Characterization of Cobalt Oxalate Dihydrate Obtained from Spent Co-Mo/Al2O3 Hydrodesulfurization Catalyst

Year 2022, , 1059 - 1070, 20.10.2022

Ahmet Orkun Kalpaklı

https://doi.org/10.16984/saufenbilder.1124183

Abstract

In this study, roasted spent Co-Mo/Al2O3 hydrodesulfurization (HDS) catalyst was dissolved in oxalic acid (H2C2O4) solution and optimum conditions were determined for obtaining cobalt oxalate dihydrate (CoC2O4∙2H2O). The thermal decomposition behavior of the obtained CoC2O4∙2H2O was investigated by TG/DTG-DTA analysis. The characterization of CoC2O4∙2H2O was carried out by XRD, FT-IR and SEM-EDS analytical techniques. Optimum conditions for the production of CoC2O4∙2H2O were determined as 25 oC temperature, 0.25 M H2C2O4 concentration, 1/20 g mL-1 solid/liquid ratio and 300 rpm stirring speed. CoC2O4∙2H2O was obtained with a reaction yield of 90.9 %. TG/DTG-DTA analysis carried out in dry air atmosphere showed that CoC2O4∙2H2O decomposed in two steps. In the first step that occurs between 118-196 oC temperatures, CoC2O4∙2H2O is dehydrated. In the second step, which occurs between 248-279 oC temperatures, it was determined that metallic cobalt was formed first, and then metallic cobalt was oxidized and converted into Co3O4 compound because it was performed in the air atmosphere.

Keywords

Hydrodesulfurization catalyst, cobalt oxalate dihydrate, cobalt oxide, characterization

