Potential Alternative Utilization of Manganese Nodules

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1 UNIVERSITY OF CHEMISTRY AND TECHNOLOGY PRAGUE Potential Alternative Utilization of Manganese Nodules Ng. Hong VU

2 Utilization of leaching residues as sorbents Reductive leaching: - 90 o C, l/s= 10:1, ~ 20g SO 2 /l, ~ 100g H 2 SO 4 /l, 60 min Sorbents preparation: - A1: original leaching residue - A2/Cl: A1 activated in 10% vol. HCl - A2/N: A1 activated in 10% vol. HNO 3 - A3/1: A1 thermally activated at 250 o C, 8 h - A3/Cl: A2/Cl thermally activated at 250 o C, 8 h - A4/Cl: A2/Cl mechanically activated in a mill at 600 rpm, 30 min - A5/Fe II : precipitation of Fe II on A1, 24 h, FeSO 4 under N 2 - A5/Fe III : precipitation of Fe III on A1, 24 h, Fe(NO 3 ) 3, NaOH - A5/Al III : precipitation of Fe III on A1, 24 h, AlCl 3, NaOH Sorption tests: - 0.1g of a sorbent, 50 ml, 100 mg/l of a selected meta

3 Results: Utilization of leaching residues as sorbents Chemical composition of sorbents [%]

4 Results: Utilization of leaching residues as sorbents Mineralogical composition of the sorbent A1

5 Results: Utilization of leaching residues as sorbents Specific surface of sorbents, measured by BET [m2/g] and their moisture Particle size distribution of the sorbent A1

6 Results: Utilization of leaching residues as sorbents Effect of ph on the adsorption of Pb onto adsorbents: 200rpm, 8h

7 Results: Utilization of leaching residues as sorbents Dependence of the Pb uptake on adsorption time: 200rpm, ph 5.05

8 Results: Utilization of leaching residues as sorbents Effect of ph on the adsorption of Cd onto adsorbents: 200rpm, 8h

9 Results: Utilization of leaching residues as sorbents Dependence of the Cd uptake on adsorption time: 200rpm, ph 6.0

10 Results: Utilization of leaching residues as sorbents Effect of ph on the adsorption of Cu onto adsorbents: 200rpm, 8h

11 Results: Utilization of leaching residues as sorbents Dependence of the Cu uptake on adsorption time: 200rpm, ph 4

12 Results: Utilization of leaching residues as sorbents Effect of ph on the adsorption of Ni onto adsorbents: 200rpm, 8h

13 Results: Utilization of leaching residues as sorbents Dependence of the Ni uptake on adsorption time: 200rpm, ph 5.5

14 Results: Utilization of leaching residues as sorbents Effect of ph on the adsorption of Co onto adsorbents: 200rpm, 8h

15 Results: Utilization of leaching residues as sorbents Dependence of the Co uptake on adsorption time: 200rpm, ph 5

16 Results: Utilization of leaching residues as sorbents Dependence of the As uptake on adsorption time: 250rpm, ph 7.0

17 Results: Utilization of leaching residues as sorbents Comparison of maximum As(V) adsorption capacities of different adsorbents

18 Utilization of leaching residues as sorbents Conclusions: Prepared adsorbents are effective in a fast removal of Pb and Cd. Chemical and mechanochemical (milling) activation generally increased the maximum adsorption capacity. The activated sorbents can be used to remove Cu, Ni and Co from aqueous solution. Nanostructured sorbents were proved to be effective for arsenic removal. Especially the adsorbent A5/A liii based on nanoparticles of Al(OH) 3 can be considered one of the best materials for an effective arsenic removal at low cost Using leaching residues to treat waste water in hydrometallurgical plants

19 Nodules and Metals for E-mobility - 3 millions tones of nodules 400 tones of lithium metal 2,500 tones of Li 2 CO 3 1% of the Li world production 37,5 millions USD 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

20 a key raw material for modern technologies Li consumption is usually divided to Chemical and Technical ceramics primary baterries Metal lubricants polymers Recharable baterries Main factor for increased Li consumption air treatment glass glass ceramics others Al alloys

21 a key raw material for modern technologies

22 a key raw material for modern technologies

23 a key raw material for modern technologies Price developlment of main marketable lithium compounds

24 a key raw material for modern technologies

25 Lithium minerals a key raw material for modern technologies

26 a many junior miners want to join the league of big 4

27 OPEX price comparision 1 t of zinnwaldite concentrate 100 USD 1 t of spodumene concentrate 550 USD

28 Nodules and Metals for E-mobility - New approaches needed for recovering Li at low concentration Direct usage of manganese nodules to recover Li 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

29 Nodules and Metals for E-mobility - Titration curves for phpzc determination 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

30 Nodules and Metals for E-mobility - The point of zero charge phpzc 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

31 Nodules and Metals for E-mobility - The dependence of the Li sorption capacity of the nodules on ph 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

32 Nodules and Metals for E-mobility - 3 R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013 Li sorption kinetics of the untreated nodules, ph 4

33 Nodules and Metals for E-mobility - Desorption kinetics of Li from nodules, ph R. Hein, K. Mizell, A. Koshinsky and T. Conrad, 2013

34 Nodules and Metals for E-mobility - Another solution a new nano-adsorbent O O NH,, 2 O O N OH etc. magnetic doping silicon nanoparticle Synthesis of functionalized magnetic silicon-based nano-adsorbents

35 Nodules and Metals for E-mobility - Another solution a new nano-adsorbent magnetic silicon nanoparticle complex waste stream containing metals recovered target metal metal-chelating group Non-binding metals other magnetic nonbinding metals dialysis or membrane filtration Schematic representation cycle of functionalized magnetic silicon-based nano-adsorbents process for metal recovery from leach solutions

36 Thank you

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