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Hydrophobic functional liquids based on TOPO and its analogues

Hydrophobic functional liquids based on TOPO and its analogues. Emily Byrne Supervised by Gosia Swadźba-Kwaśny and John Holbrey QUILL meeting, September 2019. Uses of TOPO. TOPO. Nanoparticle synthesis in combination with a reducing agent.

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Hydrophobic functional liquids based on TOPO and its analogues

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  1. Hydrophobic functional liquids based on TOPO and its analogues Emily Byrne Supervised by Gosia Swadźba-Kwaśny and John Holbrey QUILL meeting, September 2019

  2. Uses of TOPO TOPO Nanoparticle synthesis in combination with a reducing agent Extraction of organics (e.g. carboxylic acids / phenolics) Metal extraction (e.g. uranium / gallium) Focusing on extraction

  3. TOPO liquified through ‘DES strategy’ DES strategy TOPO is liquified in combination with a hydrogen bond donor (HBD) in the correct molar ratio HBA HBD • Tm = +52 C Malonic acid TOPO Levulinic acid Phenol TOPO 0.20 - 0.501 0.30 - 0.50 0.55 - 0.67 • Room temperature liquids  3 M. Gilmore, E.N. McCourt, F. Connolly, P. Nockemann, M. Swadźba-Kwaśny, J.D. Holbrey, ACS Sustainable Chem. Eng., 2018, 6, 17323.

  4. TOPO DES used in extraction Uranium1 New DES system1 Acidic chloride system Metal Gallium Zinc leach residue Phenol • Hydrophobic • Non-ionic • Low viscosity Basic sources Extraction Extracting phase Red mud Organic • Active extractants • TOPO = 0.67 Malonic acid (MA) TOPO Bio-refinery application TOPO Gilmore et al. ACS Sustainable Chem. Eng., 2018, 6, 17323.

  5. 2ZnS + 3O2 → 2ZnO + 2SO2 • 2SO2 + O2 → 2SO3 • 10% of zinc sulfite (ZnS) reacts with Fe to form Zinc Ferrite (ZnO·Fe2O3) Zinc manufacturing process ‘Pyrometallurgical process’ Sinter Molten zinc Retorting Casting Sintering Roasting Slab Zinc Concentrate Calcine Leaching Melting & casting Zinc solution Cathode Zinc Leachsolution Purifying Electrolysis Weak H2SO4 Strong H2SO4 Waste Most common production route ‘Electrolysis process’ Zinc leach residue

  6. 2ZnS + 3O2 → 2ZnO + 2SO2 • 2SO2 + O2 → 2SO3 • 10% of zinc sulfite (ZnS) reacts with Fe to form Zinc Ferrite (ZnO·Fe2O3) Zinc manufacturing process Roasting Slab Zinc Concentrate Calcine Leaching Melting & casting Zinc solution Cathode Zinc Leachsolution Purifying Electrolysis Weak H2SO4 Strong H2SO4 Waste Focusing on extraction from zinc leach residue Zinc leach residue • Main components: • *Zinc ferrite (ZnFe2O4) • Gypsum (CaSO4·2H2O) • Hemihydrate gypsum (CaSO4·0.5H2O) • Anglesite (PbSO4) • Sphalerite ((Zn,Fe)S) • *Quartz (SiO2) 98% Ga comes into the leach residue Kinoshita et al. Sep. Purif. Technol., 2011, 78, 181. Wu et al. Hydrometallurgy, 2012, 113-114, 195.

  7. Ga extraction from zinc leach residue Current zinc leach residue processing limited to lab scale (High cost / technical issues) Kinoshita et al. Sep. Purif. Technol., 2011, 78, 181. Wu et al. Hydrometallurgy, 2012, 113-114, 195. Liu et al. Hydrometallurgy, 2016, 164, 313.

