most
promising lithium minerals are aluminosilicates compounds such as spodumene and petalite, and micas such as lepidolite and those in the polylithionite group (including the now discredited, but commonly referenced, mineral zinnwaldite) (Meshram et al., 2014). There are many processes for recovery of lithium from lithium ores/ concentrates. These processes are based on breaking down the lithium aluminosilicate minerals during heating with additives including sulphuric acid, limestone/lime, sodium sulphide and sodium/potassium salts, and then followed by water/acid leaching of the calcine products. Some processes for lithium recovery from minerals such as spodumene and lepidolite have been recently reported (Vieceli et al., 2017a; Lee, 2015; Yan et al., 2012a; Meshram et al., 2014; Chen et al., 2011; Luong et al., 2013). Chlorination process is another process for lithium extraction form lepidolite using of chlorine gas or HCl (Meshram et al., 2014; Yan et al., 2012b). Some investigations have been done for treating and extraction of lithium from β-spodumene using hydrofluoric acid leaching in literatures (Rosales et al., 2016, 2014). Preparation of lithium carbonate salts from alkaline leach liquors originating from processing of zinnwaldite with CaCO3 have been performed by Jandová et al. (2010). Sintering zinnwaldite with CaCO3 and water leaching the obtained sinters was also done by Vu et al. (2013) for recovering
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Corresponding author at: Materials Engineering Department, Yasouj University, Yasouj 75918-74831, Iran. E-mail address: [email protected] (N. Setoudeh). 1 Deceased. https://doi.org/10.1016/j.mineng.2020.106294 Received 18 July 2019; Received in revised form 27 November 2019; Accepted 20 February 2020 Available online 06 March 2020 0892-6875/ © 2020 Elsevier Ltd. All rights reserved.
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Table 1 Chemical composition of petalite concentrate by X-Ray Fluorescence and AAS (Li) analysis. Element % Petalite Element % Petalite
Al2O3 16.49 Na2O 0.48
BaO < 0.01 P2O5 0.02
CaO 0.03 SO3 < 0.01
Cr2O3 < 0.01 SiO2 77.04
Fe2O3 < 0.01 SrO < 0.01
K2O 0.97 TiO2 < 0.01
MgO 0.09 Li2O 4.367
Fig. 1. XRD pattern of petalite concentrate as starting material.
Fig. 2. TGA curves of the petalite concentrate and 5 h milled mixtures of petalite-Na2SO4 with mass ratios of 1:0.5 and 1:1.
2
MnO < 0.01 L.O.I 0.64
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Fig. 3. XRD patterns of TGA solid residues for petalite-Na2SO4 mixtures with mass ratios of 1:0.5 (a) and mass ratio of 1:1 (b).
as a product and the preference for petalite over spodumene by ceramic manufacturers. Petalite concentrate from the Bikita deposits in Zimbabwe was processed to high-purity Li2CO3 by roasting petalite concentrate with concentrated sulphuric acid (H2SO4) followed by water leaching to produce Li2SO4 solution which was purified and ultimately precipitated to give high purity lithium carbonate (Sitando and Crouse 2012). Although acid digestion is largely effective, the omnivorous nature of the process leads to significant requirements to purify the solution prior to lithium recovery. Alternative processes which have greater selectivity for lithium do not have such problems and would
lithium and rubidium. Despite this considerable body of work, only spodumene is presently used to economically produce lithium chemicals via the conventional calcine, acid roast, leach, purification, crystallisation process (Welham, 2019). The few plants processing micas are at the high end of the cost curve. Among lithium minerals, there is very limited published work on the processing of petalite concentrates to battery grade materials. As far as the authors are aware there are no plants currently operating on petalite. This is believed to be due to the comparative rarity of petalite 3
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Fig. 4. XRD patterns for calcines from petalite-Na2SO4 mixture with mass ratio of 1:0.5 after heating at temperatures of 800, 900 and 1000 °C for 1 h (a), and more detailed XRD pattern of calcine after 1 h at 1000 °C (b).
