Preparation of sodium molybdate from molybdenum concentrate by microwave roasting and alkali leaching

Abstract

The preparation process of sodium molybdate has the disadvantages of high energy consumption, low thermal efficiency, and high raw material requirement of molybdenum trioxide, in order to realize the green and efficient development of molybdenum concentrate resources, this paper proposes a new process for efficient recovery of molybdenum from molybdenum concentrate and preparation of sodium molybdate by microwave-enhanced roasting and alkali leaching. Thermodynamic analysis indicated the feasibility of oxidation roasting of molybdenum concentrate. The effects of roasting temperature, holding time, and power-to-mass ratio on the oxidation product and leaching product sodium molybdate (Na₂MoO₄·2H₂O) were investigated. Under the optimal process conditions: roasting temperature of 700°C, holding time of 110 min, and power-to-mass ratio of 110 W/g, the molybdenum state of existence was converted from MoS₂ to MoO₃. The process of preparing sodium molybdate by alkali leaching of molybdenum calcine was investigated, the optimal leaching conditions include a solution concentration of 2.5 mol/L, a liquid-to-solid ratio of 2 mL/g, a leaching temperature of 60°C, and leaching solution termination at pH 8. The optimum conditions result in a leaching rate of sodium molybdate of 96.24%. Meanwhile, the content of sodium molybdate reaches 94.08wt% after leaching and removing impurities. Iron and aluminum impurities can be effectively separated by adjusting the pH of the leaching solution with sodium carbonate solution. This research avoids the shortcomings of the traditional process and utilizes the advantages of microwave metallurgy to prepare high-quality sodium molybdate, which provides a new idea for the high-value utilization of molybdenum concentrate.

Keywords

molybdenum metallurgy / microwave oxidation roasting / removing impurities / sodium hydroxide leaching

References

[[1]] Zhou QS, Yun WT, Xi JT, et al.. Molybdenite–limestone oxidizing roasting followed by calcine leaching with ammonium carbonate solution. Trans. Nonferrous Met. Soc. China, 2017, 27(7): 1618,

[[2]] W. Yang, B.J. Deng, L.Q. Hou, et al., Sulfur-fixation strategy toward controllable synthesis of molybdenum-based/carbon nanosheets derived from petroleum asphalt, Chem. Eng. J., 380(2020), art. No. 122552.

[[3]] Parenago OP, Kuz’mina GN, Zaimovskaya TA. Sulfurcontaining molybdenum compounds as high-performance lubricant additives (Review). Pet. Chem., 2017, 57(8): 631,

[[4]] Kapri S, Bhattacharyya S. Molybdenum sulfide-reduced graphene oxide p–n heterojunction nanosheets with anchored oxygen generating manganese dioxide nanoparticles for enhanced photodynamic therapy. Chem. Sci., 2018, 9(48): 8982,

[[5]] Mendel RR, Bittner F. Cell biology of molybdenum. Biochim. Biophys. Acta, 2006, 1763(7): 621,

[[6]] Kaiser BN, Gridley KL, Ngaire Brady J, Phillips T, Tyerman SD. The role of molybdenum in agricultural plant production. Ann. Bot., 2005, 96(5): 745,

[[7]] Wang SC, Wang LZ. Recent progress of tungsten- and molybdenum-based semiconductor materials for solar-hydrogen production. Tungsten, 2019, 1(1): 19,

[[8]] W.W. Zhang, C.Y. Li, W.J. Wang, et al., Laminarin and sodium molybdate as efficient sustainable inhibitor for Q235 steel in sodium chloride solution, Colloids Surf., A, 637(2022), art. No. 128199.

[[9]] D.Q. Wang, M. Wu, J. Ming, and J.J. Shi, Inhibitive effect of sodium molybdate on corrosion behaviour of AA6061 aluminium alloy in simulated concrete pore solutions, Constr. Build. Mater., 270(2021), art. No. 121463.

[[10]] Zhou Y, Zuo Y, Lin B. The compounded inhibition of sodium molybdate and benzotriazole on pitting corrosion of Q235 steel in NaCl+NaHCO₃ solution. Mater. Chem. Phys., 2017, 192: 86,

[[11]] Lopez-Garrity O, Frankel GS. Corrosion inhibition of aluminum alloy 2024-T3 by sodium molybdate. J. Electrochem. Soc., 2013, 161(3): C95,

[[12]] Heravi MM, Zakeri M. Use of sodium molybdate dihydrate as an efficient heterogeneous catalyst for the synthesis of benzopyranopyrimidine derivatives. Synth. React. Inorg. Met. Org. Nano Met. Chem., 2013, 43(2): 211,

[[13]] F. Torun, B. Hostins, P. De Schryver, N. Boon, and J. De Vrieze, Molybdate effectively controls sulphide production in a shrimp pond model, Environ. Res., 203(2022), art. No. 111797.