  8. Ga extraction from zinc leach residue • Simulated acid filtrate: GaCl3, FeCl3·6H2O, CuCl2·2H2O, ZnCl2 / 6 M HCl (0.03 wt% Ga) • Zinc leach residue: Immersed in 6 M HCl for 24 hours / diluted / used as feedstock • Addition of ascorbic acid to reduce Fe(lll) to Fe(ll) • Poly(oxyethylene) nonyl phenyl ether = surfactant and metal collector • Complete Ga extraction Current zinc leach residue processing limited to lab scale (High cost / technical issues) Kinoshita et al. Sep. Purif. Technol., 2011, 78, 181. Wu et al. Hydrometallurgy, 2012, 113-114, 195. Liu et al. Hydrometallurgy, 2016, 164, 313.

  9. Ga extraction from zinc leach residue • H2SO4 / SO2 / 100 C / 2h • Slurry stirred in autoclave / SO2 injected • 91% Ga extracted (also 90% Zn, 96% Fe) • More than 95% Fe(lll) [R] to Fe(ll) • SO2 + H2O → H2SO3 • ZnO·Fe2O3 + H2SO3 + 2H2SO4 → ZnSO4 + 2FeSO4 + 3H2O Current zinc leach residue processing limited to lab scale (High cost / technical issues) Kinoshita et al. Sep. Purif. Technol., 2011, 78, 181. Wu et al. Hydrometallurgy, 2012, 113-114, 195. Liu et al. Hydrometallurgy, 2016, 164, 313.

  10. Ga extraction from zinc leach residue • 150 C / H2SO4 / liquid:solid = 8 / Ca(NO3)2 / 3h • Calcium nitrate addition increases leaching of Ge and increase filtering performance of leach slurry • 98% Ga leached, 94% Ge Current zinc leach residue processing limited to lab scale (High cost / technical issues) Kinoshita et al. Sep. Purif. Technol., 2011, 78, 181. Wu et al. Hydrometallurgy, 2012, 113-114, 195. Liu et al. Hydrometallurgy, 2016, 164, 313.

  11. Extraction using DES strategy DES strategy TOPO is liquified in combination with a hydrogen bond donor (HBD) in the correct molar ratio acac Advantages: • No solvent leaching • Use in membranes • Low processing volumes / high extractant concentration • If selectivity achievable:better than current extraction systems 2:1 Malonic acid Active Extractant 2 ActiveExtractant 1 ExtractiveDES +

  12. Comparison of TOPO:Malonic acid DES extractant with literature benchmark Extraction conditions: • GaCl3 (0.006 M) • Room temperature • Extraction time (10 min) • equivolume organic and aqueous phases Results: • 100% extraction reached at 4 M HCl • LogDGa is approximately 3 times greater than literature benchmark when conditions replicated Sato et al. Solvent Extr. Ion Exch., 1984, 2, 201

  13. Increasing initial GaCl3 concentration in aqueous solution Results: Results: • Although LogDGa values decrease, absolute quantities of gallium extracted are much higher • Much greater extractant loading capacity

  14. Malonic acid leaching determined by infrared spectroscopy and total organic carbon content Results: • [Malonic acid]aq is low after contact in comparison to the high solubility of malonic acid in H2O • Linear dependence on intensity of infra-red absorption with malonic acid concentration • NMR / UV-Vis proved unsuitable for leaching analysis • Total organic carbon content will also be used TOPO:malonic acid, shaking time: 20 mins, RT, 0 M HCl (H2O) H2O solubility: 763 gL-1 TOPO:malonic acid, shaking time: 20 mins, RT, 6 M HCl

  15. Malonic acid leaching determined by infrared spectroscopy and total organic carbon content Results: • [Malonic acid]aq is low after contact in comparison to the high solubility of malonic acid in H2O • Linear dependence on intensity of infra-red absorption with malonic acid concentration • NMR / UV-Vis proved unsuitable for leaching analysis • Total organic carbon content will also be used TOPO:malonic acid, shaking time: 20 mins, RT, 0 M HCl (H2O) H2O solubility: 763 gL-1 TOPO:malonic acid, shaking time: 20 mins, RT, 6 M HCl