greatly simplify the flow sheet. Work on other lithium minerals have shown that roasting of lithium concentrates or ores with sodium sulphate (Na2SO4) followed by water leaching may be an alternatively route for lithium extraction (Setoudeh et al., 2019, 2018). The extraction of metals from ore/concentrate is typically improved by mechanical activation/mechanical milling of starting materials using high energy ball milling. Mechanical activation process is one of the most important pre-treatment methods which can affect the leachability of a solid phase (Fletcher and Welham 2000; Welham, 2001, 2002; Zhang et al., 2010; Setoudeh et al., 2018; Vieceli et al., 2017b, 2018). The works of Vieceli et al. (2017b, 2018) indicated that mechanical activation of lepidolite concentrate can improve the
reactivity of lepidolite during sulphuric acid digestion and water leaching. Recent results have shown that sulfation roasting of spodumene concentrate or lepidolite ore milled for 5 h with Na2SO4 result in the conversion of lithium in the concentrate to a > 99% water-soluble form (Setoudeh et al., 2018, 2019; Setoudeh, 2019). Improved extraction of cobalt and lithium from spent lithium-ion batteries was also done using mechanical activation process (Guo et al., 2018). There does not appear to be any literature about the influence of mechanical activation (ball milling) on lithium extraction from petalite roasted with Na2SO4. Therefore, investigation the effect of mechanical activation on the petalite-Na2SO4 mixtures can be useful to study the phase changes/formations in the milled mixtures during subsequent 4
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Fig.5. XRD patterns for calcines after heating milled 1:1 mass ratio petalite-Na2SO4 mixture at temperatures of 800, 900 and 1000 °C for 1 h (a), and more detailed XRD pattern of produced calcine at temperature1000°C for 1 h (b).
(contained lithium ~2.03%) and > 99% sodium sulphate (Na2SO4). The chemical composition of the petalite concentrate in Table 1 indicates that concentrate has a very low level of impurities. The X-ray diffraction (XRD) trace in Fig. 1 shows that the concentrate contains primarily petalite (JCPDS 005-0381), quartz (JCPDS 87-2096) and spodumene (JCPDS 33-0786). There are also a few unassigned weak peaks (i.e. at 2θ ~31.9°) which are probably related to minor impurities. From the chemical formula of petalite and its head grade, it is estimated that the concentrate was ~90% petalite. Mixtures of petalite and Na2SO4 (combined mass ~4.12 g) were prepared with two different mass ratios of 1:0.5 and 1:1. These mixtures were mechanically milled in a closed zirconia chamber using a planetary ball mill (PMQW series Planetary Ball Mill) for 5 h. The milling
roasting process. This study gives detailed information on the characterization and phase changes/formations of mechanically activated of petalite-Na2SO4 mixtures in a planetary ball mill using zirconia medium. After finishing milling processes, the milled samples were isothermally heated at different temperatures. Water leaching of the produced calcines was done using hot water and characterizations of all solid phases/residuals were studied using XRD techniques. Thermogravimetric analyses for petalite concentrate and milled mixtures of petalite-Na2SO4 were also done under flow of air atmosphere. 2. Experimental The starting materials were a petalite flotation concentrate 5
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Fig. 6. XRD patterns of dried solid residues after hot water leaching of calcine produced for petalite-Na2SO4 with mass ratio of 1:0.5.
residues however these peaks are shifted to higher angles in the mixture with mass ratio of 1:1. The presence of petalite peaks in the solid residues of TGA analysis (Fig. 3) show that reaction between petalite and Na2SO4 was not complete after heating to 950 °C. The relative intensities of petalite peaks at 2θ ~22.2° and ~27.7° in the XRD pattern of 5 h milled mixture with a mass ratio of 1:0.5 are lower than those for the 1:1 mass ratio. Sodium sulphate (Na2SO4) is softer than petalite and therefore, the amount of Na2SO4 plays a significant role in mechanical activation of petalite-Na2SO4 mixtures. The 5 h milled mixtures of petalite-Na2SO4 with mass ratios of 1:0.5 and 1:1 were heated in a muffle furnace. Fig. 4a shows the XRD traces of the residues after heating 1:0.5 mass ratio petalite-Na2SO4 mixtures at 800 °C, 900 °C and 1000 °C for 1 h. The peaks for petalite at 2θ ~27.7° and ~28.3° are seen in the sample heated at 900 °C, however these peaks weaken after heating at 1000 °C (Fig. 4b). New peaks for LiNaSO4 are present at 2θ ~26° and ~27° indicating that reaction between petalite and Na2SO4 takes place at increasing temperatures. The peak for spodumene at 2θ ~37.3° is observed at temperatures of 800 °C and 900 °C, however the relative intensity of this peak is decreased at 1000 °C suggesting consumption by reaction. Peaks for albite (the Na analogue of petalite, NaAlSi3O8) are present in the samples heated at all temperatures suggesting that there may be an ion exchange occurring between the two major phases present in the mixture (reaction (1)).