References

• [1] M. Marafi, A. Stanislaus, E. Furimsky, Handbook of Spent Hydroprocessing Catalysts: Second Edition. Elsevier Inc., 2017.
• [2] P. Dufresne, “Hydroprocessing catalysts regeneration and recycling,” Applied Catalysis A: General, vol. 322, pp. 67–75, 2007.
• [3] “Federal Register : Hazardous Waste Management System: Petroleum Refining Process Wastes; Identification of Characteristically Hazardous Self-Heating Solids; Land Disposal Restrictions: Treatment Standards for Spent Hydrorefining Catalyst (K172) Hazardous Waste.” https://www.federalregister.gov/documents/2003/10/20/03-26411/hazardous-waste-management-system-petroleum-refining-process-wastes-identification-of (accessed April 25, 2022).
• [4] C. Yang, J. Zhanga, Y. Chen, C. Wang, “Efficient removal of oil from spent hydrodesulphurization catalysts using microwave pyrolysis method,” Journal of Analytical and Applied Pyrolysis, vol. 135, pp. 169–175, 2018.
• [5] J. Z. Wang, H. Du, A. Olayiwola, B. Liu, F. Gao, M. L. Jia, M. H. Wang, M. L. Gao, X. D. Wang, S. N. Wang, “Recent advances in the recovery of transition metals from spent hydrodesulfurization catalysts,” Tungsten, vol. 3, pp. 305–328, 2021.
• [6] S. P. Barik, K. H. Park, P. K. Parhi, J. T. Park, C. W. Nam, “Extraction of metal values from waste spent petroleum catalyst using acidic solutions,” Separation and Purification Technology, vol. 101, pp. 85–90, 2012.
• [7] E. Furimsky, “Spent refinery catalysts: Environment, safety and utilization,” Catalysis Today, vol. 30, no. 4, pp. 223–286, 1996.
• [8] L. Zeng, C. Y. Cheng, “A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts: Part I: Metallurgical processes,” Hydrometallurgy, vol. 98, no. 1–2, pp. 1–9, 2009.
• [9] M. S. Villarreal, B. I. Kharisov, L. M. Torres-Martinez, V. N. Elizondo, “Recovery of vanadium and molybdenum from spent petroleum catalyst of PEMEX,” Industrial and Engineering Chemistry Research, vol. 38, no. 12, pp. 4624–4628, 1999.
• [10] M. Marafi, A. Stanislaus, “Waste catalyst utilization: Extraction of valuable metals from spent hydroprocessing catalysts by ultrasonic-assisted leaching with acids,” Industrial and Engineering Chemistry Research, vol. 50, no. 16, pp. 9495–9501, 2011.
• [11] A. Akcil, F. Vegliò, F. Ferella, M. D. Okudan, A. Tuncuk, “A review of metal recovery from spent petroleum catalysts and ash,” Waste Management, vol. 45, pp. 420–433, 2015.
• [12] R. Banda, T. H. Nguyen, S. H. Sohn, M. S. Lee, “Recovery of valuable metals and regeneration of acid from the leaching solution of spent HDS catalysts by solvent extraction,” Hydrometallurgy, vol. 133, pp. 161–167, 2013.
• [13] A. K. Nayak, N. Devi, K. Sarangi, “Use of Cyanex 572 as an effective extractant for the recovery of Mo(VI) and V(V) from HDS spent catalyst leach liquor,” Separation and Purification Technology, vol. 275, p. 118960, 2021.
• [14] P. C. Rout, G. K. Mishra, B. Padh, K. R. Suresh, B. Ramachandra Reddy, “Solvent extraction separation of molybdenum as thio-molybdate complex from alkaline tungsten leach liquor of spent HDS catalyst – A pilot study,” Hydrometallurgy, vol. 174, pp. 140–146, 2017. [15] K. H. Park, D. Mohapatra, C. W. Nam, “Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272,” Journal of Hazardous Materials, vol. 148, no. 1–2, pp. 287–295, 2007.
• [16] D. D. Sun, J. H. Tay, H. K. Cheong, D. L. K. Leung, G. R. Qian, “Recovery of heavy metals and stabilization of spent hydrotreating catalyst using a glass–ceramic matrix,” Journal of Hazardous Materials, vol. 87, no. 1–3, pp. 213–223, 2001.
• [17] I. M. Valverde, J. F. Paulino, J. C. Afonso, “Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium,” Journal of Hazardous Materials, vol. 160, no. 2–3, pp. 310–317, 2008.
• [18] S. P. Barik, K. H. Park, P. K. Parhi, J. T. Park, “Direct leaching of molybdenum and cobalt from spent hydrodesulphurization catalyst with sulphuric acid,” Hydrometallurgy, vol. 111–112, no. 1, pp. 46–51, 2012.
• [19] I. Susoglu, “Dissolution of used cobalt-molybdenum hydrodesulfurization (HDS) catalyst in nitric acid solutions”, MSc thesis, Department of Metallurgical and Materials Engineering, Istanbul University-Cerrahpasa, Istanbul, 2019.
• [20] H. I. Kim, K. H. Park, D. Mishra, “Sulfuric acid baking and leaching of spent Co-Mo/Al2O3 catalyst,” Journal of Hazardous Materials, vol. 166, no. 2–3, pp. 1540–1544, 2009.
• [21] M. D. Okudan, “Acidic and alkaline leaching application to spent hydrodesulfurization (HDS) catalysts including cobalt and molybdenum”, Msc thesis, Department of Mining Engineering, Suleyman Demirel University, Isparta, 2009.
• [22] D. Mohapatra, K. H. Park, “Selective recovery of Mo, Co and Al from spent Co/Mo/γ-Al2O3 catalyst: Effect of calcination temperature,” Journal of Environmental Science and Health, Part A, vol. 42, no. 4, pp. 507–515, 2007.