  16. Competitive metal extraction Results: • Competing metals found in zinc leach residue: Zn, Fe, Na, Ca, Pb • Zn and Fe extracted to limits of detection across all HCl concentrations • Na and Ca not competitively extracted • Pb insoluble in HCl concentrations studied – not competitively extracted

  17. Metal stripping strategies Electrowinning pH change • Hold at voltage past reduction overnight to electrodeposit Ga and SEM electrode • Add base to change pH and crash out insoluble Ga species

  18. Cyclic Voltammetry (CV) of 0.1 M GaCl3 in TOPO:MA Similar to: Cl-oxidation [GaCl4]- anion in [C8mim]Cl-GaCl3 systems Phys.Chem. Chem. Phys., 2013, 15, 4518 0.1 M GaCl3, TOPO = 0.67 TOPO:MA pre-contacted with 6 M HCl. Glassy carbon (W), platinum (C), Ag+/Ag (R)electrodes. 10 mV s-1, RT. J. Phys. Chem. C, 2015, 119, 23572−23579.

  19. Cyclic Voltammetry (CV) of 0.1 M FeCl3 in TOPO:MA Add in Fe CV Photo of Ga crashing out 0.1 M FeCl3, TOPO = 0.67 TOPO:MA pre-contacted with 6 M HCl. Glassy carbon (W), platinum (C), Ag+/Ag (Aq) (R)electrodes. 10 mV s-1, RT. J. Phys. Chem. C, 2015, 119, 23572−23579.

  20. Raman speciation studies Maybe unknown peak is some sort of Ga-Cl bond but at a different wavelength due to co-ord to TOPO Results: Results: • Ga speciation in the eutectic: • [GaCl4]- • Ga-Cl stretch co-ord to TOPO and/or MA • Literature: • [GaCl4]- in LCC paper was 349cm-1 • [GaCl4]- in Oye and bues paper was 343cm-1 (H. A. OYE and W. BUES, Inorg. nucl. them. Lett. 8, 31 (1972). ) • [GaCl4]- in Taylor paper was 343cm-1 (M. J. TAYLOR, J. chem. Soc. (A) 2812 (1970).) • [GaCl4]- in Mamantov paper was 345cm-1 (Spectrochimica Acta, Vol. 45A, No. 7, pp. 759-762, 1989.) • My assignment is 338cm-1 • 346 cm-1 in low frequency vibrations of inorganic and coordination compounds page 128 (Td geometry) • [Ga2Cl7]- in LCC paper was 365 cm-1 • [Ga2Cl7]- in Oye and bues paper was 366 cm-1 • [Ga2Cl7]- in Taylor paper was 365 cm-1 • My assignment is 361cm-1 • 35Cl2 (soln) = 548 cm-1 338 cm-1 324 cm-1 [GaCl4]- J. chem. Soc. (A), 1970, 2812. Spectrochimica Acta, 45A, 1989, 759. Inorg. nucl. chem. Lett., 1972, 8, 31. Angew. Chem. Int. Ed. 2013, 52, 12582.

  21. Conclusions and future work • Conclusions: • Only 14-50 gL-1 malonic acid leaches from eutectic extractant under typical extraction conditions (713 gL-1 less than pure malonic acid) • Zn and Fe are competitively extracted, but Na, Ca, Pb are not • Ga or Fe [R] and [O] peaks are not present in current CV system • [GaCl4]- present in eutectic phase • Future work on application: • Extraction studies on mixed competing metal system simulating an acid leached zinc leach residue • Remove gallium from extractant phase

  22. Acknowledgements Dr. Gosia Swadźba-Kwaśny Prof. John Holbrey Dr. Mark Gilmore ASEP QUILL Solvay DfE

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