conditions for all samples were the same: rotation of speed of 600 rpm, zirconia chamber, zirconia balls and the ball-to-powder weight ratio of 20:1. After milling, ~2 g samples were placed into alumina crucibles and heated in a muffle furnace at 800–1000 °C for 1 h. After heating, the calcined products were stored in sealed containers for further experimental and/or characterization. Thermogravimetric analysis (TGA) was carried out on un-milled petalite concentrate and the 5 h milled mixtures of petalite-Na2SO4 a heating rate of 10 °C min−1 up to 950 °C under a flowing air atmosphere using a Perkins Elmer 4000. The samples were held at 950 °C for one minute then cooled to room temperature at 50 °C min−1 under air flow. The produced calcine was subjected to agitated deionised water leach at 80 °C for 1 h using a slurry density of ~40 g L−1 (i.e., one gram of calcine was dissolved in 25 mL of deionised water). After the required time, the slurry was filtered and the solution analysed for lithium by MP-AES (Agilent Technologies 4200). The leach residues were dried at 120 °C in an oven for two hours. All solid products were analysed using X-ray diffraction (XRD, Co kα radiation, 40 kV, 40 mA) over a 2θ range of 15–60° with a count time of 2 s per 0.026° scan step. 3. Results and discussion 3.1. TGA results
LiAlSi4O10 + Na2SO4 = NaAlSi3O8 + SiO2 + LiNaSO4
Fig. 2 shows the TGA mass loss curves for petalite concentrate and the 5 h milled mixtures of petalite-Na2SO4. The mass loss was < 0.5% up to 950 °C for all samples, this was reasonably expected since the reactions were expected to be solid state and not involve either mass gain or loss.
(1)
Fig. 5 shows the XRD traces for petalite-Na2SO4 mixtures with mass ratio of 1:1 after heating at 800 °C, 900 °C and 1000 °C for 1 h. The major peaks of petalite at 2θ ~27.7° and ~28.3° were absent after heating at 1000 °C. The main peak for spodumene at 2θ ~37.3° was clear at 800 °C but weakened with temperature. New peaks at 2θ ~29.8°and ~36.8° were observed at 900 °C and their intensity decreased at temperature of 1000 °C. These peaks can be assigned to βspodumene phase, however these also overlap with albite peaks (Fig. 5b). Earlier work on spodumene concentrate (Setoudeh, 2019) showed that conversion to β-spodumene was required for reaction with Na2SO4. Thus, the appearance of β-spodumene is a kinetic effect at
3.2. Phase changes/formations XRD patterns for the residues after TGA analysis are shown in Fig. 3 along with patterns for unheated samples. The traces of starting materials (petalite concentrate and Na2SO4) are clearly observed in the 5 h as-milled mixtures (Fig. 3a and b). The main peaks of petalite at 2θ ~27.7° and ~28.3° are also observed in the XRD patterns of TGA 6
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Fig. 7. XRD patterns of dried solid residues after hot water leaching of calcine produced for petalite-Na2SO4 with mass ratio of 1:1 (a) and more detailed XRD pattern of solid residues for 1000 °C (b).