• [23] W. T. Mohammed, N. S. Ahmedzeki, M. F. AbdulNabi, “Extraction of valuable metals from spent hydrodesulfurization catalyst by two stage leaching method,” Iraqi Journal of Chemical and Petroleum Engineering, vol. 12, no. 4, pp. 21–35, 2011.
• [24] S. Ilhan, “Extraction of molybdenum, nickel and aluminium from spent Ni–Mo hydrodesulphurization (HDS) catalyst in oxalic acid solutions,” Canadian Metallurgical Quarterly, vol. 59, no. 1, pp. 26–35, 2020.
• [25] A. Taskinen, P. Taskinen, M. H. Tikkanen, “Thermal decomposition of cobalt oxalate,” Reactivity of Solids, pp. 617–624, 1977.
• [26] S. Ilhan, “Kullanılmış Ni–Mo hidrode-sülfürizasyon katalizöründen nikel okzalat dihidrat üretimi,” Politeknik Dergisi, vol. 23, no. 1, pp. 105–110, 2020.
• [27] E. Tóth-Szeles, G. Schuszter, Á. Tóth, Z. Kónya, D. Horváth, “Flow-driven morphology control in the cobalt–oxalate system,” CrystEngComm, vol. 18, no. 12, pp. 2057–2064, 2016.
• [28] G. M. Armitage, H. S. Dunsmore, “Stability of the hydrogen–oxalate complexes of calcium and strontium,” Journal of Inorganic and Nuclear Chemistry, vol. 35, no. 3, pp. 817–822, 1973.
• [29] E. Romero, M. E. Mendoza, R. Escudero, “Weak ferromagnetism in cobalt oxalate crystals,” Physica Status Solidi (B), vol. 248, no. 6, pp. 1519–1525, 2011.
• [30] S. Majumdar, I. G. Sharma, A. C. Bidaye, A. K. Suri, “A study on isothermal kinetics of thermal decomposition of cobalt oxalate to cobalt,” Thermochimica Acta, vol. 473, no. 1–2, pp. 45–49, 2008.
• [31] M. Maciejewski, E. Ingier-Stocka, W. D. Emmerich, A. Baiker, “Monitoring of the gas phase composition: A prerequisite for unravelling the mechanism of decomposition of solids. Thermal decomposition of cobalt oxalate dihydrate,” Journal of Thermal Analysis and Calorimetry, vol. 60, no. 3, pp. 735–758, 2000.
• [32] Y. P. Prananto, M. M. Khunur, D. T. Wahyuni, R. A. Shobirin, Y. R. Nata, E. Riskah, “Study of gel growth cobalt (II) oxalate crystals as precursor of Co3O4 nano particles,” Bulletin of Chemical Reaction Engineering and Catalysis, vol. 7, no. 3, pp 198–204, 2013.
• [33] D. D. M. Prabaharan, K. Sadaiyandi, M. Mahendran, S. Sagadevan, “Precipitation method and characterization of cobalt oxide nanoparticles,” Applied Physics A, vol. 123, pp. 264, 2017.
• [34] G. Asha, V. Rajeshwari, G. Stephen, S. Gurusamy, D. C. J. Rachel, “Eco–friendly synthesis and characterization of cobalt oxide nanoparticles by sativum species and its photo-catalytic activity,” Materials Today: Proceedings, vol. 48, no. 2, pp. 486–493, 2022.
• [35] M. Salavati-Niasari, N. Mir, F. Davar, “Synthesis and characterization of Co3O4 nanorods by thermal decomposition of cobalt oxalate,” Journal of Physics and Chemistry of Solids, vol. 70, no. 5, pp. 847–852, 2009.
• [36] M. T. Makhlouf, B. M. Abu-Zied, T. H. Mansoure, “Effect of calcination temperature on the H2O2 decomposition activity of nano-crystalline Co3O4 prepared by combustion method,” Applied Surface Science, vol. 274, pp. 45–52, 2013.
• [37] S. Farhadi, K. Pourzare, S. Sadeghinejad, “Simple preparation of ferromagnetic Co3O4 nanoparticles by thermal dissociation of the [CoII(NH3)6](NO3)2 complex at low temperature,” Journal of Nanostructure in Chemistry, vol.3, no. 1, pp. 16, 2013.
• [38] P. Zhang, G. X. Hu, S. J. Bao, J. Guo, C. Lei, C. J. Cai, D. Z. Jia, R. Y. Wang, “One step microwave synthesis and magnetic properties of Co3O4 octahedrons,” Materials Letters, vol. 83, 195–197, 2012.
• [39] S. Thota, A. Kumar, J. Kumar, “Optical, electrical and magnetic properties of Co3O4 nanocrystallites obtained by thermal decomposition of sol–gel derived oxalates,” Materials Science and Engineering: B, vol. 164, no. 1, pp. 30–37, 2009.
• [40] C. Dong, X. Xiao, G. Chen, H. Guan, Y. Wang, “Hydrothermal synthesis of Co3O4 nanorods on nickel foil,” Materials Letters, vol. 123, pp. 187–190, 2014.
• [41] A. T. Khalil, M. Ovais, I. Ullah, M. Ali, Z. K. Shinwari, M. Maaza, “Physical properties, biological applications and biocompatibility studies on biosynthesized single phase cobalt oxide (Co3O4) nanoparticles via Sageretia thea (Osbeck.),” Arabian Journal of Chemistry, vol. 13, no. 1, pp. 606–619, 2020.
• [42] A. Waris, M. Din, A. Ali, S. Afridi, A. Baset, A. U. Khan, M. Ali, “Green fabrication of Co and Co3O4 nanoparticles and their biomedical applications: A review,” Open Life Sciences, vol. 16, pp. 14–30, 2021.
• [43] V. K. Patel, J. R. Saurav, K. Gangopadhyay, S. Gangopadhyay, S. Bhattacharya, “Combustion characterization and modeling of novel nanoenergetic composites of Co3O4/nAl,” RSC Advances, vol. 5, pp. 21471–21479, 2015.