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Heavy metals removal from wastewater by ferrogels Wojciech Hyk, Konrad Kitka Faculty of Chemistry University of Warsaw Naxos 2018 The aim To develop a method for metal removal from waste water samples using thermoresponsive ferrogel


  1. Heavy metals removal from wastewater by ferrogels Wojciech Hyk, Konrad Kitka Faculty of Chemistry University of Warsaw Naxos 2018

  2. The aim • To develop a method for metal removal from waste water samples using thermoresponsive ferrogel sorbents („magnetic sponge”) Wojciec jciech Hyk Hyk

  3. Realization – general scheme • The synthesis procedure of hydrogel matrix for the implementation of a metal sorbent in aqueous systems with strictly defined composition of the sorption system • Gel matrix – thermoresponsive poly(N-isopropylacrylamide) Δ T hydrogel • Metal sorbent – nanosized magnetite (ferromagnetic properties) • Examination of the composite material for silver and copper removal from aqueous media Wojciec jciech Hyk Hyk

  4. Realization - details • Preparation of pNIPA gel swollen by water – free-radical polymerization of N-isopropylacrylamide (NIP A) using well documented procedures • Purification and drying the resulting polymeric material (pNIPA) • Grinding the pNIPA material to a fine powder • Preparation of the ferro-pNIPA system – mixing the pNIP A powder with known amount of nanosized magnetite • Formation of the pNIPA ferrogel swollen by the aqueous solution – transferring the ferro/ pNIP A mixture into the aqueous solution containing heavy metal cations • Aqueous solution purification – inducing volume phase transition of the gel system and removing the collapsed gel by an external magnetic field Wojciec jciech Hyk Hyk

  5. Realization – the idea • Water purification using sponge like behaviour of poly(N- isopropylacrylamide) ferrogels Δ T t B solvent molecule metal cation sorbent particle dry polymer fragment Wojciec jciech Hyk Hyk

  6. Results – silver removal from water samples • Effect of pNIPA matrix on the silver adsorption efficiency magnetite solution 14 pNIP A / magnetite gel 12 10 Q e [mg/g] 8 6 4 2 0 0 50 100 150 1 / m(Fe 3 O 4 ) [1/g] Wojciec jciech Hyk Hyk

  7. Results – silver removal from water samples • Determination of adsorption isotherm A aqueous solution of magnetite – 10 Langmuir isotherm 8 c e (Ag + ) / Q e 6 4 Q max : 9.1 ± 3.4 mg / g 2 0 0 10 20 30 40 50 60 70 c e (Ag + ) [mg/L] B pNIPA / magnetite ferrogel – 0.8 Freundlich isotherm 0.6 log(Q e ) 0.4 Q max : 13.6 ± 3.8 mg / g 0.2 -0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 log(c e (Ag + )) Wojciec jciech Hyk Hyk

  8. Results – mechanism of silver adsorption on magnetite • Chemical reduction of silver (I) cations on the surface of magnetite (silver chemical deposition) • Diffusion of silver (I) cations to iron oxide grains 2Fe 3 O 4 ( s ) + H 2 O + 2Ag + ↔ 3Fe 2 O 3 ( s ) + 2H + + 2Ag( s ) • • Extraction of silver requires concentrated nitric (V) acid Wojciec jciech Hyk Hyk

  9. Method validation for real wastewater samples • Sample prepared to mimic copper ore post - flotation waste c Ag : 100 mg / L Ag(I) 100 c Cu : 664 mg / L 80 60 %R Cu(II) 40 20 0 0 2 4 6 8 10 12 14 16 %(Fe 3 O 4 ) in pNIPA gel Wojciec jciech Hyk Hyk

  10. Conclusions • Synthesis procedure of universal hydrogel matrix for controlled implementation of metal sorbents • Highly efficient silver removal by a “magnetic sponge” (pNIPA / magnetite thermoresponsive ferrogel) • Silver adsorption on magnetite in pNIPA ferrogel is described by the Freundlich model • The presence of gel matrix increases efficiency of silver sorption on magnetite Wojciec jciech Hyk Hyk

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