react directly with sodium sulphate or transformed to β-spodumene form which then reacts with Na2SO4. The presence of peaks for βspodumene, albite and LiNaSO4 phases in the produced calcine (Fig. 5) after heating are in good agreement with thermodynamic assessments of reaction (2). The LiNaSO4 phase was also observed in the reaction between lepidolite and mixtures of sodium and calcium sulphate during heating at 750–900 °C for 0.5 h (Vieceli et al., 2017a). Similar results showed that the peaks for NaAlSi3O8 were very weak at 750 °C but strengthened at 800 °C (Yan et al., 2012a). The XRD patterns of Figs. 4 and 5 reveal that presence of some of the spodumene may have been due to decomposition of petalite
800 °C with conversion to β-spodumene occurring more rapid than the reaction with Na2SO4. The results from Figs. 4 and 5 indicate that reaction between petalite and sodium sulphate is given by reaction (2). 2LiAlSi4O10 + Na2SO4 = LiNaSO4 + 3SiO2 + NaAlSi3O8 + LiAlSi2O6 (2) A thermodynamic appreciation using HSC software (HSC, version 6.12, 2007) indicated that reaction (2) is thermodynamically feasible at 520 °C (ΔG°520 = –177 kJ). If reaction (2) occurs between petalite and Na2SO4 at higher temperatures, the product phases can be expected in the produced calcine. With increasing temperature, the spodumene can 7
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Fig. 8. Solubility of lithium as a function of mass ratio and calcination temperature.
4. Conclusions
concentrate with sodium sulphate by reaction (2). Therefore, this is maybe the main reason for occurring α → β spodumene phase transformation with increasing heating temperatures. The α → β spodumene phase transition was also observed in previous research with increasing heating temperature (Setoudeh, 2019; Setoudeh et al., submitted for publication; Salakjani et al., 2016; Meshram et al., 2014; Chen et al., 2011).
The results indicated that heating of 5 h mechanically activated petalite-Na2SO4 mixtures leads to significantly increased lithium solubility in water. Increasing temperature and amount of sodium sulphate in the mixture resulted in decomposition of petalite and formation of LiNaSO4, quartz, spodumene and albite. Of these phases, only LiNaSO4 is water soluble. The absence of any lithium bearing phases in the residue after heating a mixture with mass ratio of 1:1 at temperature of 1000 °C for 1 h indicated essentially complete conversion to water soluble LiNaSO4. Solution analysis indicated > 99% Li solubility for these conditions.
3.3. Leaching experiments The samples heated at 900 °C and 1000 °C were leached in hot water. The XRD traces of the leach residues are shown in Figs. 6 and 7. Comparing the XRD patterns for solid leach residues in Figs. 6 and 7 indicates that hot water leaching for calcines produced at 900 °C did not dissolve all contained lithium in the petalite concentrate owing to incomplete reaction. Fig. 7 shows that increasing the amount of sodium sulphate in the mixture is very important. All peaks for petalite disappeared after heating at 1000 °C. The peaks for quartz (SiO2) and albite phases in the dried residues (Fig. 7b) indicate that reaction (2) occurred between petalite and sodium sulphate during heating. Fig. 8 shows the lithium dissolution during water leaching of the calcines after heating at temperatures of 900 °C and 1000 °C. Clearly, lithium recovery increases with both increasing temperature and sodium sulphate content. However, the effect of temperature on lithium recovery is more significant than the amount of sodium sulphate in mixture. The > 99% Li recovery after heating the 1:1 mass ratio sample at 1000 °C is consistent with the XRD trace (Fig. 7b) with only peaks for insoluble quartz and albite phases present, lithium bearing phases were absent. The absence of petalite peaks in the leach residues indicates that heating at 1000 °C was sufficient to convert all contained lithium to the water soluble phase. Further refinement of the amount of Na2SO4 would seem to be possible, the lower mass ratio giving 70% Li extraction suggests a ratio closer to 0.71 could be expected to give 100% Li extraction.
Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgment This research work was undertaken at Edith Cowan University (ECU) as part of a larger research project entitled “Lithium Ore Processing” during Dr. Setoudeh’s sabbatical leave from Yasouj University. The authors thank Yasouj University for granting sabbatical leave to Dr. Setoudeh and the School of Engineering at Edith Cowan University for hosting Dr. Setoudeh. Financial support for the project was provided by the Deputy of Research and Technology of Yasouj University, Edith Cowan University (ECU) and Welham Metallurgical Services. The authors gratefully acknowledge Dr. Guanliang Zhou for his kind cooperation in the chemical laboratory at ECU. Also gratefully acknowledged are the anonymous providers of the petalite concentrate. References Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011. Preparation of lithium carbonate from spodumene by a sodium carbonate autoclave process. Hydrometallurgy 109, 43–46.
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