[[14]] Bolitschek J, Luidold S, O’Sullivan M. A study of the impact of reduction conditions on molybdenum morphology. Int. J. Refract. Met. Hard Mater., 2018, 71: 325,

[[15]] Wang L, Zhang GH, Wang JS, Chou KC. Influences of different components on agglomeration behavior of MoS₂ during oxidation roasting process in air. Metall. Mater. Trans. B, 2016, 47(4): 2421,

[[16]] Lessard JD, Gribbin DG, Shekhter LN. Recovery of rhenium from molybdenum and copper concentrates during the Looping Sulfide Oxidation process. Int. J. Refract. Met. Hard Mater., 2014, 44: 1,

[[17]] Jakhar R, Yap JE, Joshi R. Microwave reduction of graphene oxide. Carbon, 2020, 170: 277,

[[18]] Wang JP, Jiang T, Liu YJ, Xue XX. Influence of microwave treatment on grinding and dissociation characteristics of vanadium titano-magnetite. Int. J. Miner. Metall. Mater., 2019, 26(2): 160,

[[19]] He Y, Liu J, Liu JH, Chen CL, Zhuang CL. Carbothermal reduction characteristics of oxidized Mn ore through conventional heating and microwave heating. Int. J. Miner. Metall. Mater., 2021, 28(2): 221,

[[20]] Das S, Mukhopadhyay AK, Datta S, Basu D. Prospects of microwave processing: An overview. Bull. Mater. Sci., 2008, 31(7): 943,

[[21]] Anklekar RM, Agrawal DK, Roy R. Microwave sintering and mechanical properties of PM copper steel. Powder Metall., 2001, 44(4): 355,

[[22]] Liu J, Liu CH, Hong Y, Zhang LB. Basic study on microwave carbon-thermal reduction senarmontite (Sb₂O₃) to produce antimony: High-temperature dielectric properties and a microwave reduction mechanism. Powder Technol., 2021, 389: 482,

[[23]] V.Kvapilová, Evaluation of microwave drying effects on historical brickwork and modern building materials, IOP Conf. Ser.: Mater. Sci. Eng., 867(2020), No. 1, art. No. 012026.

[[24]] Oghbaei M, Mirzaee O. Microwave versus conventional sintering: A review of fundamentals, advantages and applications. J. Alloys Compd., 2010, 494(1–2): 175,

[[25]] Zhu GY, Peng ZW, Yang L, Tang HM, Fang XL, Rao MJ. Facile preparation of thermal insulation materials by microwave sintering of ferronickel slag and fly ash cenosphere. Ceram. Int., 2023, 49(8): 11978,

[[26]] Parhi P, Misra P. Hydrometallurgical investigation routed through microwave (MW) assisted leaching and solvent extraction using ionic liquids for extraction and recovery of molybdenum from spent desulphurization catalyst. Inorg. Chem. Commun., 2023, 149: 110394,

[[27]] P.K. Parhi and P.K. Misra, Environmental friendly approach for selective extraction and recovery of molybdenum (Mo) from a sulphate mediated spent Ni-Mo/Al₂O₃ catalyst baked leach liquor, J. Environ. Manage., 306(2022), art. No. 114474.

[[28]] Kan S, Benzeşik K, Odabaş C, Yücel O. Investigation of molybdenite concentrate roasting in chamber and rotary furnaces. Min. Metall. Explor., 2021, 38(3): 1597

[[29]] Jiang YL, Liu BG, Liu P, Peng JH, Zhang LB. Dielectric characterization and microwave roasting of molybdenite concentrates at 915 MHz frequency. J. Harbin Inst. Technol. (New Series), 2019, 26(3): 58

[[30]] Pervaiz M, Munawar A, Hussain S, et al.. A green approach for extraction of ammonium molybdate from molybdenite using indigenous resources. Pol. J. Environ. Stud., 2021, 30(2): 1771,

[[31]] M.P. Zhang, C.H. Liu, X.J. Zhu, et al., Preparation of ammonium molybdate by oxidation roasting of molybdenum concentrate: A comparison of microwave roasting and conventional roasting, Chem. Eng. Process.: Process. Intensif., 167(2021), art. No. 108550.

[[32]] Lane MD, Bishop JL, Dyar MD, et al.. Mid-infrared emission spectroscopy and visible/near-infrared reflectance spectroscopy of Fe-sulfate minerals. Am. Mineral., 2015, 100(1): 66,

[[33]] Wang L, Zhang GH, Dang J, Chou KC. Oxidation roasting of molybdenite concentrate. Trans. Nonferrous Met. Soc. China, 2015, 25(12): 4167,

[[34]] Sun H, Li GH, Bu QZ, et al.. Features and mechanisms of self-sintering of molybdenite during oxidative roasting. Trans. Nonferrous Met. Soc. China, 2022, 32(1): 307,

[[35]] Kansomket C, Laokhen P, Yingnakorn T, Patcharawit T, Khumkoa S. Extraction of molybdenum from a spent HDS catalyst using alkali leaching reagent. J. Met. Mater. Miner., 2022, 32(2): 88,

[[36]] Wang C, Guo YF, Wang S, et al.. Characteristics of the reduction behavior of zinc ferrite and ammonia leaching after roasting. Int. J. Miner. Metall. Mater., 2020, 27(1): 26,

[[37]] Nam YI, Seo SY, Kang YC, Kim MJ, Senanayake G, Tran T. Purification of molybdenum trioxide calcine by selective leaching of copper with HCl-NH₄Cl. Hydrometallurgy, 2011, 109(1–2): 9,

[[38]] H. Sun, J.J. Yu, G.H. Li, et al., Co-volatilizing-water leaching process for efficient utilization of rhenium-bearing molybdenite concentrate, Hydrometallurgy, 192(2020), art. No. 105284.

[[39]] J.H. Chen, D. Tang, S.P. Zhong, W. Zhong, and B.Z. Li, The influence of micro-cracks on copper extraction by bioleaching, Hydrometallurgy, 191(2020), art. No. 105243.

[[40]] L.P. Jia, Z.W. Zhao, X.H. Liu, and L.H. He, Recovery of valuable metals from molybdenum-removal sludge by reverse sulfurization leaching, Hydrometallurgy, 193(2020), art. No. 105323.

[[41]] Y.B. Li, Q.H. Xiao, Z.M. Li, and Gerson A, Enhanced leaching of Mo by mechanically co-grinding and activating MoS₂ with NaClO₃ as an oxidizing additive, Hydrometallurgy, 203(2021), art. No. 105625.

[[42]] Ali S, Iqbal Y, Khan I, et al.. Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid. Int. J. Miner. Metall. Mater., 2021, 28(2): 193,

[[43]] Liu J, Qiu ZF, Yang J, Cao LM, Zhang W. Recovery of Mo and Ni from spent acrylonitrile catalysts using an oxidation leaching-chemical precipitation technique. Hydrometallurgy, 2016, 164: 64,

[[44]] Liu ZX, Sun L, Hu J, et al.. Selective extraction of molybdenum from copper concentrate by air oxidation in alkaline solution. Hydrometallurgy, 2017, 169: 9,

[[45]] P. Wang, Y.J. Pan, X. Sun, and Y.Q. Zhang, Leaching molybdenum from a low-grade roasted molybdenite concentrate, SN Appl. Sci., 1(2019), No. 4, art. No. 311.

[[46]] Vosough M, Khayati GR, Sharafi S. Ammonia leaching of MoO₃ concentrate: Finding the reaction mechanism and kinetics analysis. Chem. Pap., 2022, 76(5): 3227,

[[47]] Zhao ZP, Guo M, Zhang M. Extraction of molybdenum and vanadium from the spent diesel exhaust catalyst by ammonia leaching method. J. Hazard. Mater., 2015, 286: 402,

[[48]] Liu Y, Zhang YF, Chen FF, Zhang Y. The alkaline leaching of molybdenite flotation tailings associated with galena. Hydrometallurgy, 2012, 129–130: 30,

[[49]] Guo Y, Li HY, Yuan YH, et al.. Microemulsion leaching of vanadium from sodium-roasted vanadium slag by fusion of leaching and extraction processes. Int. J. Miner. Metall. Mater., 2021, 28(6): 974,

[[50]] Olson GJ, Clark TR. Bioleaching of molybdenite. Hydrometallurgy, 2008, 93(1–2): 10,

[[51]] Fu YF, Xiao QG, Gao YY, Ning PG, Xu HB, Zhang Y. Pressure aqueous oxidation of molybdenite concentrate with oxygen. Hydrometallurgy, 2017, 174: 131,

[[52]] Wang JP, Zhang YM, Huang J, Liu T. Synergistic effect of microwave irradiation and CaF₂ on vanadium leaching. Int. J. Miner. Metall. Mater., 2017, 24(2): 156,

[[53]] Kapole SA, Bhanvase BA, Pinjari DV, et al.. Investigation of corrosion inhibition performance of ultrasonically prepared sodium zinc molybdate nanopigment in two-pack epoxy-polyamide coating. Compos. Interfaces, 2014, 21(9): 833,

[[54]] Nakagaki S, Bail A, dos Santos VC, et al.. Use of anhydrous sodium molybdate as an efficient heterogeneous catalyst for soybean oil methanolysis. Appl. Catal. A, 2008, 351(2): 267,

[[55]] Y. Mochizuki, J. Bud, J.Q. Liu, M. Takahashi, and N. Tsubouchi, Adsorption of phosphate from aqueous using iron hydroxides prepared by various methods, J. Environ. Chem. Eng., 9(2021), No. 1, art. No. 104645.

[[56]] S.Q. Wang, J. Xie, J.D. Hu, H.Y. Qin, and Y.L. Cao, Fe-doped α-MoO₃ nanoarrays: Facile solid-state synthesis and excellent xylene-sensing performance, Appl. Surf. Sci., 512(2020), art. No. 145722.